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Structure Determination of Organic Compounds

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Structure Determination of Organic Compounds Powered By Docstoc
					Structure Determination of Organic Compounds
Ern¨ Pretsch · Philippe B¨ hlmann ·
   o                     u
Martin Badertscher




Structure Determination
of Organic Compounds
Tables of Spectral Data



Fourth, Revised and Enlarged Edition




123
              o
Prof. Dr. Ern¨ Pretsch                                                      u
                                                        Prof. Dr. Philippe B¨ hlmann
        u
ETH Z¨ rich                                             University of Minnesota
Institute of Biogeochemistry and                        Dept. of Chemistry
Pollutant Dynamics                                      209 Pleasant Street SE.,
Universit¨ tsstr. 16
          a                                             Minneapolis, MN 55455
8092 Z¨ rich
        u                                               USA
Switzerland                                             buhlmann@umn.edu
pretsche@ethz.ch
Dr. Martin Badertscher
       u
ETH Z¨ rich
Laboratory of Organic Chemistry
Wolfgang-Pauli-Str. 10
       u
8093 Z¨ rich
Switzerland
badertscher@org.chem.ethz.ch




ISBN 978-3-540-93809-5                                             e-ISBN 978-3-540-93810-1

DOI 10.1007/978-3-540-93810-1
Library of Congress Control Number: 2009920112

c Springer-Verlag Berlin Heidelberg 2009

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Preface




The ongoing success of the earlier versions of this book motivated us to prepare
a new edition. While modern techniques of nuclear magnetic resonance spectros-
copy and mass spectrometry have changed the ways of data acquisition and greatly
extended the capabilities of these methods, the basic parameters, such as chemical
shifts, coupling constants, and fragmentation pathways remain the same. However,
since the amount and quality of available data has considerably increased over the
years, we decided to prepare a significantly revised manuscript. It follows the same
basic concepts, i.e., it provides a representative, albeit limited set of reference data
for the interpretation of 13C NMR, 1H NMR, IR, mass, and UV/Vis spectra. We also
added a new chapter with reference data for 19F and 31P NMR spectroscopy and, in
the chapter on infrared spectroscopy, we newly refer to important Raman bands.
   Since operating systems of computers become outdated much faster than printed
media, we decided against providing a compact disk with this new edition. The
limited versions of the NMR spectra estimation programs can be downloaded from
the home page of the developing company (www.upstream.ch/support/book_down-
loads.html).
   We thank numerous colleagues who helped us in many different ways to com-
plete the manuscript. We are particularly indebted to Dr. Dorothée Wegmann for her
expertise with which she eliminated many errors and inconsistencies of the earlier
versions. Special thanks are due to Prof. Wolfgang Robien for providing us with
reference data from his outstanding 13C NMR database, CSEARCH. Another high-
quality source of information was the Spectral Database System of the National
Institute of Advanced Industrial Science and Technology (http://riodb01.ibase.aist.
go.jp/sdbs/), Tsukuba, Ibaraki (Japan).
   In spite of great efforts and many checks to eliminate errors, it is likely that some
mistakes or inconsistencies remain. We would like to encourage our readers to con-
tact us with comments and suggestions under one of the following addresses: Prof.
Ernö Pretsch, Institute of Biogeochemistry and Pollutant Dynamics, ETH Zürich,
CH-8092 Zürich, Switzerland, e-mail: pretsche@ethz.ch, Prof. Philippe Bühlmann,
Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minne-
apolis, MN 55455, USA, e-mail: buhlmann@umn.edu, or Dr. Martin Badertscher,
Laboratory of Organic Chemistry, ETH Zürich, CH-8093 Zürich, Switzerland,
e-mail: badertscher@org.chem.ethz.ch.

Zürich and Minneapolis, November 2008
Contents




1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
  1.1 Scope and Organization. . . . . . . . . . . . . . . . . . . . . . . . . . 1
  1.2 Abbreviations and Symbols . . . . . . . . . . . . . . . . . . . . . . . . 3

2 Summary Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
  2.1 General Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
        2.1.1 Calculation of the Number of Double Bond Equivalents from
                the Molecular Formula . . . . . . . . . . . . . . . . . . . . 5
        2.1.2 Properties of Selected Nuclei . . . . . . . . . . . . . . . . . . . . . . . 6
  2.2 13C NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 7
  2.3 1H NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 10
  2.4 IR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
  2.5 Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
        2.5.1 Average Masses of Naturally Occurring Elements with Masses
                and Representative Relative Abundances of Isotopes . . . . 18
        2.5.2 Ranges of Natural Isotope Abundances of Selected Elements 25
        2.5.3 Isotope Patterns of Naturally Occurring Elements . . . . . . 26
        2.5.4 Calculation of Isotope Distributions. . . . . . . . . . . . . . 27
        2.5.5 Isotopic Abundances of Various Combinations of Chlorine,
                Bromine, Sulfur, and Silicon . . . . . . . . . . . . . . . . 29
        2.5.6 Isotope Patterns of Combinations of Cl and Br . . . . . . . . 31
        2.5.7 Indicators of the Presence of Heteroatoms . . . . . . . . . . 32
        2.5.8 Rules for Determining the Relative Molecular Weight (Mr) . 34
        2.5.9 Homologous Mass Series as Indications of Structural Type . 35
        2.5.10 Mass Correlation Table. . . . . . . . . . . . . . . . . . . . 37
        2.5.11 References . . . . . . . . . . . . . . . . . . . . . . . . . . 45
  2.6 UV/Vis Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 46

3 Combination Tables . . . . . . . . . . . . . . . . . . . . . . . . . . .              49
  3.1 Alkanes, Cycloalkanes . . . . . . . . . . . . . . . . . . . . . . . . .           49
  3.2 Alkenes, Cycloalkenes . . . . . . . . . . . . . . . . . . . . . . . . .           50
  3.3 Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .         51
VIII      Contents

    3.4 Aromatic Hydrocarbons . . . .            .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    52
    3.5 Heteroaromatic Compounds . .             .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    53
    3.6 Halogen Compounds . . . . . .            .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    54
    3.7 Oxygen Compounds . . . . . .             .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    56
         3.7.1 Alcohols and Phenols .            .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    56
         3.7.2 Ethers . . . . . . . . .          .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    57
    3.8 Nitrogen Compounds . . . . . .           .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    59
         3.8.1 Amines . . . . . . . . .          .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    59
         3.8.2 Nitro Compounds . . .             .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    60
    3.9 Thiols and Sulfides . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    61
    3.10 Carbonyl Compounds . . . . .            .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    62
         3.10.1 Aldehydes . . . . . .            .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    62
         3.10.2 Ketones . . . . . . . .          .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    63
         3.10.3 Carboxylic Acids . . .           .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    64
         3.10.4 Esters and Lactones .            .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    65
         3.10.5 Amides and Lactams .             .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    67

4   13C   NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . .                                                      69
    4.1 Alkanes . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    69
         4.1.1 Chemical Shifts . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    69
         4.1.2 Coupling Constants        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    78
         4.1.3 References . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    79
    4.2 Alkenes . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    80
         4.2.1 Chemical Shifts . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    80
         4.2.2 Coupling Constants        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    84
         4.2.3 References . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    84
    4.3 Alkynes . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    85
         4.3.1 Chemical Shifts . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    85
         4.3.2 Coupling Constants        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    85
         4.3.3 References . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    86
    4.4 Alicyclics . . . . . . . . . .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    87
         4.4.1 Chemical Shifts . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    87
         4.4.2 Coupling Constants        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    92
    4.5 Aromatic Hydrocarbons . .        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    93
         4.5.1 Chemical Shifts . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .    93
         4.5.2 Coupling Constants        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   100
         4.5.3 References . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   100
    4.6 Heteroaromatic Compounds         .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   101
         4.6.1 Chemical Shifts . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   101
                                                              Contents                        IX

     4.6.2 Coupling Constants . . . . . . . . . . . . . . .       .   .   .   .   .   .   .   108
4.7 Halogen Compounds . . . . . . . . . . . . . . . . . . .       .   .   .   .   .   .   .   109
     4.7.1 Fluoro Compounds . . . . . . . . . . . . . . .         .   .   .   .   .   .   .   109
     4.7.2 Chloro Compounds . . . . . . . . . . . . . . .         .   .   .   .   .   .   .   111
     4.7.3 Bromo Compounds . . . . . . . . . . . . . . .          .   .   .   .   .   .   .   112
     4.7.4 Iodo Compounds . . . . . . . . . . . . . . . .         .   .   .   .   .   .   .   113
     4.7.5 References . . . . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   113
4.8 Alcohols, Ethers, and Related Compounds . . . . . . . .       .   .   .   .   .   .   .   114
     4.8.1 Alcohols . . . . . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   114
     4.8.2 Ethers . . . . . . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   115
4.9 Nitrogen Compounds . . . . . . . . . . . . . . . . . . .      .   .   .   .   .   .   .   117
     4.9.1 Amines . . . . . . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   117
     4.9.2 Nitro and Nitroso Compounds . . . . . . . . .          .   .   .   .   .   .   .   119
     4.9.3 Nitrosamines and Nitramines . . . . . . . . . .        .   .   .   .   .   .   .   120
     4.9.4 Azo and Azoxy Compounds . . . . . . . . . . .          .   .   .   .   .   .   .   120
     4.9.5 Imines and Oximes . . . . . . . . . . . . . . .        .   .   .   .   .   .   .   120
     4.9.6 Hydrazones and Carbodiimides . . . . . . . . .         .   .   .   .   .   .   .   121
     4.9.7 Nitriles and Isonitriles . . . . . . . . . . . . . .   .   .   .   .   .   .   .   122
     4.9.8 Isocyanates, Thiocyanates, and Isothiocyanates         .   .   .   .   .   .   .   122
4.10 Sulfur Compounds . . . . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   123
     4.10.1 Thiols . . . . . . . . . . . . . . . . . . . . . .    .   .   .   .   .   .   .   123
     4.10.2 Sulfides . . . . . . . . . . . . . . . . . . . . .    .   .   .   .   .   .   .   123
     4.10.3 Disulfides and Sulfonium Salts . . . . . . . .        .   .   .   .   .   .   .   124
     4.10.4 Sulfoxides and Sulfones . . . . . . . . . . . .       .   .   .   .   .   .   .   125
     4.10.5 Sulfonic and Sulfinic Acids and Derivatives . .       .   .   .   .   .   .   .   126
     4.10.6 Sulfurous and Sulfuric Acid Derivatives . . . .       .   .   .   .   .   .   .   126
     4.10.7 Sulfur-Containing Carbonyl Derivatives. . . .         .   .   .   .   .   .   .   127
4.11 Carbonyl Compounds . . . . . . . . . . . . . . . . . .       .   .   .   .   .   .   .   128
     4.11.1 Aldehydes . . . . . . . . . . . . . . . . . . .       .   .   .   .   .   .   .   128
     4.11.2 Ketones . . . . . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   129
     4.11.3 Carboxylic Acids . . . . . . . . . . . . . . . .      .   .   .   .   .   .   .   131
     4.11.4 Esters and Lactones . . . . . . . . . . . . . .       .   .   .   .   .   .   .   133
     4.11.5 Amides and Lactams . . . . . . . . . . . . . .        .   .   .   .   .   .   .   135
     4.11.6 Miscellaneous Carbonyl Derivatives. . . . . .         .   .   .   .   .   .   .   137
4.12 Miscellaneous Compounds . . . . . . . . . . . . . . .        .   .   .   .   .   .   .   139
     4.12.1 Compounds with Group IV Elements . . . . .            .   .   .   .   .   .   .   139
     4.12.2 Phosphorus Compounds . . . . . . . . . . . .          .   .   .   .   .   .   .   140
     4.12.3 Miscellaneous Organometallic Compounds . .            .   .   .   .   .   .   .   142
X         Contents

    4.13 Natural Products . . . . . . . . . . . . . . . . . . . . . . . . . .                  .   .   144
         4.13.1 Amino Acids . . . . . . . . . . . . . . . . . . . . . . .                      .   .   144
         4.13.2 Carbohydrates . . . . . . . . . . . . . . . . . . . . . .                      .   .   148
         4.13.3 Nucleotides and Nucleosides. . . . . . . . . . . . . . .                       .   .   150
         4.13.4 Steroids . . . . . . . . . . . . . . . . . . . . . . . . . .                   .   .   152
    4.14 Spectra of Solvents and Reference Compounds. . . . . . . . . .                        .   .   153
         4.14.1 13C NMR Spectra of Common Deuterated Solvents . .                              .   .   153
         4.14.2 13C NMR Spectra of Secondary Reference Compounds                               .   .   155
         4.14.3 13C NMR Spectrum of a Mixture of Common
                     Nondeuterated Solvents . . . . . . . . . . . . . . . .                    . . 156

5   1H   NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 157
    5.1 Alkanes . . . . . . . . . . . . . . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   157
         5.1.1 Chemical Shifts . . . . . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   157
         5.1.2 Coupling Constants . . . . . . . . . . . . .        .   .   .   .   .   .   .   .   .   162
    5.2 Alkenes . . . . . . . . . . . . . . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   164
         5.2.1 Substituted Ethylenes . . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   164
         5.2.2 Conjugated Dienes . . . . . . . . . . . . .         .   .   .   .   .   .   .   .   .   170
         5.2.3 Allenes . . . . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   .   .   171
    5.3 Alkynes . . . . . . . . . . . . . . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   172
    5.4 Alicyclics . . . . . . . . . . . . . . . . . . . . . . .   .   .   .   .   .   .   .   .   .   173
    5.5 Aromatic Hydrocarbons . . . . . . . . . . . . . . .        .   .   .   .   .   .   .   .   .   177
    5.6 Heteroaromatic Compounds . . . . . . . . . . . . .         .   .   .   .   .   .   .   .   .   184
         5.6.1 Non-Condensed Heteroaromatic Rings . . .            .   .   .   .   .   .   .   .   .   184
         5.6.2 Condensed Heteroaromatic Rings . . . . . .          .   .   .   .   .   .   .   .   .   191
    5.7 Halogen Compounds . . . . . . . . . . . . . . . . .        .   .   .   .   .   .   .   .   .   196
         5.7.1 Fluoro Compounds . . . . . . . . . . . . .          .   .   .   .   .   .   .   .   .   196
         5.7.2 Chloro Compounds . . . . . . . . . . . . .          .   .   .   .   .   .   .   .   .   197
         5.7.3 Bromo Compounds . . . . . . . . . . . . .           .   .   .   .   .   .   .   .   .   198
         5.7.4 Iodo Compounds . . . . . . . . . . . . . .          .   .   .   .   .   .   .   .   .   199
    5.8 Alcohols, Ethers, and Related Compounds . . . . . .        .   .   .   .   .   .   .   .   .   200
         5.8.1 Alcohols . . . . . . . . . . . . . . . . . . .      .   .   .   .   .   .   .   .   .   200
         5.8.2 Ethers . . . . . . . . . . . . . . . . . . . .      .   .   .   .   .   .   .   .   .   202
    5.9 Nitrogen Compounds . . . . . . . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   205
         5.9.1 Amines . . . . . . . . . . . . . . . . . . . .      .   .   .   .   .   .   .   .   .   205
         5.9.2 Nitro and Nitroso Compounds . . . . . . .           .   .   .   .   .   .   .   .   .   207
         5.9.3 Nitrites and Nitrates . . . . . . . . . . . . .     .   .   .   .   .   .   .   .   .   208
         5.9.4 Nitrosamines, Azo and Azoxy Compounds .             .   .   .   .   .   .   .   .   .   208
         5.9.5 Imines, Oximes, Hydrazones, and Azines . .          .   .   .   .   .   .   .   .   .   209
                                                                   Contents            XI

          5.9.6 Nitriles and Isonitriles . . . . . . . . . . . . . . . . . . . .   .   210
          5.9.7 Cyanates, Isocyanates, Thiocyanates, and Isothiocyanates .         .   211
  5.10    Sulfur Compounds . . . . . . . . . . . . . . . . . . . . . . . . . .     .   212
          5.10.1 Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . .    .   212
          5.10.2 Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . .    .   213
          5.10.3 Disulfides and Sulfonium Salts . . . . . . . . . . . . . .        .   214
          5.10.4 Sulfoxides and Sulfones . . . . . . . . . . . . . . . . . .       .   214
          5.10.5 Sulfonic, Sulfurous, and Sulfuric Acids and Derivatives .         .   215
          5.10.6 Thiocarboxylate Derivatives . . . . . . . . . . . . . . . .       .   215
  5.11    Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . .       .   216
          5.11.1 Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . .       .   216
          5.11.2 Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . .     .   217
          5.11.3 Carboxylic Acids and Carboxylates . . . . . . . . . . . .         .   218
          5.11.4 Esters and Lactones . . . . . . . . . . . . . . . . . . . .       .   219
          5.11.5 Amides and Lactams . . . . . . . . . . . . . . . . . . . .        .   220
          5.11.6 Miscellaneous Carbonyl Derivatives. . . . . . . . . . . .         .   224
  5.12    Miscellaneous Compounds . . . . . . . . . . . . . . . . . . . . .        .   226
          5.12.1 Compounds with Group IV Elements . . . . . . . . . . .            .   226
          5.12.2 Phosphorus Compounds . . . . . . . . . . . . . . . . . .          .   227
          5.12.3 Miscellaneous Compounds . . . . . . . . . . . . . . . .           .   230
          5.12.4 References . . . . . . . . . . . . . . . . . . . . . . . . .      .   231
  5.13    Natural Products . . . . . . . . . . . . . . . . . . . . . . . . . . .   .   232
          5.13.1 Amino Acids . . . . . . . . . . . . . . . . . . . . . . . .       .   232
          5.13.2 Carbohydrates . . . . . . . . . . . . . . . . . . . . . . .       .   235
          5.13.3 Nucleotides and Nucleosides. . . . . . . . . . . . . . . .        .   237
  5.14    Spectra of Solvents and Reference Compounds. . . . . . . . . . .         .   239
          5.14.1 1H NMR Spectra of Common Deuterated Solvents . . . .              .   239
          5.14.2 1H NMR Spectra of Secondary Reference Compounds . .               .   241
          5.14.3 1H NMR Spectrum of a Mixture of Common
                     Nondeuterated Solvents . . . . . . . . . . . . . . . . .      . 242

6 Heteronuclear NMR Spectroscopy . . . . . . . . . . . . . . . . . . 243
  6.1    19FNMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . .     . . 243
          6.1.1 19F Chemical Shifts of Perfluoroalkanes . . . . . . . . .      . . 243
          6.1.2 Estimation of 19F Chemical Shifts of Substituted
                  Fluoroethylenes . . . . . . . . . . . . . . . . . . . . .    . . 247
          6.1.3 Coupling Constants in Fluorinated Alkanes and Alkenes .        . . 248
          6.1.4 19F Chemical Shifts of Allenes and Alkynes . . . . . . .       . . 249
XII     Contents

          6.1.5   19F
                   Chemical Shifts and Coupling Constants of Fluorinated
                  Alicyclics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
        6.1.6 19F Chemical Shifts and Coupling Constants of Aromatics
                   and Heteroaromatics . . . . . . . . . . . . . . . . . . . . . . . . . 251
        6.1.7  19F Chemical Shifts of Alcohols and Ethers . . . . . . . . . 254

        6.1.8 19F Chemical Shifts of Fluorinated Amine, Imine, and
                   Hydroxylamine Derivatives . . . . . . . . . . . . . . . . 255
        6.1.9  19F Chemical Shifts of Sulfur Compounds . . . . . . . . . . 256

        6.1.10 19F Chemical Shifts of Carbonyl and Thiocarbonyl
                   Compounds . . . . . . . . . . . . . . . . . . . . . . . . 257
        6.1.11 19F Chemical Shifts of Fluorinated Boron, Phosphorus, and
                   Silicon Compounds . . . . . . . . . . . . . . . . . . . . 258
        6.1.12  19F Chemical Shifts of Natural Product Analogues . . . . . 259

        6.1.13 References . . . . . . . . . . . . . . . . . . . . . . . . . . 260
  6.2 31P NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 261

        6.2.1 31P Chemical Shifts of Tricoordinated Phosphorus, PR1R2R3 261
        6.2.2 31P Chemical Shifts of Tetracoordinated Phosphonium
                  Compounds . . . . . . . . . . . . . . . . . . . . . . . . 262
        6.2.3 31P Chemical Shifts of Compounds with a P=C or P=N Bond 263
        6.2.4 31P Chemical Shifts of Tetracoordinated P(=O) and P(=S)
                  Compounds . . . . . . . . . . . . . . . . . . . . . . . . 264
        6.2.5  31P Chemical Shifts of Penta- and Hexacoordinated
                  Phosphorus Compounds . . . . . . . . . . . . . . . . . . 266
        6.2.6 31P Chemical Shifts of Natural Phosphorus Compounds . . . 267

7 IR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
  7.1 Alkanes . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   269
  7.2 Alkenes . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   272
       7.2.1 Monoenes . . . . .           .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   272
       7.2.2 Allenes . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   275
  7.3 Alkynes . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   276
  7.4 Alicyclics . . . . . . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   277
  7.5 Aromatic Hydrocarbons . .           .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   279
  7.6 Heteroaromatic Compounds            .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   282
  7.7 Halogen Compounds . . . .           .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   284
       7.7.1 Fluoro Compounds             .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   284
       7.7.2 Chloro Compounds             .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   285
       7.7.3 Bromo Compounds              .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   286
       7.7.4 Iodo Compounds .             .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   286
                                                                      Contents                        XIII

7.8 Alcohols, Ethers, and Related Compounds . . . .       .   .   .   .   .   .   .   .   .   .   .   287
     7.8.1 Alcohols and Phenols . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   287
     7.8.2 Ethers, Acetals, and Ketals . . . . . . .      .   .   .   .   .   .   .   .   .   .   .   288
     7.8.3 Epoxides . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   .   .   .   .   290
     7.8.4 Peroxides and Hydroperoxides . . . . .         .   .   .   .   .   .   .   .   .   .   .   291
7.9 Nitrogen Compounds . . . . . . . . . . . . . . .      .   .   .   .   .   .   .   .   .   .   .   292
     7.9.1 Amines and Related Compounds . . . .           .   .   .   .   .   .   .   .   .   .   .   292
     7.9.2 Nitro and Nitroso Compounds . . . . .          .   .   .   .   .   .   .   .   .   .   .   294
     7.9.3 Imines and Oximes . . . . . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   296
     7.9.4 Azo, Azoxy, and Azothio Compounds. .           .   .   .   .   .   .   .   .   .   .   .   298
     7.9.5 Nitriles and Isonitriles . . . . . . . . . .   .   .   .   .   .   .   .   .   .   .   .   299
     7.9.6 Diazo Compounds . . . . . . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   300
     7.9.7 Cyanates and Isocyanates . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   301
     7.9.8 Thiocyanates and Isothiocyanates . . . .       .   .   .   .   .   .   .   .   .   .   .   302
7.10 Sulfur Compounds . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   .   .   .   .   304
     7.10.1 Thiols and Sulfides . . . . . . . . . . .     .   .   .   .   .   .   .   .   .   .   .   304
     7.10.2 Sulfoxides and Sulfones . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   305
     7.10.3 Thiocarbonyl Derivatives . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   307
     7.10.4 Thiocarbonic Acid Derivatives . . . . .       .   .   .   .   .   .   .   .   .   .   .   307
7.11 Carbonyl Compounds . . . . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   310
     7.11.1 Aldehydes . . . . . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   310
     7.11.2 Ketones . . . . . . . . . . . . . . . . .     .   .   .   .   .   .   .   .   .   .   .   311
     7.11.3 Carboxylic Acids . . . . . . . . . . . .      .   .   .   .   .   .   .   .   .   .   .   314
     7.11.4 Esters and Lactones . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   316
     7.11.5 Amides and Lactams . . . . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   319
     7.11.6 Acid Anhydrides . . . . . . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   322
     7.11.7 Acid Halides . . . . . . . . . . . . . .      .   .   .   .   .   .   .   .   .   .   .   323
     7.11.8 Carbonic Acid Derivatives . . . . . . .       .   .   .   .   .   .   .   .   .   .   .   324
7.12 Miscellaneous Compounds . . . . . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   327
     7.12.1 Silicon Compounds . . . . . . . . . .         .   .   .   .   .   .   .   .   .   .   .   327
     7.12.2 Phosphorus Compounds . . . . . . . .          .   .   .   .   .   .   .   .   .   .   .   328
     7.12.3 Boron Compounds . . . . . . . . . . .         .   .   .   .   .   .   .   .   .   .   .   331
7.13 Amino Acids . . . . . . . . . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   .   .   332
7.14 Solvents, Suspension Media, and Interferences .      .   .   .   .   .   .   .   .   .   .   .   333
     7.14.1 Infrared Spectra of Common Solvents .         .   .   .   .   .   .   .   .   .   .   .   333
     7.14.2 Infrared Spectra of Suspension Media .        .   .   .   .   .   .   .   .   .   .   .   334
     7.14.3 Interferences in Infrared Spectra . . . .     .   .   .   .   .   .   .   .   .   .   .   335
XIV    Contents

8 Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
  8.1 Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
  8.2 Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
  8.3 Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
  8.4 Alicyclics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
  8.5 Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . 345
  8.6 Heteroaromatic Compounds . . . . . . . . . . . . . . . . . . . . . . 347
  8.7 Halogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 352
  8.8 Alcohols, Ethers, and Related Compounds .          .   .   .   .   .   .   .   .   .   .   .   .   .   .   354
       8.8.1 Alcohols and Phenols . . . . . . .          .   .   .   .   .   .   .   .   .   .   .   .   .   .   354
       8.8.2 Hydroperoxides . . . . . . . . . .          .   .   .   .   .   .   .   .   .   .   .   .   .   .   356
       8.8.3 Ethers . . . . . . . . . . . . . . .        .   .   .   .   .   .   .   .   .   .   .   .   .   .   356
       8.8.4 Aliphatic Epoxides . . . . . . . .          .   .   .   .   .   .   .   .   .   .   .   .   .   .   359
         8.8.5 Aliphatic Peroxides . . . . . . . . . . . . . . . . . . . . . . 360
         8.8.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
  8.9 Nitrogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . .                                   .   362
       8.9.1 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . .                                  .   362
       8.9.2 Nitro Compounds . . . . . . . . . . . . . . . . . . . . . .                                     .   364
       8.9.3 Diazo Compounds and Azobenzenes . . . . . . . . . . . .                                         .   364
       8.9.4 Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . .                                  .   365
       8.9.5 Nitriles and Isonitriles . . . . . . . . . . . . . . . . . . . .                                .   366
       8.9.6 Cyanates, Isocyanates, Thiocyanates, and Isothiocyanates .                                      .   367
       8.9.7 References . . . . . . . . . . . . . . . . . . . . . . . . . .                                  .   369
  8.10 Sulfur Compounds . . . . . . . . . . . . . . . . . . .                    .   .   .   .   .   .   .   .   371
       8.10.1 Thiols . . . . . . . . . . . . . . . . . . . . .                   .   .   .   .   .   .   .   .   371
       8.10.2 Sulfides and Disulfides . . . . . . . . . . . .                    .   .   .   .   .   .   .   .   371
       8.10.3 Sulfoxides and Sulfones . . . . . . . . . . .                      .   .   .   .   .   .   .   .   373
       8.10.4 Sulfonic Acids and Their Esters and Amides                         .   .   .   .   .   .   .   .   376
         8.10.5 Thiocarboxylic Acid Esters . . . . . . . . . . . . . . . . . 377
         8.10.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . 378
  8.11 Carbonyl Compounds . . . . . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   379
       8.11.1 Aldehydes . . . . . . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   379
       8.11.2 Ketones . . . . . . . . . . . .    .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   380
       8.11.3 Carboxylic Acids . . . . . . .     .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   381
       8.11.4 Carboxylic Acid Anhydrides .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   382
       8.11.5 Esters and Lactones . . . . .      .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   382
       8.11.6 Amides and Lactams . . . . .       .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   .   384
                                                               Contents                XV

       8.11.7 Imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
       8.11.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . 387
  8.12 Miscellaneous Compounds . . . . . . . . . . . . . . . . . . . . . . 388
       8.12.1 Trialkylsilyl Ethers . . . . . . . . . . . . . . . . . . .   .   .   .   388
       8.12.2 Phosphorus Compounds . . . . . . . . . . . . . . . .         .   .   .   388
       8.12.3 References . . . . . . . . . . . . . . . . . . . . . . .     .   .   .   389
  8.13 Mass Spectra of Common Solvents and Matrix Compounds . .            .   .   .   390
       8.13.1 Electron Impact Ionization Mass Spectra of Common
                Solvents . . . . . . . . . . . . . . . . . . . . . . .     . . . 390
       8.13.2 Spectra of Common FAB MS Matrix and Calibration
                Compounds . . . . . . . . . . . . . . . . . . . . . .      . . . 393
       8.13.3 Spectra of Common MALDI MS Matrix Compounds.                 . . . 398
       8.13.4 References . . . . . . . . . . . . . . . . . . . . . . .     . . . 400

9 UV/Vis Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 401
  9.1 Correlation between Wavelength of Absorbed Radiation and Observed
       Color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
  9.2 Simple Chromophores . . . . . . . . . . . . . . . . . . . . . . . . . 401
  9.3 Conjugated Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
        9.3.1 Dienes and Polyenes. . . . . . . . . . . . . . . . . . . . . . 403
        9.3.2 α,β-Unsaturated Carbonyl Compounds . . . . . . . . . . . . 404
  9.4 Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . 406
        9.4.1 Monosubstituted Benzenes . . . . . . . . . . . . . . . . . . 406
        9.4.2 Polysubstituted Benzenes . . . . . . . . . . . . . . . . . . . 407
        9.4.3 Aromatic Carbonyl Compounds . . . . . . . . . . . . . . . . 408
  9.5 Reference Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
        9.5.1 Alkenes and Alkynes . . . . . . . . . . . . . . . . . . . . . 409
        9.5.2 Aromatic Compounds . . . . . . . . . . . . . . . . . . . . . 410
        9.5.3 Heteroaromatic Compounds . . . . . . . . . . . . . . . . . . 415
        9.5.4 Miscellaneous Compounds . . . . . . . . . . . . . . . . . . 417
        9.5.5 Nucleotides . . . . . . . . . . . . . . . . . . . . . . . . . . 419
  9.6 Common Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
1 Introduction




1.1 Scope and Organization
The present data collection is intended to serve as an aid in the interpretation of
molecular spectra for the elucidation and confirmation of the structure of organic
compounds. It consists of reference data, spectra, and empirical correlations from
1H, 13C, 19F, and 31P nuclear magnetic resonance (NMR), infrared (IR), mass, and
ultraviolet–visible (UV/Vis) spectroscopy. It is to be viewed as a supplement to
textbooks and specific reference works dealing with these spectroscopic techniques.
The use of this book to interpret spectra only requires the knowledge of basic prin-
ciples of the techniques, but its content is structured in a way that it will serve as a
reference book also to specialists.
   Chapters 2 and 3 contain Summary Tables and Combined Tables of the most
relevant spectral characteristics of structural elements. While Chapter 2 is orga-
nized according to the different spectroscopic methods, Chapter 3 for each class
of structural elements supplies spectroscopic information obtained with various
techniques. These two chapters should assist users less familiar with spectra inter-
pretation to identify the classes of structural elements present in samples of their
interest. The four chapters with data from 13C NMR, 1H NMR, IR spectroscopy,
and mass spectrometry are ordered in the same manner by compound types. These
cover the various carbon skeletons (alkyl, alkenyl, alkynyl, alicyclic, aromatic, and
heteroaromatic), the most important substituents (halogen, single-bonded oxygen,
nitrogen, sulfur, and carbonyl), and some specific compound classes (miscellaneous
compounds and natural products). Finally, a spectra collection of common solvents,
auxiliary compounds (such as matrix materials and references), and commonly
found impurities is provided with each method. Not only the strictly analogous
order of the data but also the optical marks on the edge of the pages help fast cross-
referencing between the various spectroscopic techniques. Because their data sets
are less comprehensive, the chapters on 19F and 31P NMR and UV/Vis are organized
somewhat differently. Although currently UV/Vis spectroscopy is only marginally
relevant to structure elucidation, its importance might increase by the advent of
high-throughput analyses. Also, the reference data presented in the UV/Vis chapter
are useful in connection with optical sensors and the widely applied UV/Vis detec-
tors in chromatography and electrophoresis.
   Since a great part of the tabulated data either comes from our own measurements
or is based on a large body of literature data, comprehensive references to published
sources are not included. Whenever possible, the data refer to conventional modes
and conditions of measurement. For example, unless the solvent is indicated, the
NMR chemical shifts were normally determined with deuterochloroform. Likewise,
the IR spectra were measured using solvents of low polarity, such as chloroform or
2       1 Introduction

carbon disulfide. Mass spectral data were recorded with electron impact ionization
at 70 eV.
   While retaining the basic structure of the previous editions, numerous reference
entries have been updated and new entries have been added. Altogether, about 20%
of the data is new. The chapter on 19F and 31P NMR is entirely new, and the section
on IR spectroscopy now includes references to important Raman bands.
                               1.2 Abbreviations and Symbols   3

1.2 Abbreviations and Symbols
al      aliphatic
alk     alkyl
alken   alkenyl
ar      aromatic
as      asymmetric
ax      axial
comb    combination vibration
d       doublet
δ       IR: deformation vibration
        NMR: chemical shift
DFTMP   1,1-difluoro-1-(trimethylsilyl)methylphosphonic acid
DMSO    dimethyl sulfoxide
eq      equatorial
ε       molar absorptivity
frag    fragment
γ       skeletal vibration
gem     geminal
hal     halogen
ip      in plane vibration
J       coupling constant
liq     liquid
M+.     molecular radical ion
m/z     mass to charge ratio
~
ν       wavenumber
oop     out of plane vibration
sh      shoulder
st      stretching vibration
sy      symmetric
TFA     trifluoroacetic acid
THF     tetrahydrofuran
TMS     tetramethylsilane
vic     vicinal
2 Summary Tables




2.1 General Tables

2.1.1 Calculation of the Number of Double Bond Equivalents from
the Molecular Formula

General Equation

        double bond equivalents = 1 + ½ ∑ni (vi – 2)
                                         i

  ni: number of atoms of element i in molecular formula
  vi: formal valence of element i

Short Cut
For compounds containing only C, H, O, N, S, and halogens, the following steps
permit a quick and simple calculation of the number of double bond equivalents:

  1. O and divalent S are deleted from the molecular formula
  2. Halogens are replaced by hydrogen
  3. Trivalent N is replaced by CH
  4. The resulting hydrocarbon, CnHx, is compared with the saturated hydrocar-
     bon, CnH2n+2. Each double bond equivalent reduces the number of hydrogen
     atoms by 2:

        double bond equivalents = ½ (2 n + 2 – x)
6       2 Summary Tables

2.1.2 Properties of Selected Nuclei

Isotope Natural   Spin        Frequency Relative    Relative     Electric
        abundance quantum     [MHz] at sensitivity sensitivity   quadrupole
           [%]    number, I   2.35 Tesla of nucleus at natural   moment
                                                    abundance    [e × 10-24
                                                                     cm2]
1H        99.985     1/2       100.0     1          1
2H         0.015      1         15.4     9.6×10-3   1.5×10-6     2.8×10-3
3H         0.000     1/2       106.7     1.2        0
10B       19.58       3         10.7     2.0×10-2   3.9×10-3     7.4×10-2
11B       80.42      3/2        32.1     1.6×10-1   1.3×10-1     3.6×10-2
13C        1.108     1/2        25.1     1.6×10-2   1.8×10-4
14N       99.635      1          7.3     1.0×10-3   1.0×10-3     1.9×10-2
15N        0.365     1/2        10.1     1.0×10-3   3.8×10-6
17O        0.037     5/2        13.6     2.9×10-2   1.1×10-5     -2.6×10-2
19F      100.000     1/2        94.1     8.3×10-1   8.3×10-1
31P      100.000     1/2        40.5     6.6×10-2   6.6×10-2
33S        0.76      3/2         7.6     2.3×10-3   1.7×10-5     -6.4×10-2
117Sn      7.61      1/2        35.6     4.5×10-2   3.4×10-3
119Sn      8.58      1/2        37.3     5.2×10-2   4.4×10-3
195Pt     33.8       1/2        21.5     9.9×10-3   3.4×10-3
199Hg     16.84      1/2        17.8     5.7×10-3   9.5×10-4
207Pb     22.6       1/2        20.9     9.2×10-3   2.1×10-4
                                         2.2 13C NMR Spectroscopy                            7

2.2      13C   NMR Spectroscopy

Summary of the Regions of Chemical Shifts, δ (in ppm), for Carbon Atoms in
Various Chemical Environments (carbon atoms are specified as follows: Q for
CH3, T for CH2, D for CH, and S for C)
                         240 220 200 180 160 140 120 100 80 60        40 20          0 ppm

H3C C     H3C C X H3C C X                                                        Q
 H3C S                                                                           Q
  C CH2 C                                                             T
  C CH2 S                                                                T
  C
  C
    CH C                                                             D
 H3C COX; X: C, O, N                                                         Q
  C C                                                        D,S
 CH3Cl                                                                    Q
  C
  C
    CH S                                                          D
 H3C N                                                                   Q
  C C
   C
  C C                                                            S
  C CH2COX; X: C, O, N                                               T
  C
  C
    CHCOX; X: C, O, N                                            D
  C CH2 N                                                        T
  C S
   C
  C C                                                         S
  C CH2Cl                                                            T
 C
   CH N                                                      D
 C
 C COX; X: C,O,N
   C
 C C                                                     S
H3C O                                                         Q
 C N
   C
 C C                                                     S
 C
   CH Cl                                                  D
 C
H3C NO2                                                           Q
                         240 220 200 180 160 140 120 100 80 60        40 20          0 ppm
8               2 Summary Tables

                                     240 220 200 180 160 140 120 100 80 60                     40 20   0 ppm

    C CH2 O                                                                            T
    C
      CH O                                                                         D
    C
    C CH2 NO2                                                                          T
 C Cl
   C
 C C                                                                           S
 C
   CH NO2                                                                          D
 C
 C O
   C
 C C                                                                           S           D
 C NO2
   C
 C C                                                                           S
H
  C C                                                                      T
H
X
         C H; X: any substituent                                           D
    C C                                                               D, S
        O
    C                                                           T, D, S
        O
        C X; X: any substituent                                        S
     C X
N
     C
      C X: any substituent                                        D, S
    C N                                                                S
 C       X
N
 C
                X: any substituent                             D, S
            C               O
    C N               C N                                  D, S
                                                           S

                                                           S
    C COX; X: O, N, Cl                                 S
    C COOH                                             S
                                                   S
    C CSX; X: O, N                             S
                                               S
    C CHO                                  D
    C
      C O                                  S
    C
    C
      C S                              S
    C
                                     240 220 200 180 160 140 120 100 80 60                     40 20   0 ppm
                                        2.2 13C NMR Spectroscopy   9

13C   Chemical Shifts of Carbonyl Groups (δ in ppm)

R                R–CHO          R–COCH3       R–COOH      R–COO–
–H               197.0          200.5          166.3      171.3
–CH3             200.5          206.7          176.9      182.6
–CH2CH3          202.7          207.6          180.4      185.1
–CH(CH3)2        204.6          211.8          184.1
–C(CH3)3         205.6          213.5          185.9      188.6
–n-C8H17         202.6          207.9          180.7      183.1
–CH2Cl           193.3          200.1          173.7      175.9
–CHCl2                          193.6          170.4      171.8
–CCl3            176.9          186.3          167.1      167.6
–cyclohexyl      204.7          209.4          182.1      185.4
–CH=CH2          194.4          197.5          171.7      174.5
–C – CH
   –
   –             176.8          183.6          156.5
–phenyl          192.0          196.9          172.6      177.6


R                R–CHO          R–COCH3       R–COOH      R–COO–
–H               161.6          167.6          158.5
–CH3             171.3          173.4          167.4      170.4
–CH2CH3          173.3          177.2          170.3      174.7
–CH(CH3)2        177.4                         172.8      178.0
–C(CH3)3         178.8          180.9          173.9      180.3
–n-C8H17         174.4          176.3          169.4      173.8
–CH2Cl           167.8          168.3          162.1      167.7
–CHCl2           165.1                         157.6      165.5
–CCl3            162.5                         154.1
–cyclohexyl      175.3          177.3                     176.3
–CH=CH2          166.5          168.3                     165.6
–C – CH
   –
   –             153.4
–phenyl          166.8          169.7         162.8       168.0
10     2 Summary Tables

2.3   1H   NMR Spectroscopy

Summary of the Regions of Chemical Shifts, δ (in ppm), for Hydrogen Atoms
in Various Chemical Environments

                       14 13 12 11 10 9   8   7   6   5   4   3   2   1   0 ppm




                       14 13 12 11 10 9   8   7   6   5   4   3   2   1   0 ppm
            2.3 1H NMR Spectroscopy                  11

14 13 12 11 10 9   8   7   6   5   4   3   2   1   0 ppm




14 13 12 11 10 9   8   7   6   5   4   3   2   1   0 ppm
12            2 Summary Tables

                                 14 13 12 11 10 9   8   7   6   5   4   3   2   1   0 ppm

         CH2 Cl

    O
H 2C
    S
    O
H2C
    O
         OH

       Cl
H 2C
       S
 O
   CH O               Cl CH2 N
 O
         CH2 O

 C        O
   CH O C
 C
O CH2 N

N CO
H
 O CH2Cl

         H; heteroaromatic CH

     H                H
 O       N        O       O

heteroaromatic NH
    O
 O       H
             OH
 C N

CHO

COOH

                                 14 13 12 11 10 9   8   7   6   5   4   3   2   1   0 ppm
                                           2.4 IR Spectroscopy         13

2.4 IR Spectroscopy

Summary of the Most Important IR Absorption Bands ( ~ in cm-1)
                                                    ν
                     3500   3000    2500    2000   1500   1000    500 cm -1




     δ




     δ
         δ


                     3500    3000   2500    2000   1500    1000   500 cm -1
14     2 Summary Tables

Summary of IR Absorption Bands of Carbonyl Groups ( ~ in cm-1)
                                                    ν
                      1900   1850   1800   1750   1700   1650   1600 1550 cm-1




                      1900   1850   1800   1750   1700   1650   1600 1550 cm-1
                      2.4 IR Spectroscopy           15

1900   1850   1800   1750   1700   1650   1600 1550 cm-1




1900   1850   1800   1750   1700   1650   1600 1550 cm-1
16   2 Summary Tables

                1900    1850   1800   1750   1700   1650   1600 1550 cm-1




                1900    1850   1800   1750   1700   1650   1600 1550 cm-1
                                      2.4 IR Spectroscopy           17

                1900   1850   1800   1750   1700   1650   1600 1550 cm-1

(in solution)




 (solid)




                1900   1850   1800   1750   1700   1650   1600 1550 cm-1
18         2 Summary Tables

2.5 Mass Spectrometry

2.5.1 Average Masses of Naturally Occurring Elements with Masses
and Representative Relative Abundances of Isotopes [1–3]
Element                                    Element
Isotope         Mass        Abundance      Isotope       Mass      Abundance
H              1.00794a,b     (in water)   F           18.998403
     1H        1.007825     100c                19F    18.998403   100
     2H        2.014102       0.0115
                                           Ne          20.1797a       (in air)
He             4.002602a   (in air)             20Ne   19.992440   100c
     3He       3.016029   0.000134              21Ne   20.993847     0.38
     4He       4.002603 100                     22Ne   21.991385    10.22

Li             6.941a                      Na          22.989769
     6Li       6.015123       8.21d             23Na   22.989769   100
     7Li       7.016005     100
                                           Mg          24.3050
Be             9.012182                         24Mg   23.985042   100
     9Be       9.012182     100                 25Mg   24.985837    12.66
                                                26Mg   25.982593    13.94
B             10.811a
     10B      10.012937      24.8c         Al          26.981538
     11B      11.009305     100                 27Al   26.981538   100

C             12.0107a                     Si          28.0855a
     12C      12.000000     100                 28Si   27.976927   100
     13C      13.003355       1.08              29Si   28.976495     5.080
                                                30Si   29.973770     3.353
N             14.0067a
     14N      14.003074     100            P           30.973762
     15N      15.000109       0.365             31P    30.973762   100

O             15.9994a                     S           32.065a
     16O      15.994915     100                 32S    31.972071   100c
     17O      16.999132       0.038             33S    32.971459     0.79
     18O      17.999161       0.205             34S    33.967867     4.47
                                                36S    35.967081     0.01
                                           2.5 Mass Spectrometry         19

Element                               Element
Isotope      Mass      Abundance      Isotope       Mass      Abundance
Cl         35.453                     Cr          51.9961
    35Cl   34.968853   100c            50Cr       49.946044     5.186
    37Cl   36.965903    32.0           52Cr       51.940508   100
                                       53Cr       52.940649    11.339
Ar         39.948a         (in air)    54Cr       53.938880     2.823
    36Ar   35.967545     0.3379
    38Ar   37.962732     0.0635       Mn          54.938045
    40Ar   39.962383   100             55Mn       54.938045   100

K          39.0983                    Fe          55.845
    39K    38.963707   100             54Fe       53.939611     6.370
    40K    39.963998     0.0125        56Fe       55.934938   100
    41K    40.961826     7.2167        57Fe       56.935394     2.309
                                       58Fe       57.933276     0.307
Ca         40.078
    40Ca   39.962591   100            Co          58.933195
    42Ca   41.958618     0.667         59Co       58.933195   100
    43Ca   42.958767     0.139
    44Ca   43.955482     2.152        Ni          58.6934
    46Ca   45.953693     0.004         58Ni       57.935343   100
    48Ca   47.952534     0.193         60Ni       59.930786    38.5198
                                       61Ni       60.931056     1.6744
Sc         44.955912                   62Ni       61.928345     5.3388
    45Sc   44.955912   100             64Ni       63.927966     1.3596

Ti         47.867                     Cu          63.546a
    46Ti   45.952632    11.19          63Cu       62.929598   100
    47Ti   46.951763    10.09          65Cu       64.927790    44.61
    48Ti   47.947946   100
    49Ti   48.947870     7.34         Zn          65.409
    50Ti   49.944791     7.03          64Zn       63.929142   100
                                       66Zn       65.926033    57.96
V          50.9415                     67Zn       66.927127     8.49
    50V    49.947159     0.251         68Zn       67.924844    39.41
    51V    50.943960   100             70Zn       69.925319     1.31
20          2 Summary Tables

Element                                   Element
Isotope          Mass      Abundance      Isotope      Mass      Abundance
Ga             69.723                     Rb         85.4678
     69Ga      68.925574   100c               85Rb   84.911790   100
     71Ga      70.924701    66.36             87Rb   86.909181    38.56

Ge             72.64                      Sr         87.62a
     70Ge      69.924247    55.50             84Sr   83.913425     0.68
     72Ge      71.922076    74.37             86Sr   85.909260    11.94
     73Ge      72.923459    21.13             87Sr   86.908877     8.48
     74Ge      73.921178   100                88Sr   87.905612   100
     76Ge      75.921403    21.32
                                          Y          88.905848
As             74.921597                      89Y    88.905848   100
     75As      74.921597   100
                                          Zr         91.224
Se             78.96                          90Zr   89.904704   100
     74Se      73.922476     1.79             91Zr   90.905646    21.81
     76Se      75.919214    18.89             92Zr   91.905041    33.33
     77Se      76.919914    15.38             94Zr   93.906315    33.78
     78Se      77.917309    47.91             96Zr   95.908273     5.44
     80Se      79.916521   100
     82Se      81.916699    17.60         Nb         92.906378
                                              93Nb   92.906378   100
Br             79.904
     79Br      78.918337   100            Mo         95.94
     81Br      80.916291    97.28             92Mo   91.906811    61.06
                                              94Mo   93.905088    38.16
Kr             83.798          (in air)       95Mo   94.905842    65.72
     78Kr      77.920382     0.623c           96Mo   95.904680    68.95
     80Kr      79.916379     4.011            97Mo   96.906022    39.52
     82Kr      81.913484    20.343            98Mo   97.905408   100
     83Kr      82.914136    20.180        100Mo      99.907477    39.98
     84Kr      83.911507   100
     86Kr      85.910611    30.321
                                        2.5 Mass Spectrometry        21

Element                            Element
Isotope      Mass      Abundance   Isotope        Mass      Abundance
Ru        101.07                   In          114.818
 96Ru      95.907598    17.56          113In   112.904058     4.48
 98Ru      97.905287     5.93          115In   114.903878   100
 99Ru      98.905939    40.44
 100Ru     99.904220    39.94      Sn          118.710
 101Ru    100.905582    54.07          112Sn   111.904818     2.98
 102Ru    101.904349   100             114Sn   113.902779     2.03
 104Ru    103.905433    59.02          115Sn   114.903342     1.04
                                       116Sn   115.901741    44.63
Rh        102.905504                   117Sn   116.902952    23.57
 103Rh    102.905504   100             118Sn   117.901603    74.34
                                       119Sn   118.903309    26.37
Pd        106.42                       120Sn   119.902195   100
 102Pd    101.905609     3.73          122Sn   121.903439    14.21
 104Pd    103.904036    40.76          124Sn   123.905274    17.77
 105Pd    104.905085    81.71
 106Pd    105.903486   100         Sb          121.760
 108Pd    107.903892    96.82          121Sb   120.903816   100
 110Pd    109.905153    42.88          123Sb   122.904214    74.79

Ag        107.8682                 Te          127.60
 107Ag    106.905097   100             120Te   119.904020     0.26
 109Ag    108.904752    92.90          122Te   121.903044     7.48
                                       123Te   122.904270     2.61
Cd        112.411                      124Te   123.902818    13.91
 106Cd    105.906459     4.35          125Te   124.904431    20.75
 108Cd    107.904184     3.10          126Te   125.903312    55.28
 110Cd    109.903002    43.47          128Te   127.904463    93.13
 111Cd    110.904178    44.55          130Te   129.906224   100
 112Cd    111.902758    83.99
 113Cd    112.904402    42.53      I           126.904473
 114Cd    113.903359   100             127I    126.904473   100
 116Cd    115.904756    26.07
22           2 Summary Tables

Element                                 Element
Isotope           Mass      Abundance   Isotope      Mass      Abundance
Xe             131.293                  Nd        144.242
     124Xe     123.905893     0.354c     142Nd    141.907723   100
     126Xe     125.904274     0.330      143Nd    142.909815    44.9
     128Xe     127.903531     7.099      144Nd    143.910087    87.5
     129Xe     128.904779    98.112      145Nd    144.912574    30.5
     130Xe     129.903508    15.129      146Nd    145.913117    63.2
     131Xe     130.905082    78.906      148Nd    147.916893    21.0
     132Xe     131.904154   100          150Nd    149.920891    20.6
     134Xe     133.905395    38.782
     136Xe     135.907219    32.916     Sm        150.36
                                         144Sm    143.911999    11.48
Cs             132.905452                147Sm    146.914898    56.04
     133Cs     132.905452   100          148Sm    147.914823    42.02
                                         149Sm    148.917185    51.66
Ba             137.327                   150Sm    149.917276    27.59
     130Ba     129.906321     0.148      152Sm    151.919732   100
     132Ba     131.905061     0.141      154Sm    153.922209    85.05
     134Ba     133.904508     3.371
     135Ba     134.905689     9.194     Eu        151.964
     136Ba     135.904576    10.954      151Eu    150.919850    91.61
     137Ba     136.905827    15.666      153Eu    152.921230   100
     138Ba     137.905247   100
                                        Gd        157.25
La             138.90547                 152Gd    151.919791     0.81
     138La     137.907112     0.090      154Gd    153.920866     8.78
     139La     138.906353   100          155Gd    154.922622    59.58
                                         156Gd    155.922123    82.41
Ce             140.116                   157Gd    156.923960    63.00
     136Ce     135.907172     0.209      158Gd    157.924104   100
     138Ce     137.905991     0.284      160Gd    159.927054    88.00
     140Ce     139.905439   100
     142Ce     141.909244    12.565     Tb        158.925347
                                         159Tb    158.925347   100
Pr             140.907653
     141Pr     140.907653   100
                                        2.5 Mass Spectrometry          23

Element                            Element
Isotope      Mass      Abundance   Isotope         Mass      Abundance
Dy        162.500                  Hf           178.49
 156Dy    155.924283     0.20           174Hf   173.940046     0.46
 158Dy    157.924409     0.34           176Hf   175.941409    14.99
 160Dy    159.925198     8.24           177Hf   176.943221    53.02
 161Dy    160.926933    66.84           178Hf   177.943699    77.77
 162Dy    161.926798    90.15           179Hf   178.944816    38.83
 163Dy    162.928731    88.10           180Hf   179.946550   100
 164Dy    163.929175   100
                                   Ta           180.94788
Ho        164.930322                    180Ta   179.947465     0.012
 165Ho    164.930322   100              181Ta   180.947996   100

Er        167.259                  W            183.84
 162Er    161.928778     0.41           180W    179.946704     0.39
 164Er    163.929200     4.78           182W    181.948204    86.49
 166Er    165.930293   100              183W    182.950223    46.70
 167Er    166.932048    68.26           184W    183.950931   100.0
 168Er    167.932370    80.52           186W    185.954364    92.79
 170Er    169.935464    44.50
                                   Re           186.207
Tm        168.934213                    185Re   184.952955    59.74
 169Tm    168.934213   100              187Re   186.955753   100

Yb        173.04                   Os           190.23
 168Yb    167.933897     0.41           184Os   183.952489     0.05
 170Yb    169.934762     9.55           186Os   185.953838     3.90
 171Yb    170.936326    44.86           187Os   186.955751     4.81
 172Yb    171.936382    68.58           188Os   187.955838    32.47
 173Yb    172.938211    50.68           189Os   188.958148    39.60
 174Yb    173.938862   100              190Os   189.958447    64.39
 176Yb    175.942572    40.09           192Os   191.961481   100

Lu        174.967                  Ir           192.217
 175Lu    174.940772   100              191Ir   190.960594    59.49
 176Lu    175.942686     2.66           193Ir   192.962926   100.0
24           2 Summary Tables

Element                                       Element
Isotope           Mass         Abundance      Isotope         Mass         Abundance
Pt             195.084                        Tl          204.3833
     190Pt     189.959932       0.041             203Tl   202.972344       41.88
     192Pt     191.961038       2.311             205Tl   204.974428      100
     194Pt     193.962680      97.443
     195Pt     194.964791     100             Pb          207.2a
     196Pt     195.964952      74.610             204Pb   203.973044        2.7
     198Pt     197.967893      21.172             206Pb   205.974465       46.0
                                                  207Pb   206.975897       42.2
Au             196.966569                         208Pb   207.976653      100
     197Au     196.966569     100
                                              Bi          208.980399
Hg             200.59                             209Bi   208.980399      100
     196Hg     195.965833       0.50
     198Hg     197.966769      33.39          Th          232.038055
     199Hg     198.968280      56.50              232Th   232.038055      100
     200Hg     199.968326      77.36
     201Hg     200.970302      44.14          U           238.02891
     202Hg     201.970643     100                 234U    234.040952        0.0054e
     204Hg     203.973494      23.01              235U    235.043930        0.7257
                                                  238U    238.050788      100

a   Natural variations in the isotopic composition of terrestrial materials do not allow
    to give a more precise value.
b   The mole ratio of 2H in hydrogen from gas cylinders was reported to be as low as
    0.000032.
c   Commercially available materials may have substantially different isotopic
    compositions if they were subjected to undisclosed or inadvertent isotopic
    fractionation.
d   Materials depleted in 6Li are commercial sources of laboratory shelf reagents and
    are known to have 6Li abundances in the range of 2.0007–7.672 atom percent,
    with natural materials at the higher end of this range. Average atomic masses
    vary between 6.939 and 6.996; if a more accurate value is required, it must be
    determined for the specific material.
e   Materials depleted in 235U are commercial sources of laboratory shelf reagents.
                                           2.5 Mass Spectrometry           25

2.5.2 Ranges of Natural Isotope Abundances of Selected Elements [3]

Element          Range     Element          Range    Element          Range
Isotope       [atom %]     Isotope       [atom %]    Isotope       [atom %]
H                          Si                        Sr
1H     99.9816–99.9974     28Si      92.205–92.241   84Sr          0.55–0.58
2H       0.0026–0.0184     29Si        4.678–4.692   86Sr          9.75–9.99
                           30Si        3.082–3.102   87Sr          6.94–7.14
He                                                   88Sr        82.29–82.75
3He    4.6×10-8–0.0041     S
4He       99.9959–100      32S       94.454–95.281   Ce
                           33S         0.730–0.793   136Ce       0.185–0.186
Li                         34S         3.976–4.734   138Ce       0.251–0.254
6Li         7.225–7.714    36S         0.013–0.019   140Ce     88.446–88.449
7Li       92.275–92.786                              142Ce     11.114–11.114
                           Cl
B                          35Cl      75.644–75.923   Nd
10B        18.929–20.386   37Cl      24.077–24.356   142Nd       26.80–27.30
11B       79.614– 81.071                             143Nd       12.12–12.32
                           Ca                        144Nd       23.79–23.97
C                          40Ca      96.933–96.947   145Nd         8.23–8.35
12C       98.853–99.037    42Ca        0.646–0.648   146Nd       17.06–17.35
13C         0.963–1.147    43Ca        0.135–0.135   148Nd         5.66–5.78
                           44Ca        2.082–2.092   150Nd         5.53–5.69
N                          46Ca        0.004–0.004
14N       99.579–99.654    48Ca        0.186–0.188   Pb
15N         0.346–0.421                              204Pb         1.04–1.65
                           V                         206Pb       20.84–27.48
O                          50V      0.2487–0.2502    207Pb       17.62–23.65
16O       99.738–99.776    51V    99.7498–99.7513    208Pb       51.28–56.21
17O         0.037–0.040
18O         0.188–0.222    Cu                        U
                           63Cu      68.983–69.338   234U       0.0050–0.0059
Ne                         65Cu      30.662–31.017   235U       0.7198–0.7207
20Ne        88.47–90.51                              238U    99.2739–99.2752
21Ne           0.27–1.71
22Ne          9.20– 9.96
26      2 Summary Tables

2.5.3 Isotope Patterns of Naturally Occurring Elements

The mass of the most abundant isotope is given under the symbol of the element.
The lightest isotope is shown at the left end of the x axis.


        H            He           Li           Be           B            C
        1            4            7            9            11           12

        N            O            F            Ne           Na           Mg
        14           16           19           20           23           24

        Al           Si           P            S            Cl           Ar
        27           28           31           32           35           40

        K            Ca           Sc           Ti           V            Cr
        39           40           45           48           51           52

        Mn           Fe           Co           Ni           Cu           Zn
        55           56           59           58           63           64

        Ga           Ge           As           Se           Br           Kr
        69           74           75           80           79           84

        Rb           Sr           Y            Zr           Nb           Mo
        85           88           89           90           93           98

        Ru           Rh           Pd           Ag           Cd            In
        102          103          106          107          114          115

        Sn           Sb           Te            I           Xe           Cs
        120          121          130          127          132          133

        Ba           La           Ce            Pr          Nd           Sm
        138          139          140          141          142          152

        Eu           Gd           Tb           Dy           Ho           Er
        153          158          159          164          165          166

        Tm           Yb           Lu           Hf           Ta           W
        169          174          175          180          181          184

        Re           Os            Ir           Pt          Au           Hg
        187          192          193          195          197          202

         Tl          Pb           Bi           Th            U
        205          208          209          232          238
                                                         2.5 Mass Spectrometry       27

2.5.4 Calculation of Isotope Distributions

The characteristic abundance patterns resulting from the combination of more
than one polyisotopic element can be calculated from the relative abundances
of the different isotopes. The following polynomial expression gives the isotope
distribution of a polyisotopic molecule:

   {pi1 Α0 + pi2 Α(mi2 - mi1) + pi3 Α(mi3 - mi1) + …}ni ×

      {pj1 Α0 + pj2 Α(mj2 - mj1) + pj3 Α(mj3 - mj1) + …}nj × {…

where pix is the relative abundance of the xth isotope of element i, mix is the mass of
the xth isotope of the element i, and the exponent ni stands for the number of atoms
of the element i in the molecule. The expansion of this polynomial expression after
inserting the pix and mix values for all the isotopes 1, 2, 3, … of the elements i, j, …
of a given molecule yields an expression that represents the isotope distribution:

   w0 Α0 + wr Αr + ws Αs + wt Αt + …

where the values of w0, wr, ws, wt, … are the relative abundances of M+·, [M + r]+·,
[M + s]+·, [M + t]+·,… , respectively. The use of Α(mix - mi1) allows to determine the
values of r, s, t,… simply by expanding the general polynomial. A numerical value
for A, which has no intrinsic meaning, is never needed.
   For example, for CBr2Cl2, the above equation gives rise to the following
expression:

   {p12 Α0 + p13 Α(m13C - m12C ) } ×
       C             C
                 0
      {p79      Α + p81         Α(m81Br - m79Br ) }2 ×
           Br              Br
      {p35      Α0 + p37        Α(m37Cl - m35Cl) }2
           Cl            Cl

For sufficient resolution, (mix - mi1) and (mjx - mj1) differ from one another. This
results in very complex isotope patterns even for very small molecules. Thus, owing
to the occurrence of 12C, 13C, 79Br, 81Br, 35Cl, and 37Cl, there are 18 signals for
CBr2Cl2. However, the limited resolution of many real life experiments can make
many pairs of (mix - mi1) and (mjx - mj1) indistinguishable within experimental error,
thereby reducing the number of separate peaks. For example, at unit resolution, one
obtains (m13C - m12C) = 1 and (m81Br - m79Br) = (m37Cl - m35Cl) = 2. Consequently,
the expression for CBr2Cl2 becomes:
28          2 Summary Tables

     {p12 Α0 + p13 Α1 } × {p79        Α0 + p81 Α2 }2 × {p35 Α0             + p37     Α2 }2 =
           C           C           Br         Br           Cl                   Cl
               2      2       0
     {   p12 p79 p35 } Α +
             C   Br     Cl

          { p13 p79 p25 } Α1 +
                 2
               C    Br 3 Cl

     {   p12 p79 p81 p25 + p12 p29 p35 p37 } Α2 +
             C   Br     Br 3 Cl     C 7 Br     Cl    Cl

          { p13 p79 p81 p35 + p13 p79 p35 p37 } Α3 +
                              2          2
               C    Br     Br   Cl     C   Br     Cl    Cl

     { p12 p21      p2    + 4 p12 p79 p81 p35 p37 + p12 p29 p27 } Α4 +
           C8    Br 35Cl         C    Br     Br    Cl    Cl      C 7 Br 3 Cl

          { p13 p81 p35 + 4 p13 p79 p81 p35 p37 + p13 p29 p27 } Α5
                  2    2
                                                                                               +
               C    Br    Cl       C     Br     Br    Cl    Cl     C 7 Br 3 Cl
                           2            2                      6
     {   p12 p79 p81 p37 + p12 p81 p35 p37 } Α +
             C   Br    Br    Cl      C    Br     Cl    Cl

         { p13 p79  p    p2          + p13 p21        p35 p37     } Α7 +
              C   Br 81Br 37Cl           C  8    Br     Cl   Cl

     {   p12 p21 p27 } Α8 +
            C 8 Br 3 Cl

         { p13 p21        p27 } Α9
               C8    Br    3Cl

This shows that at unit resolution, CBr2Cl2 gives rise to only 10 peaks (M+·,
[M+1]+·, [M+2]+·, ... [M+9]+·) rather than 18 peaks, as they would be expected for
very high resolution. Moreover, the contribution of isotopes of low abundance can
often be neglected without sacrificing much precision. For example, the effect of
2H on isotope patterns is usually insignificant. Also, 13C is often negligible when
focussing on peaks of the series [M+2n]+·, which then results in patterns that are
characteristic for halogens, sulfur, and silicon. In large molecules, however, iso-
topes of low abundance cannot be neglected. For example, in the case of buckmin-
ster fullerene (C60), not only M+· (relative intensity, 100%) and [M+1]+· (64.80%),
but also [M+2]+· (20.65%), [M+3]+· (4.31%), and even [M+4]+· (0.66%) are quite
significant ions.
   With the above algorithm, typical isotope patterns can be readily calculated man-
ually by applying the general equation and neglecting isotopes of low abundance.
The outlined procedure can also be easily implemented and evaluated with generic
computer software that allows simple calculations. Dedicated and user-friendly pro-
grams that already contain the necessary isotope abundances and masses are avail-
able. Incidentally, because the use of the above equation for systems with 1000 or
more polyisotopic atoms results in excessive calculation times, more efficient but
somewhat more complicated algorithms have been developed for implementation in
dedicated programs [4]. Typical isotope patterns are given on the following pages.
                                       2.5 Mass Spectrometry         29

2.5.5 Isotopic Abundances of Various Combinations of Chlorine, Bro-
mine, Sulfur, and Silicon

Ele-    Mass   Relative Ele-    Mass   Relative Ele-    Mass   Relative
ments          abun-    ments          abun-    ments          abun-
               dance                   dance                   dance
  Cl1    35    100       Br1     79    100       S1      32    100
         37     31.96            81     97.28            33      0.80
                                                         34      4.52
  Cl2    70    100       Br2    158     51.40
         72     63.92           160    100       S2      64    100
         74     10.21           162     48.64            65      1.60
                                                         66      9.05
  Cl3   105    100       Br3    237     34.27            68      0.20
        107     95.88           239    100
        109     30.64           241     97.28    S3      96    100
        111      3.26           243     31.54            97      2.40
                                                         98     13.58
  Cl4   140     78.22    Br4    316     17.61            99      0.22
        142    100              318     68.53           100      0.61
        144     47.94           320    100
        146     10.21           322     64.85    S4     128    100
        148      0.82           324     15.77           129      3.20
                                                        130     18.12
  Cl5   175     62.53    Br5    395     10.57           131      0.43
        177    100              397     51.40           132      1.23
        179     63.92           399    100
        181     20.43           401     97.28    S5     160    100
        183      3.26           403     47.32           161      4.00
        185      0.21           405      9.21           162     22.66
                                                        163      0.72
  Cl6   210     52.15    Br6    474      5.43           164      2.05
        212    100              476     31.70           166      0.09
        214     79.90           478     77.10
        216     34.05           480    100
        218      8.16           482     72.96
        220      1.04           484     28.39
        222      0.06           486      4.60
30         2 Summary Tables

Ele-        Mass   Relative Ele-     Mass   Relative Ele-     Mass   Relative
ments              abun-    ments           abun-    ments           abun-
                   dance                    dance                    dance
     Si1     28    100       Si2      56    100       Si3      84    100
             29      5.08             57     10.15             85     15.23
             30      3.35             58      6.95             86     10.82
                                      59      0.34             87      1.03
                                      60      0.11             88      0.36

Cl1Br1      114     77.38 Cl1Br2     193     44.14 Cl1Br3     272     26.51
            116    100               195    100               274     85.85
            118     24.06            197     69.23            276    100
                                     199     13.35            278     48.46
                                                              280      7.80

Cl1Br4      351     14.45   Cl2Br1   149     62.03   Cl2Br2   228     38.69
            353     60.84            151    100               230    100
            355    100               153     44.91            232     88.68
            357     79.42            155      6.16            234     31.09
            359     29.94                                     236      3.74
            361      4.14

Cl3Br1      184     51.77   Cl3Br2   263     32.07   Cl4Br1   219     44.42
            186    100               265     93.14            221    100
            188     64.15            267    100               223     82.47
            190     17.12            269     49.27            225     32.28
            192      1.64            271     11.34            227      6.11
                                     273      0.99            229      0.45

Cl1S1        67    100      Cl1S2     99    100      Cl2S1    102    100
             68      0.80            100      1.60            103      0.80
             69     36.48            101     41.01            104     68.44
             70      0.26            102      0.58            105      0.51
             71      1.44            103      3.10            106     13.10
                                                              108      0.46
                                              2.5 Mass Spectrometry                  31

Ele-        Mass   Relative Ele-       Mass   Relative Ele-        Mass     Relative
ments              abun-    ments             abun-    ments                abun-
                   dance                      dance                         dance
Cl1Si1        63   100      Cl2Si1       98   100       Cl3Si1       133    100
              64     5.08                99     5.08                 134      5.08
              65    35.31               100    67.27                 135     99.23
              66     1.62               101     3.25                 136      4.87
              67     1.07               102    12.35                 137     33.85
                                        103     0.52                 138      1.56
                                        104     0.34                 139      4.29


2.5.6 Isotope Patterns of Combinations of Cl and Br

The signals are separated by 2 mass units. The mass for the most abundant
signal is shown under the symbol of the element. The combination of the
lightest isotopes is given on the left side of the x axis. See Chapter 2.5.5 for
exact abundances of many of these combinations.
 Signals            Br          Br2            Br3         Br4              Br5
 separated          79          160            239         320              399
 by 2 units

      Cl            ClBr        ClBr2          ClBr3       ClBr4            ClBr5
      35            116         195            276         355              436


      Cl2           Cl2Br       Cl2Br2         Cl2Br3       Cl2Br4          Cl2Br5
      70            151          230            311          390             471


      Cl3           Cl3Br       Cl3Br2         Cl3Br3      Cl3Br4
      105           186          267            346         427


      Cl4           Cl4Br       Cl4Br2         Cl4Br3      Cl4Br4
      142           221          302            381         462


      Cl5           Cl5Br       Cl5Br2         Cl5Br3
      177           256          337            418



      Cl6           Cl9         Cl12                        Br6       Br9
      212           319         426                         480       718
32      2 Summary Tables

2.5.7 Indicators of the Presence of Heteroatoms

In low-resolution mass spectra, one often observes characteristic isotope patterns,
specific masses of fragment ions, and characteristic mass differences (Δm) between
the molecular ion (M+·) and fragment ions (frag+) or between fragment ions. High
resolution mass spectra can be used to confirm the elemental composition provided
that the resolution is sufficient to discriminate alternative compositions. Moreover,
tandem mass spectrometry (also called MS/MS) may be used to identify character-
istic losses of heteroatoms from parent or fragment ions:

Indication of O: Δm 17 from M+·, in N-free compounds
                 Δm 18 from M+·
                 Δm 18 from frag+, particularly in aliphatic compounds
                 Δm 28, 29 from M+· for aromatic compounds
                 Δm 28 from frag+ for aromatic compounds
                 m/z 15, relatively abundant
                 m/z 19
                 m/z 31, 45, 59, 73, … + (14)n
                 m/z 32, 46, 60, 74, … + (14)n
                 m/z 33, 47, 61, 75, … + (14)n for 2 × O, in absence of S
                 m/z 69 for aromatic compounds meta-disubstituted by O

Indication of N: M+· odd-numbered (indicates odd number of N in M+·)
                 Large number of even-numbered fragment ions
                 Δm 17 from M+· or frag+, in O-free compounds
                 Δm 27 from M+· or frag+, for aromatic compounds or nitriles
                 Δm 30, 46 for nitro compounds
                 m/z 30, 44, 58, 72, … + (14)n for aliphatic compounds

Indication of S: Isotope peak [M+2]+· ≥ 5% of M+·
                 Δm 33, 34, 47, 48, 64, 65 from M+·
                 Δm 34, 48, 64 from frag+
                 m/z 33, 34, 35
                 m/z 45 in O-free compounds
                 m/z 47, 61, 75, 89, … + (14)n unless compound with 2 × O
                 m/z 48, 64 for S-oxides

Indication of F: Δm 19, 20, 50 from M+·
                 Δm 20 from frag+
                 m/z 20
                 m/z 57 without m/z 55 in aromatics
                                              2.5 Mass Spectrometry               33

Indication of Cl: Isotope peak [M+2]+· ≥ 33% of M+·
                  Δm 35, 36 from M+·
                  Δm 36 from frag+
                  m/z 35/37, 36/38, 49/51

Indication of Br: Isotope peak [M+2]+· ≥ 98% of M+·
                  Δm 79, 80 from M+·
                  Δm 80 from frag+
                  m/z 79/81, 80/82

Indication of I:   Isotope peak [M+1]+ of very low abundance at relatively high
                   mass
                   Δm 127 from M+·
                   Δm 127, 128 from frag+
                   m/z 127, 128, 254

Indication of P: m/z 47 in compounds without S or 2 × O
                 m/z 99 without isotope peak at m/z 100 in alkyl phosphates
34      2 Summary Tables

2.5.8 Rules for Determining the Relative Molecular Weight (Mr)

The molecular ion (M+·) is defined as the ion that comprises the most abundant
isotopes of the elements in the molecule. Interestingly, the lightest isotopes of most
elements frequently occurring in organic compounds and their common salts (H, C,
N, O, F, Si, P, S, Cl, As, Br, I, Na, Mg, Al, K, Ca, Rb, Cs) are also the most abundant
ones. Notable exceptions are B, Li, Se, Sr, and Ba.
   M+· is always accompanied by isotope peaks. Their relative abundance depends
on the number and kind of the elements present and their natural isotopic distribution.
The abundance of [M+1]+· indicates the maximum number of carbon atoms (Cmax)
according to the following relationship:
              Cmax = 100 × intensity([M + 1]+·) / {1.1 × intensity(M+·)}
   [M + 2]+· and higher masses indicate the number and kind of elements that have
a relatively abundant heavier isotope (such as S, Si, Cl, Br). Note that, in analogy
to the calculation of Cmax, the ratio of the intensities of [M + 2]+· and M+· for a
compound with n silicon, o sulfur, p chlorine, or q bromine atoms can be approxi-
mated with quite high accuracy from n × 3.35%, o × 4.52%, p × 31.96%, or q ×
97.28%, respectively (see also Chapters 2.5.4 to 2.5.6).
   The mass of M+· is always an even number if the molecule contains only
elements for which the atomic mass and valence are both even- (C, O, S, Si) or both
odd-numbered (H, P, F, Cl, Br, I). In the presence of other elements (e.g., 14N) and
isotope labels (e.g., 13C, 2H), M+· becomes an odd number if they are present in an
odd number.
   The molecular ion can only form fragment ions of masses that differ from that
of M+· by chemically logical values (Δm). In this context, chemically illogical
differences are Δm = 3 (in the absence of Δm = 1) to Δm = 14, Δm = 21 (in the
absence of Δm = 1) to Δm = 24, Δm = 37, 38, and all Δm less than the mass of an
element of characteristic isotope pattern in cases where the same isotope pattern is
not retained in the fragment ion.
   M+· must contain all elements (and the maximum number of each) that are shown
to be present in the fragment ions.
   If ionization is performed by electron impact, M+· is the ion with the lowest
appearance potential.
   If a pure sample flows into the ion source through a molecular leak, M+· exhibits
the same effusion rate as can be determined from the fragment ions. The abundance
of M+· is proportional to the sample pressure in the ion source.
   For polar compounds, [M + H]+ is often observed in mass spectra obtained not
only with fast atom bombardment and atmospheric pressure chemical ionization but
also with electron impact ionization. In this latter case, the abundance of [M + H]+
changes in proportion to the square of the sample pressure in the ion source.
   In the absence of a signal for M+·, the relative molecular weight must have a
value that shows a logical and reasonable mass difference, Δm, to all the observed
fragment ions.
                                               2.5 Mass Spectrometry              35

2.5.9 Homologous Mass Series as Indications of Structural Type

Certain sequences of intensity maxima in the lower mass range and the masses of
unique signals are often characteristic of a particular compound type. The intensity
distribution of such ion series is in general smooth. Therefore, abrupt changes (max-
ima and minima) are of structural significance. The ion or ion series most indicative
of a particular compound type is set in italics.


Mass        Elemental          Compound types
values, m/z composition
12 + 14n     CnH2n-2           alkenes, monocycloalkanes, alkynes, dienes,
                               cycloalkenes, polycyclic alicyclics, cyclic alcohols
13 + 14n     CnH2n-1           alkanes, alkenes, monocycloalkanes, alkynes,
                               dienes, cycloalkenes, polycyclic alicyclics,
                               alcohols, alkyl ethers, cyclic alcohols, cyclo-
                               alkanones, aliphatic acids, esters, lactones, thiols,
                               sulfides, glycols, glycol ethers, alkyl chlorides
             CnH2n-3O          cycloalkanones
14 + 14n     CnH2n             alkanes, alkenes, monocycloalkanes, polycyclic
                               alicyclics, alcohols, alkyl ethers, thiols, sulfides,
                               alkyl chlorides
             CnH2n-2O          cycloalkanones
15 + 14n     CnH2n+1           alkanes, alkenes, monocycloalkanes, alkynes,
                               dienes, cycloalkenes, polycyclic alicyclics,
                               alkanones, alkanals, glycols, glycol ethers, alkyl
                               chlorides, acid chlorides
             CnH2n-1O          alkanones, alkanals, cyclic alcohols, acid chlorides
16 + 14n     CnH2nO            alkanones, alkanals
             CnH2n+2N          alkyl amines, aliphatic amides
             CnH2nNO           aliphatic amides
17 + 14n     CnH2n+1O          alcohols, alkyl ethers, aliphatic acids, esters,
                               lactones, glycols, glycol ethers
             CnH2n-1O2         aliphatic acids, esters, lactones
18 + 14n     CnH2nO2           aliphatic acids, esters, lactones
19 + 14n     CnH2n+3O          alcohols, alkyl ethers
             CnH2n+1O2         aliphatic acids, esters, lactones
             CnH2n+1O2         glycols, glycol ethers
             CnH2n+1S          thiols, sulfides
20 + 14n     C8H8 + CnH2n      alkylbenzenes
             CnH2n+2O2         glycols, glycol ethers
             CnH2n+2S          thiols, sulfides
36     2 Summary Tables

Mass         Elemental       Compound types
values m/z   composition
21 + 14n     C7H7 + CnH2n    alkylbenzenes
             C7H5O           aryl ketones
             CnH2nCl         alkyl chlorides
             CnH2nCOCl       acid chlorides
22 + 14n     C6H6N + CnH2n   alkylanilines
             CnH2n–6         polycyclic alicyclics
23 + 14n     CnH2n–5         polycyclic alicyclics
24 + 14n     CnH2n–4         polycyclic alicyclics
25 + 14n     CnH2n–3         alkynes, dienes, cycloalkenes, polycyclic
                             alicyclics
39, 52±1,    CnHn±1          alkylbenzenes, aromatic hydrocarbons, phenols,
 64±1, 76±2,                 aryl ethers, aryl ketones
 91±1
                                                2.5 Mass Spectrometry            37

2.5.10 Mass Correlation Table

Note: As long as it makes sense chemically, CH2, CH4, CH3O, and O2 in the
formulae of the second column may be replaced by N, O, P, and S, respectively.

Mass Ion             Product ion              Substructure or compound type
                     (and neutral
                     particle lost)

1                    [M+1]+, [M-1]–           particularly in FAB spectra, in which
                                              M±1 occurs even for moderately
                                              basic and acidic compounds, but
                                              intensive M+· without M±1 is unusual
7      Li+·                                   in FAB spectra in the presence of Li+
                     [M+7]+
                                              (with isotope signal for 6Li)
                     [M-7]–                   in FAB spectra of organic Li+ salts
12     C+·
13     CH+
14     CH2+·, N+,
       N2++, CO++
15     CH3+       [M-15]+·            (CH3) nonspecific; abundant: methyl,
                                            N-ethylamines
16     O+·, NH2+,    [M-16]+·         (CH4) methyl (rare)
       O2++                             (O) nitro compounds, sulfones, epoxides,
                                            N-oxides
                                      (NH2) primary amines

17     OH+, NH3+· [M-17]+·             (OH) acids (especially aromatic acids),
                                             hydroxylamines, N-oxides, nitro com-
                                             pounds, sulfoxides, tertiary alcohols
                                      (NH3) primary amines
18     H2O+·,        [M-18]+·         (H2O) nonspecific; abundant: alcohols,
       NH4+                                  some acids, aldehydes, ketones, lac-
                                             tones, cyclic ethers      O indicator
19     H3O+, F+      [M-19]+             (F) fluoro compounds           F indicator
20     HF+·, Ar++,   [M-20]+·           (HF) fluoro compounds           F indicator
       CH2CN++
21     C2H2O++
22     CO2++
38    2 Summary Tables

Mass Ion            Product ion         Substructure or compound type
                    (and neutral
                     particle lost)

23   Na+            [M+23]+             in FAB spectra in the presence of
                                        Na+; sometimes strong even if Na+ is
                                        only an impurity
                    [M-23]–             in FAB spectra of organic Na+ salts
24   C2+·

25   C2H+           [M-25]+ (C2H)       terminal acetylenyl
26   C2H2+·, CN+    [M-26]+· (C2H2)     aromatics
                               (CN)     nitriles
27   C2H3  +,       [M-27] + (C H )     terminal vinyl, some ethyl esters and
                                2 3
     HCN+·                              N-ethylamides, ethyl phosphates
                   [M-27] +· (HCN) aromatic N, nitriles

28   C2H4+·, CO+·, [M-28]+· (C2H4) nonspecific; abundant: cyclohexenes,
     N2+·, HCNH+                        ethyl esters, propyl ketones, propyl-
                                        substituted aromatics
                                  (CO) aromatic O, quinones, lactones,
                                        lactams, unsaturated cyclic ketones,
                                        allyl aldehydes
                                   (N2) diazo compounds; air (intensity 3.7
                                        times larger than for O2+·, m/z 32)
29   C2H5  +, CHO+ [M-29]+ (C H ) nonspecific; abundant: ethyl
                                  2 5
                               (CHO) phenols, furans, aldehydes
30   CH2O+·,       [M-30]+· (C2H6) ethylalkanes, polymethyl compounds
     CH2NH2+,                (CH2O) cyclic ethers, lactones, primary
     NO+, C2H6+·,                       alcohols
     BF+·, N2H2+·                (NO) nitro and nitroso compounds
                                                                  N indicator
31   CH3O+,        [M-31]+ (CH3O) methyl esters, methyl ethers, primary
     CH3NH2+·,                          alcohols                 O indicator
     CF+, N2H3+          (CH3NH2) N-methylamines
                              (N2H3) hydrazides
32   O2+·,         [M-32]+·       (O2) cyclic peroxides; air (intensity 3.7
     CH3OH+·,                           times smaller than for N2+·, m/z 28)
     N2H4  +·, S+·
                           (CH3OH) methyl esters, methyl ethers
                                    (S) sulfides (with 34S isotope signal)
                                                                 O indicator
                                        2.5 Mass Spectrometry               39

Mass Ion          Product ion          Substructure or compound type
                  (and neutral
                   particle lost)

33   CH3OH2+,     [M-33]+      (SH)  nonspecific (with isotope signal for
     SH+, CH2F+                      34S)                      S indicator
                      (CH3 + H2O) nonspecific                  O indicator
                            (CH2F) fluoromethyl
34   SH2+·        [M-34] +·   (SH2) nonspecific (with 34S isotope signal)
                                                               S indicator
                         (OH + OH) nitro compounds
35   SH3+, Cl+    [M-35]+       (Cl) chloro compounds (with 37Cl isotope
                                     signal)
                        (OH + H2O) nitro compounds         2 × O indicator
36   HCl+·, C3+   [M-36] +·   (HCl) chloro compounds
                      (H2O + H2O)                          2 × O indicator
37   C3H+
     37Cl+                             chloro compounds (with isotope
                                       signal for 35Cl)
38   C3H2+·
39   C3H3+        [M-39]+     (C3H3)   aromatics
     K+           [M+39]+              in FAB spectra often strong even if
                                       K+ is only an impurity (with isotope
                                       signal for 41K)
                   [M-39]–             in FAB spectra of organic K+ salts
40   C3H4+·, Ar+·, [M-40]+·
     CH2CN+                 (CH2CN)    cyanomethyl
41   C3H5+,        [M-41]+ (C3H5)      alicyclics (especially polyalicyclics),
     CH3CN+·                           alkenes
                            (CH3CN)    2-methyl-N-aromatics, N-methyl-
                                       anilines
42   C3H6+·,      [M-42]+·    (C3H6)   nonspecific; abundant: propyl
     C2H2O+·,                          esters, butyl ketones, butylaromatics,
     CON+,                             methylcyclohexenes
     C2H4N+                  (C2H2O)   acetates (especially enol acetates),
                                       acetamides, cyclohexenones,
                                       a,b-unsaturated ketones
43   C3H7+,       [M-43]+ (C3H7)       nonspecific; abundant: propyl,
     C2H3O+,                           alicyclics, cycloalkanones,
     CONH+·                            cycloalkylamines, cycloalkanols,
                                       butylaromatics
                             (CH3CO)   methyl ketones, acetates, aromatic
                                       methyl ethers
40    2 Summary Tables

Mass Ion            Product ion         Substructure or compound type
                    (and neutral
                     particle lost)

44   CO2+·,        [M-44]+· (C3H8)     propylalkanes
     C2H6N  +,             (C2H6N)     N,N-dimethylamines, N-ethylamines
     C2H4O+·,              (C2H4O)     cycloalkanols, cyclic ethers,
     CS+·, C3H8+·,                     ethylene ketals, aliphatic aldehydes
     CH4Si+·                           (McLafferty rearrangement)
                             (CO2)     anhydrides, lactones, carboxylic
                                       acids
45   C2H5O   +,      [M-45] + (C H O) ethyl esters, ethyl ethers, lactones,
                                 2 5
     C2H7N+·,                          ethyl sulfonates, ethyl sulfones
     CHS+ (with                (CHO2) carboxylic acids
     isotope signal           (C2H7N) N,N-dimethylamines, N-ethylamines
     for 34S)                                                     O indicator
                                                                   S indicator
46   C2H5OH+·,       [M-46]+· (C2H6O) ethyl esters, ethyl ethers, ethyl
     NO2+                              sulfonates
                       (H2O + C2H4) primary alcohols
                         (H2O + CO) carboxylic acids
                                 (NO2) nitro compounds
47   CH3S+, CCl+, [M-47]+ (CH3S) methyl sulfides (with isotope signal
     C2H5OH2+,                         for 34S)
     CH(OH)2    +,                                           2 × O indicator
     PO+                                                          S indicator
                                                                  P indicator
48   CH3SH+·,        [M-48]+· (CH4S) methyl sulfides
     SO+·, CHCl+·                 (SO) sulfoxides, sulfones, sulfonates (with
                                       isotope signal for 34S)
49   CH2Cl  +,       [M-49] + (CH Cl) chloromethyl (with 37Cl isotope
                                   2
     CH3SH2+                           signal)
     (with isotope
     signal for 34S)
50   C4H2+·,         [M-50]+· (CF2) trifluoromethylaromatics, perfluoro-
     CH3Cl  +·,                        alicyclics
     CF2+·
51   C4H3+,
     CHF2+
                                               2.5 Mass Spectrometry              41

Mass Ion           Product ion                Substructure or compound type
                   (and neutral
                    particle lost)

52   C4H4+·
53   C4H5+
54   C4H6+·,       [M-54]+·   (C4H6)          cyclohexenes
     C2H4CN+               (C2H4CN)           cyanoethyl
55   C4H7+,        [M-55]+    (C4H7)          nonspecific; abundant: alicyclics,
     C3H3O+                                   butyl esters, N-butylamides
56   C4H8+·,       [M-56]+·     (C4H8)        butyl esters, N-butylamides, pentyl
     C3H4O+·                                  ketones, cyclohexenes, tetralins,
                                              pentylaromatics
                              (C3H4O)         methylcyclohexenones, b-tetralones
57   C4H9+,        [M-57]+      (C4H9)        nonspecific
     C3H5O+,                  (C3H5O)         ethyl ketones
     C3H2F+
58   C3H8N+,       [M-58]+·    (C4H10)        alkanes
     C3H6O+·                  (C3H6O)         a-methylalkanals, methyl ketones,
                                              isopropylidene glycols N indicator
                                                                       O indicator
59   C3H7O+,       [M-59]+  (C3H7O)           propyl esters, propyl ethers
     C2H5NO+·              (C2H3O2)           methyl esters
                            (C3H9N)           amines, amides           O indicator
60   C2H4O2+·,     [M-60]+· (C3H8O)           propyl esters, propyl ethers
     CH2NO2+,              (C2H4O2)           acetates
     C2H6NO+ ,        (CH3OH + CO)            methyl esters            O indicator
     C2H4S+·                 (C2H4S)
61   C2H5O2+,      [M-61]+ (C2H5O2)           glycols, ethylene ketals
     C2H5S+                                                          2 × O indicator
                               (C2H5S)        ethyl sulfides (with 34S isotope
                                              signal)                    S indicator
62   C2H6O2+·,     [M-62]+· (C2H6O2)          methoxymethyl ethers, ethylene
     C2H3Cl+·                                 glycols, ethylene ketals
     C2H6S+·                   (C2H6S)        ethyl sulfides (with 34S isotope
                                              signal)
63   C5H3+,        [M-63]+ (C2H4Cl)           chloroethyl
     C2H4Cl+,              (CO + Cl)          carboxylic acid chlorides (with 37Cl
     COCl+                                    isotope signal)
64   C5H4+·,       [M-64]+·          (SO2)    sulfones, sulfonates
     SO2+·, S2+·                       (S2)   disulfides (with 34S isotope signal)
42    2 Summary Tables

Mass Ion        Product ion               Substructure or compound type
                (and neutral
                 particle lost)

65   C5H5+,     [M-65]+        (S2H)      disulfides
     H2PO2+                  (SO2H)
66   C5H6+·     [M-66]+·      (C5H6)      cyclopentenes
     S2H2+·                               disulfides (with 34S isotope signal)
67   C5H7+,     [M-67]+    (C4H3O)        furyl ketones
     C4H3O+
68   C5H8+·,    [M-68]+·     (C5H8)       cyclohexenes, tetralins
     C4H4O+·,              (C4H4O)        cyclohexenones, b-tetralones
     C3H6CN+
69   C5H9+,     [M-69]+      (C5H9)       alicyclics, alkenes
     C4H5O+,
     C3HO2+
     CF3+                         (CF3)   trifluoromethyl
70   C5H10+·                              alkanes, alkenes, alicyclics
     C4H6O+·                              cycloalkanones
     C4H8N+                               pyrrolidines
71   C5H11+                               alkanes, larger alkyl groups
     C4H7O+                               alkanones, alkanals, tetrahydrofurans
72   C4H8O+·                              alkanones, alkanals        O indicator
     C4H10N+                              aliphatic amines            N indicator
     C6+·                                 perhalogenated benzenes
73   C4H9O+                               alcohols, ethers, esters O indicator
     C3H5O2+                              carboxylic acids, esters, lactones
     C3H9Si+                              trimethylsilyl compounds
74   C4H10O+·                             ethers
     C3H6O2+·                             methyl esters of carboxylic acids,
                                          a-methyl carboxylic acids
75   C3H7O2+                              methyl acetals, glycols
                                                                 2 × O indicator
     C3H7S+                               sulfides, thiols (with 34S isotope
                                            signal)                   S indicator
     C2H7SiO+                             trimethylsilyloxyl compounds
76   C6H4+·                               aromatics
77   C6H5+                                aromatics
     C3H6Cl+                              chloro compounds (with 37Cl isotope
                                          signal)
                                      2.5 Mass Spectrometry             43

Mass Ion        Compound type
78   C6H6+·     aromatics
     C5H4N+     pyridines
     C3H7Cl+·   chloro compounds (with 37Cl isotope signal)
79   C6H7+      aromatics with H-containing substituents
     C5H5N+·    pyridines, pyrroles
     Br+        bromo compounds (with 81Br isotope signal)
80   C6H8+·     cyclohexenes, polycyclic alicyclics
     C5H4O+·    cyclopentenones
     HBr+·      bromo compounds (with 81Br isotope signal)
     C5H6N+     pyrroles, pyridines
81   C6H9+      cyclohexanes, cyclohexenyls, dienes
     C5H5O+     furans, pyrans
     81Br+      bromo compounds (with 79Br isotope signal)
82   C6H10+·    cyclohexanes
     C5H6O+·    cyclopentenones, dihydropyrans
     C5H8N+     tetrahydropyridines
     C4H6N2+·   pyrazoles, imidazoles
     CCl2+·     chloro compounds (with isotope signals at m/z 84 and 86)
83   C6H11+     alkenes, alicyclics, monosubstituted alkanes
     C5H7O+     cycloalkanones
84   C5H10N+    piperidines, N-methylpyrrolidines
85   C6H13+     alkanes
     C5H9O+     alkanones, alkanals, tetrahydropyrans, fatty acid deriva-
                tives
     CClF2+     chlorofluoroalkanes (with 37Cl isotope signal)
86   C5H10O+·   alkanones, alkanals
     C5H12N+    aliphatic amines                               N indicator
87   C5H11O+    alcohols, ethers, esters                       O indicator
     C4H7O2+    esters, carboxylic acids
88   C4H8O2+·   ethyl esters of carboxylic acids, a-methyl-methyl esters,
                a-C2-carboxylic acids
89   C4H9O2+    diols, glycol ethers                       2 × O indicator
     C4H9S+     sulfides (with 34S isotope signal)

90   C7H6+·     disubstituted aromatics
91   C7H7+      aromatics
     C4H8Cl+    alkyl chlorides (with 37Cl isotope signal)
44    2 Summary Tables

Mass Ion           Compound type
92    C7H8+·       alkylbenzenes
      C6H6N+       alkylpyridines
93    C6H5O+       phenols, phenol derivatives
      C6H7N+·      anilines
      CH2Br+       bromo compounds (with 81Br isotope signal)
94    C6H6O+·      phenol esters, phenol ethers
      C5H4NO+      pyrryl ketones, pyridone derivatives
95    C5H3O2+      furyl ketones
96    C7H12+·      alicyclics
97    C7H13+       alicyclics, alkenes
      C6H9O+       cycloalkanones
      C5H5S+       alkylthiophenes (with 34S isotope signal)
98    C6H12N+      N-alkylpiperidines
99    C7H15+       alkanes
      C6H11O+      alkanones
      C5H7O2+      ethylene ketals
      H4PO4+       alkyl phosphates
104   C8H8+·       tetralin derivatives, phenylethyl derivatives
      C7H4O+·      disubstituted a-ketobenzenes
105   C8H9+        alkylaromatics
      C7H5O+       benzoyl derivatives
      C6H5N2+      diazophenyl derivatives
106   C7H8N+       alkylanilines
111   C5H3OS+      thiophenoyl derivatives (with 34S isotope signal)
115   C9H7+        aromatics
      C6H11O2+     esters
      C5H7O3+      diesters
119   C9H11+       alkylaromatics
      C8H7O+       tolyl ketones
      C2F5+        perfluoroethyl derivatives
      C7H5NO+·     phenyl carbamates
120   C7H4O2+·     g-benzopyrones, salicylic acid derivatives
      C8H10N+      pyridines, anilines
121   C8H9O+ and   hydroxybenzene derivatives
      C7H5O2+
                                              2.5 Mass Spectrometry              45

Mass Ion               Compound type
127    C10H7+          naphthalenes
       C6H7O3+         unsaturated diesters
       C6H6NCl+·       chlorinated N-aromatics (with 37Cl isotope signal)
       I+              iodo compounds
128    C10H8+·         naphthalenes
       C6H5OCl+·       chlorinated hydroxybenzene derivatives (with 37Cl
                       isotope signal)
       HI+·            iodo compounds
130    C9H8N+          quinolines, indoles
       C9H6O+·         naphthoquinones
131    C10H11+         tetralins
       C5H7S2+         thioethylene ketals (with 34S isotope signal)
       C3F5+           perfluoroalkyl derivatives
135    C4H8Br+         alkyl bromides (with 81Br isotope signal at m/z 137)
141    C11H9+          naphthalenes
142    C10H8N+         quinolines
149    C8H5O3+         phthalates
152    C12H8+·         diphenyl aromatics
165    C13H9+          diphenylmethane derivatives (fluorenyl cation)
167    C8H7O4+         phthalates
205    C12H13O3+       phthalates
223    C12H15O4+       phthalates

2.5.11 References

[1] M.E. Wieser, Atomic weights of the elements 2005, J. Phys. Chem. Ref. Data
    2007, 36, 485.
[2] G. Audi, A.H. Wapstra, The AME2003 atomic mass evaluation, (II). Tables,
    graphs and references, Nucl. Phys. A 2003, 729, 337.
[3] J.K. Böhlke, J.R. de Laeter, P. De Bièvre, H. Hidaka, H.S. Peiser, K.J.R.
    Rosman, P.P.D. Taylor, Isotopic compositions of the elements, 2001, J. Phys.
    Chem. Ref. Data 2005, 34, 57.
[4] H. Kubinyi, Calculation of isotope distributions in mass spectrometry. A trivial
    solution for a non-trivial problem, Anal. Chim. Acta 1991, 247, 107.
46      2 Summary Tables

2.6 UV/Vis Spectroscopy

UV/Vis Absorption Bands of Various Compound Types (Α: alkyl or H; R:
alkyl; sh: shoulder)
Compound Type Transition (log ε)   200   300   400   500   600    700 nm

              π→π    (3–4)

              n→σ    (3.6)

              n→σ    (2.4)

              π→π    (3.7–4)

              n→σ    (2.5)

              n→σ    (3.5)
              π→π    (3–4)
              n→π    (1–2)
              π→π    (2)
              n→π    (0.9–1.4)

              n→σ    (3.5)
              n→σ    (3.2)
              n→σ    (2.2 sh)
              n→σ    (3–3.6)
              n→σ    (2–3 sh)
              n→σ    (3–4)
              n→σ    (2.6)

              n→σ    (2.5)

              n→π    (1.7)

              n→π    (1.7)

              n→π    (1.8)
              π→π    (≈4)
              n→π    (1–2)


             π→π     (3.9–4.4)


              π→π    (4.2–4.8)


               π→π    (4.3–5.2)

                                   200   300   400   500   600    700 nm
                                                        2.6 UV/Vis Spectroscopy                47

Compound Type Transition (log ε)          200          300        400       500      600   700 nm
  R
        O       n→π* (1.7)
 Cl
                                   a
                         (4 – 5)
               n=0–4

 R I            n→σ* (2.6)
                (2.0)
 R NO
                (1.3)
                                    a
                        (2.4–4.1)
            n=0–4
                                                             n→π* (conjugated systems)

                                                n→π*

                                                 π→π* (conjugated systems)

                                          π→π*

                                          n→σ*

                                       σ→σ*

a longest   wavelength absorption maximum300
                                   200                            400       500      600   700 nm
      3 Combination Tables




      3.1 Alkanes, Cycloalkanes

       Assignment    Range           Comments
13C    CH3            5–35 ppm       CH3, CH2, CH, and C can be differentiated
       CH2            5–45 ppm        by multipulse experiments (DEPT, APT),
       CH            25–60 ppm        off-resonance decoupling, 2D CH correla-
       C             30–60 ppm        tion spectra, or based on relaxation times
                                     Lower shift values in three-membered rings
1H     CH3           0.8–1.2 ppm
       CH2           1.1–1.8 ppm     Lower shift values in three-membered rings
       CH            1.1–1.8 ppm
       CH st         3000–2840 cm-1 Higher frequency in three-membered rings
IR     CH3 δ as          ≈1460 cm-1
       CH2 δ             ≈1460 cm-1
       CH3 δ sy          ≈1380 cm-1 Doublet for geminal methyl groups
       CH2 γ           770–720 cm-1 In C–(CH2)n–C with n ≥ 4 at ca. 720 cm-1
MS     Molecular ion m/z 14n + 2     Weak in n-alkanes
                                     Very weak in isoalkanes
       Fragments                     n-Alkanes: local maxima at 14n + 1, intensity
                                       variations: smooth, minimum at [M-15]+
                                     Isoalkanes: local maxima at 14n + 1, intensity
                                       distribution: irregular (relative maxima due
                                       to fragmentation at branching points with
                                       charge retention at the most highly substi-
                                       tuted C)
       Rearrange-                    n-Alkanes: unspecific
       ments         m/z 14n         Isoalkanes: elimination of alkenes
                     m/z 14n - 2     Monocycloalkanes: elimination of alkanes
UV                                   No absorption above 200 nm
      50      3 Combination Tables

      3.2 Alkenes, Cycloalkenes

      Assignment         Range              Comments
13C   C=C                100–150 ppm        Considerable differences between Z and E:
      C–(C=C)              10–60 ppm           C      X                    C          H

                                                          H                           X

1H    H–(C=C)             4.5–6.5 ppm       Coupling constants, |Jgem| 0–3 Hz
                                                                     Jcis 5–12 Hz
                                                                     Jtrans 12–18 Hz
      CH3–(C=C)              ≈1.7 ppm       Coupling constants, 3JCH3–CH=C ≈ 7 Hz
      CH2–(C=C)              ≈2.0 ppm                                3JCH –CH=C ≈ 7 Hz
                                                                           2
                                            In rings, |J| smaller:       H
                                                                              n = 2, 3J ≈ 0.5 Hz
                                                                              n = 3, 3J ≈ 1.5 Hz
                                                                   H

                                                                   H
                                                                         C
                                                                              n = 4, 3J ≈ 4.0 Hz
                                                                                      n
                                            Long-range coupling, 4JHC–C=CH 0–2 Hz

IR    H–C(=C) st   3100–3000 cm-1
      C=C st       1690–1635 cm-1 Of variable intensity
      H–C(=C) δ oop 1000–675 cm-1
      CH2–(C=C) δ       1440 cm-1

MS Molecular ion          m/z 14n
                          m/z 14n - 2
                                            Alkenes: moderate intensity
                                            Monocycloalkenes: medium intensity
      Fragments           m/z 14n - 1       Local maxima for alkenes
                          m/z 14n - 3       Local maxima for monocyclic alkenes
                                            Usually, double bonds cannot be localized
      Rearrange-                            n-Alkenes: unspecific except for:
      ments                                                           +.                                       +.
                                                    R H                                                R
                                               R                  X                                R       H
                                                                           - X C H =CH 2


                                               R                                                   R

                                            Cyclohexenes: retro-Diels–Alder reaction:
                                                          +   .                            +   .
                                                                                  +




UV    C=C π      π*      < 210 nm
                          (log ε 3–4)
                                            Isolated double bonds; for highly substituted
                                              double bonds often absorption tail
      (C=C)2 π        π* 215–280 nm
                          (log ε 3.5–4.5)
                                                                3.3 Alkynes             51

      3.3 Alkynes

      Assignment      Range             Comments
13C   C–C
       –
       –              65–85 ppm         Coupling constant 2JHC – 13C ≈50 Hz; often
                                                               –
                                                               –
                                         leading to unexpected signs of signals in
                                         DEPT spectra and unexpected signals in 2D
                                         heteronuclear correlation spectra
           –
      C–(C – C)
           –            0–30 ppm
1H         –
      H–(C – C)
           –          1.5–3.0 ppm       Coupling constants, |4JCH–C – CH| ≈3 Hz
                                                                    –
                                                                    –
                                                            |5JCH–C – C–CH| ≈3 Hz
                                                                    –
                                                                    –
                –
      CH3–(C – C)
                –        ≈1.8 ppm
                –
      CH2–(C – C)
                –        ≈2.2 ppm
               –
      CH–(C – C)
               –         ≈2.6 ppm

IR    H–C(– C) st
            –
            –         3340–3250 cm-1 Sharp, intensive
        –
      C – C st
        –             2260–2100 cm-1 Sometimes very week
MS    Molecular ion                     Weak, in the case of 1-alkynes up to C7 often
                                          absent
      Fragments                         [M-1]+ often significant
      Rearrange-                        Extensive rearrangements, not very character-
      ments                              istic
      C – C π π*
        –
        –             < 210 nm          Isolated double bonds; for highly substituted
UV                    (log ε 3.7–4.0)     double bonds often absorption tail
      52       3 Combination Tables

      3.4 Aromatic Hydrocarbons

      Assignment     Range                 Comments
13C   ar C           120–150 ppm           Same ranges for polycyclic aromatic hydro-
      ar CH          110–130 ppm             carbons
      al C–C ar        10–60 ppm
1H    H–C ar          6.5–7.5 ppm          In polycyclic aromatic hydrocarbons up to ≈9
                                           ppm
                                           Coupling constants, 3Jortho ≈7 Hz
                                                               4J
                                                                  meta ≈2 Hz
                                                               5J
                                                                  para <1 Hz
      CH3–C ar          ≈2.3 ppm           Often line broadening due to long-range cou-
      CH2–C ar          ≈2.6 ppm             pling with aromatic protons
      CH–C ar           ≈2.9 ppm
IR    ar C–H st      3080–3030 cm-1        Often multiple bands, weak
      comb           2000–1650 cm-1        Very weak
      ar C–C st          ≈1600 cm-1
                                           Of variable intensity, sometimes not all bands
                         ≈1500 cm-1
                                            observable
                         ≈1450 cm-1
      ar C–H δ oop     960–650 cm-1        Strong, frequently multiple bands
MS    Molecular ion                   Strong, often base peak
      Fragments     m/z 39, 50–53,    Often doubly charged fragment ions
                    63–65, 75–78,
                    [M-26]+·, [M-39]+

                     Benzylic cleavage                CH 1-3             m/z 91 (90, 92)
                     Other typical frag-
                      ments                                              m/z 127
                                                                    +.
                                                                         m/z 152


                                                                         m/z 165
                                                  +


      Rearrange-                                               +.                               +.
      ments                                    R H                                      R
                                           R            X                           R       H
                                                                    - X C H =CH 2


                                           R                                        R
                                                    3.5 Heteroaromatics            53

      Assignment     Range              Comments
UV                   ≈200–210 nm        In benzene and alkylbenzenes
                       (log ε ≈4)
                     ≈260 nm (log ε ≈2.4)



      3.5 Heteroaromatic Compounds

      Assignment     Range              Comments
13C   ar C–X         120–160 ppm
      ar C–C         100–150 ppm
1H    H–C ar             6–9 ppm        Coupling constants in 6-membered rings
                                          similar to those in aromatic hydrocarbons;
                                          smaller in 5-membered rings
      H–N ar            7–14 ppm        Strongly solvent dependent, generally broad

IR    ar C–H st      3100–3000 cm-1     Often multiple bands, weak
      ar N–H st      3500–2800 cm-1
      ar C–C st          ≈1600 cm-1
                                        Often split, sometimes not all bands observ-
                         ≈1500 cm-1
                                         able
                         ≈1450 cm-1
      ar C–H δ oop    1000–650 cm-1     Often strong, frequently multiple bands
MS    Molecular ion                     Strong, often base peak
      Fragments     m/z 39, 50–53,
                    63–65, 75–78,       Often doubly charged fragment ions
                    [M-26]+·, [M-39]+
                    m/z 45 [CHS]+       S-Heteroaromatics
                    Benzyl-analogous
                    cleavage
      Rearrange-                         Loss of HCN (Δm 27, N-heteroaromatics)
      ments                              Loss of CO (Δm 28, O-heteroaromatics)
                                         Loss of CS (Δm 44, S-heteroaromatics)
UV                                      cf. UV/Vis Reference Spectra, Chapter 8.5.3
      54        3 Combination Tables

      3.6 Halogen Compounds

      Assignment     Range             Comments
13C   al C–F           70–100 ppm      CF3: ≈115 ppm
      (C)=C–F         125–175 ppm      Coupling, with 19F (isotope abundance,
      C=(C–F)          65–115 ppm       100%; I = 1/2): |1JCF| 100–300 Hz
      ar C–F          140–165 ppm                        |2JCF| 10–40 Hz
      ar C–(C–F)      105–135 ppm                        |3JCF| 5–10 Hz
                                                         |4JCF| 0–5 Hz
      al C–Cl            30–60 ppm
      (C)=C–Cl         100–150 ppm
      C=(C–Cl)         100–155 ppm
      ar C–Cl          120–150 ppm
      ar C–(C–Cl)      125–135 ppm
      al C–Br            10–45 ppm
      (C)=C–Br          90–140 ppm
      C=(C–Br)          90–140 ppm
      ar C–Br          110–140 ppm
      ar C–(C–Br)      125–135 ppm
      al C–I         -20 to +30 ppm
      (C)=C–I           60–110 ppm
      C=(C–I)          120–150 ppm
      ar C–I            85–115 ppm
      ar C–(C–I)       125–145 ppm
1H    CH2–F               ≈4.3 ppm     Coupling, with 19F (isotope abundance,
                                        100%; I = 1/2): |2JHF| 40–80 Hz
                                                         |3JHF| 0–50 Hz
                                                         |4JCF| 0–5 Hz
      CH2–Cl              ≈3.5 ppm
      CH2–Br              ≈3.4 ppm
      CH2–I               ≈3.1 ppm
      H–CX=C            5.5–8.0 ppm    Similar shifts for all halogens
      H–C=CF            4.0–6.0 ppm
      H–C=CCl           4.5–6.5 ppm
      H–C=CBr           5.0–7.0 ppm
      H–C=CI            5.5–7.5 ppm
      H–phenyl–hal      7.0–7.6 ppm    Shielding by F in ortho and para positions;
                                         small effects for Cl and Br; deshielding by
                                         I in ortho, and shielding in meta position
      C–F st          1400–1000 cm-1   Strong
IR    C–Cl st           850–600 cm-1   Strong
      C–Br st           700–500 cm-1   Strong
      C–I st            650–450 cm-1   Strong
                                          3.6 Halogen Compounds              55

     Assignment    Range          Comments
MS   Molecular ion                Often weak for saturated aliphatic halogen
                                   compounds, often absent from spectra of
                                   aliphatic polyhalogenated compounds
                                  Characteristic isotope pattern for Cl and Br
     Fragments    m/z 69, 50–53   CF3
                                  Upon fragmentation of the C–hal bond, the
                                   positive charge preferably remains on the
                                   alkyl side, and on the halogen side upon
                                   fragmentation of the neighboring bond:

                                  R   C   hal   >   R   C   hal



     Rearrange-   [M-20]+·        HF elimination
     ments        [M-50]+· or     CF2 elimination
                  [frag-50]+
                  [M-36]+·        HCl elimination
UV   hal n   π*   ≤280 nm         For C–I; for C–Br and C–Cl in general only
                  (log ε ≈2.5)      absorption tail, for C–F no absorption
     56       3 Combination Tables

     3.7 Oxygen Compounds

     3.7.1 Alcohols and Phenols

     Assignment   Range                Comments
13C al C–OH         50–80 ppm          Shift with respect to C–H ≈50 ppm
     al C–(C–OH)    10–60 ppm          Hardly any shift with respect to C–(C–CH3)
     al C–(C–C–OH) 10–60 ppm           Shift with respect to C–(C–C–CH3) ≈-5 ppm
     ar C–OH        140–155 ppm        Shift with respect to C–H ≈+25 ppm
     ar C–(C–OH)    100–130 ppm        Shift with respect to C–(C–H): ortho ≈-13
                                       ppm, meta ≈+1 ppm, para ≈-8 ppm
1H   HO–C al           0.5–6 ppm       Often broad; position and shape strongly
     HO–C ar            4–12 ppm        depend on experimental conditions
     CH2–(OH)        3.5–4.0 ppm
     CH–(OH)         3.8–4.2 ppm
     ar CH–(C–OH)    6.5–7.0 ppm       Shift with respect to CH–(C–H): ortho ≈-0.6
                                         ppm, meta ≈-0.1 ppm, para ≈-0.5 ppm

IR   O–H st         3650–3200 cm-1     Position and shape depend on the degree of
                                         association. Often different bands for H-
                                         bonded and free OH
     C–O(H) st       1260–970 cm-1     Strong
MS Molecular ion                      Aliphatic: weak, often missing in the case of
                                        primary and highly branched alcohols; in
                                        this case, peaks at highest mass are often
                                        due to [M-18]+· or [M-15]+
                                      Aromatic: strong
     Fragments      Aliphatic:        Primary: m/z 31 > m/z 45 ≈ m/z 59
                    m/z 31, 45, 59, … Secondary, tertiary: local maxima due to
                    [M-33]+            α-cleavage:       R           .
                                                                    +.          -R                +.
                                                      R       C     OH                    R   C   OH
                                                              H                               H

                    Aromatic:          CO and CHO elimination also from frag-
                    [M-28]+· (CO)        ments. H2O elimination ([M-18]+·) only
                    [M-29]+ (CHO)        with alkyl substituent in ortho position
     Rearrange-     Aliphatic:         Elimination of H2O from M+· followed by
     ments          [M-18]+·            alkene elimination; elimination of H2O
                    [M-46]+·            from products of α-cleavage
                    Unsaturated        Vinylcarbinols: spectra similar to those of
                                        ketones
                                       Allyl alcohols: specific aldehyde elimination:
                                                              +.                                  +.
                                                    OH
                                                                   - R 2C H O        R1
                                          R1
                                                         R2
                                                3.7 Oxygen Compounds                 57

     Assignment     Range             Comments
MS                  Aromatic:         Ortho effect with appropriate substituents:
                                                        +.              +.
                                                O                   O
                                                    H                            H
                                                                             +
                                                    Z                            Z
                                                Y                   Y

                                      with Y–Z as –CO–OR, C–hal, –O–R, and similar

UV Aliphatic
   Aromatic         ≈200–210 nm
                                     No absorption above 200 nm
                                     In alkaline solution, shift to longer wave-
                      (log ε ≈3.8)     length and increase in intensity due to
                    ≈270 nm            deprotonation
                      (log ε ≈2.4)

     3.7.2 Ethers

     Assignment   Range               Comments
13C al C–O          50–90 ppm         Oxiranes: outside the normal range
     al C–(C–O)     10–60 ppm         Hardly any shift with respect to C–(C–CH3)
     al C–(C–C–O)   10–60 ppm         Shift with respect to C–(C–C–CH3) ≈-5 ppm
     O–C–O         85–110 ppm
     (C)=C–O      115–165 ppm         Shift with respect to (C)=C–C ≈+15 ppm
     C=(C–O)       70–120 ppm         Shift with respect to C=(C–C) ≈-30 ppm
     ar C–O       140–155 ppm         Shift with respect to ar C–H ≈+25 ppm
     ar C–(C–O)   100–130 ppm         Shift with respect to ar C–(C–H):
                                                                  ortho ≈-15 ppm
                                                                  meta ≈+1 ppm
                                                                  para ≈-8 ppm
1H   CH3–O           3.3–4.0 ppm      Singlet
     CH2–O           3.4–4.2 ppm
     O–CH2–O         4.5–6.0 ppm
     CH–O            3.5–4.3 ppm
     CH(O)3            ≈ 5–6 ppm
     H–C(O)=C        5.7–7.5 ppm      Shift with respect to H–C(H)=C ≈+1.2 ppm
     H–C=C–O         3.5–5.0 ppm      Shift with respect to H–C(=C–H) ≈-1 ppm
     ar CH–C–O       6.6–7.6 ppm
IR   H–C(–O) st     2880–2815 cm-1    For CH3–O and CH2–O; similar range for
                                        corresponding amines
     H–CH(O)2 st    2880–2750 cm-1    Two bands
     C–O–C st       1310–1000 cm-1    Strong, sometimes two bands
     58     3 Combination Tables

     Assignment      Range             Comments
MS   Molecular ion                     Aliphatic: weak, tendency to protonate
                                       Aromatic: strong
     Fragments       Aliphatic:        Base peak of aliphatic ethers generally due to
                     m/z 31, 45, 59, … fragmentation of the bond next to the ether
                                                                         .
                     [M-33]+            bond:       R   C O R
                                                                 +.   -R        +
                                                                             C O R
                                                                                                    1
                                                             1                   2                                   2


                                           or due to heterolytic cleavage of the C–O
                                           bond (especially for polyethers):
                                                                                                    .
                                                                                     + . - R 1 –O
                                                                 R1    O    R2                          R2+


                     Alkyl aryl ethers    Preferential loss of the alkyl chain
                     Diaryl ethers        Preferential loss of CO (Δm 28) from M+·
                                            and/or [M-H]+ as well as:
                                                                                               ar1      O     ar2


     Rearrange-      Aliphatic:           Elimination of water or alcohol
     ments           [M-18]+·
                     [M-46]+·
                     Aromatic             Ethyl and higher alkyl ethers: alkene elimina-
                                           tion to the phenol:
                                                     H            +.                                                +.
                                                O                      - R C H =C H 2                       OH
                                                         R




UV Aliphatic
   Aromatic
                                         No absorption above 200 nm
                                         Shift to higher wavelength and increase in
                                           intensity due to the ether group
                                                3.8 Nitrogen Compounds                59

      3.8 Nitrogen Compounds

      3.8.1 Amines

      Assignment   Range                  Comments
13C   al C–N         25–70 ppm            Shift with respect to C–H ≈+20 ppm
      al C–(C–N)     10–60 ppm            Shift with respect to C–(C–CH3) ≈+2 ppm
      al C–(C–C–N)   10–60 ppm            Shift with respect to C–(C–C–CH3) ≈-2 ppm
      (C)=C–N          120–170 ppm        Shift with respect to (C)=C–C ≈+20 ppm
      C=(C–N)           75–125 ppm        Shift with respect to C=(C–C) ≈-25 ppm
      ar C–N           130–150 ppm        Shift with respect to C–H ≈+20 ppm
      ar C–(C–N)       100–130 ppm        Shift with respect to C–(C–H):
                                                                     ortho ≈-15 ppm
                                                                     meta ≈+1 ppm
                                                                     para ≈-10 ppm
1H    HN–C al           0.5–4.0 ppm
      HN–C ar           2.5–5.0 ppm
      HN+–C al or ar    6.0–9.0 ppm       Often broad
      CH3–N             2.3–3.1 ppm       Singlet
      CH2–N             2.5–3.5 ppm
      CH–N              3.0–3.7 ppm
      CH–N+             3.2–4.0 ppm
      ar CH–C–N         6.0–7.5 ppm       Shift with respect to CH–(C–H):
                                                                    ortho ≈-0.8 ppm
                                                                    meta ≈-0.2 ppm
                                                                    para ≈-0.7 ppm
      ar CH–C–N+        7.5–8.0 ppm       Shift with respect to CH–(C–H):
                                                                    ortho ≈+0.7 ppm
                                                                    meta ≈+0.4 ppm
                                                                    para ≈+0.3 ppm
IR    N–H st           3500–3200 cm-1     Position and shape depend on the degree
                                            of association. Often different bands for
                                            H-bonded and free NH. For NH2, always at
                                            least two bands
      N+–H st          3000–2000 cm-1     Broad, similar to COOH but more structured
      N–H δ            1650–1550 cm-1     Weak or absent
      N+–H   δ         1600–1460   cm-1   Often weak
      H–C(–N) st       2850–2750   cm-1   For CH3–N and CH2–N in amines; similar
                                            range for corresponding ethers
      60     3 Combination Tables

      Assignment      Range             Comments
MS    Molecular ion                     Odd nominal mass number for odd number
                                         of N atoms
                                        Aliphatic: weak, tendency to protonate,
                                         [M+H]+ is often important
                                        Aromatic: strong, no tendency to protonate
      Fragments       Aliphatic:        Base peak of aliphatic amines generally due
                      m/z 30, 44, 58, …  to fragmentation of the bond next to the
                                         amine bond:
                                                        R1
                                                                                 +.   - R3
                                                                                             .        R1
                                                                                                           +
                                                             N    CH 2     R3                              N   CH 2
                                                        R2                                            R2

      Rearrange-                           Elimination of alkenes following amine
      ments                                  cleavage:      R
                                                              +   1             +
                                                                      N   CH 2                   R1    NH      CH 2
                                                                 R2


UV Aliphatic
   Aromatic
                                           No absorption above 200 nm
                                           In acidic solutions, shift to lower wavelength
                                             and decrease in intensity


      3.8.2 Nitro Compounds

      Assignment   Range                    Comments
13C   al C–NO2      55–110 ppm              Shift with respect to C–H ≈+50 ppm
      al C–(C–NO2)   10–50 ppm              Shift with respect to C–(C–C) ≈-6 ppm
      al C–(C–CNO2) 10–60 ppm               Shift with respect to C–(C–C–C) ≈-2 ppm
      ar C–NO2     130–150 ppm              Shift with respect to C–H ≈+20 ppm
      ar C–(C–NO2) 120–140 ppm              Shift with respect to C–(C–H): ortho ≈-5
                                              ppm, meta ≈+1 ppm, para ≈+6 ppm
1H    al CH–NO2        4.2–4.6 ppm
      ar CH–C–NO2      7.5–8.5 ppm          Shift with respect to CH–(C–H): ortho ≈+1
                                              ppm, meta ≈+0.3 ppm, para ≈+0.4 ppm
IR    NO2 st as       1660–1490 cm-1        Strong to very strong
      NO2 st sy       1390–1260 cm-1        Strong to very strong
MS    Molecular ion                         Odd nominal mass number for odd number
                                              of N atoms
                                            Aliphatic: weak or absent
                                            Aromatic: strong
      Fragments       [M-16]+·, [M-46]+
      Rearrange-      m/z 30, [M-17]+,
      ments           [M-30]+, [M-47]+·
UV    Aliphatic
      Aromatic
                      ≈275 nm (log ε <2)
                      ≈350 nm (log ε ≈2)
                                                3.9 Thiols and Sulfides                         61

      3.9 Thiols and Sulfides

      Assignment   Range               Comments
13C   al C–S           5–60 ppm        No significant shift with respect to C–C
      ar C–S        120–140 ppm
1H    HS–C al        1.0–2.0 ppm       Vicinal coupling constant, J, 5–9 Hz
      HS–C ar        2.0–4.0 ppm
      al CH–S        2.0–3.2 ppm
      ar CH–S        7.0–7.5 ppm
IR S–H st           2600–2540 cm-1     Frequently weak
MS Molecular ion                       34S-isotopepeak at [M+2]+· ≈4.5%
                                     Aliphatic: intensity higher than for corre-
                                       sponding alcohols and ethers
      Fragments    m/z 47, 61, 75, … Sulfide cleavage:
                                                                      +.   - R2
                                                                                  .        +
                                                 R1   S   CH 2   R2                   R1   S   CH 2


      Rearrange-   m/z 34, 35, 48
      ments        [M-33]+             Alkene elimination after sulfide cleavage
                   [M-34]+·
UV    Aliphatic    <225 nm (log ε 3–4)
                   220–250 nm (log ε 2–3)
      62        3 Combination Tables

      3.10 Carbonyl Compounds

      3.10.1 Aldehydes

      Assignment   Range               Comments
13C   CHO           190–205 ppm        Coupling constant 1JCH 172 Hz
      al C–(CHO)      30–70 ppm        Coupling constant |2JCH| 20–50 Hz
      al C–(C–CHO)     5–50 ppm        Shift with respect to C–(C–CH3) ≈-10 ppm
      (C)=C–(CHO)   110–160 ppm
      C=(C–CHO)     110–160 ppm
      ar C–(CHO)    120–150 ppm
1H    H–(C=O)       9.0–10.5 ppm
      al CH–(CHO)    2.0–2.5 ppm       3J      0–3 Hz
                                            HH
      (CH)=CH(CHO) 5.5–7.0 ppm         3J
                                            HH ≈8 Hz
      CH=(CH–CHO) 5.5–7.0 ppm
      ar CH–(C–CHO) 7.2–8.0 ppm        Shift with respect to CH–(C–H):
                                                                ortho ≈+0.6 ppm
                                                                meta ≈+0.2 ppm
                                                                para ≈+0.3 ppm
IR    comb             2900–2700 cm-1 Two weak bands
      C=O              1765–1645 cm-1 Aliphatic: ≈1730 cm-1
                                      Conjugated: ≈1690 cm-1
MS Molecular ion                       Aliphatic: moderate
                                       Aromatic: strong
      Fragments       [M-1]+           For aliphatic aldehydes, only significant up
                                         to C7
                      [M-29]+
      Rearrange-      m/z 44           Aliphatic aldehydes
      ments           [M-44]+·                               +.                          +.
                                            R    H
                                                     O            - RCH =CH 2   OH

                                                         H                           H




UV    n    π*         270–310 nm (log ε ≈1) Saturated aldehydes
                      ≥207 nm (log ε ≈4)    α,β-Unsaturated aldehydes
                      ≥250 nm (log ε >3)    Aromatic aldehydes
                                                   3.10 Carbonyl Compounds                             63

      3.10.2 Ketones

      Assignment      Range               Comments
13C   C=O             195–220 ppm
      al C–(C=O)        25–70 ppm
      al C–(C–C=O)       5–50 ppm         Shift with respect to C–(C–CH3) ≈-6 ppm
      (C)=C–(C=O)     105–160 ppm
      C=(C–C=O)       105–160 ppm
      ar C–(C=O)      120–150 ppm
1H    al CH–(C=O)      2.0–3.6 ppm        al CH–C(=O)–C al 2.0–2.6 ppm
                                          al CH–C(=O)–C ar 2.5–3.6 ppm
      CH=CH–(C=O)      5.5–7.0 ppm
      ar CH–(C–C=O)    7.2–8.0 ppm        Shift with respect to CH–(C–H):
                                                                    ortho ≈+0.6 ppm
                                                                    meta ≈+0.1 ppm
                                                                    para ≈+0.2 ppm
      C=O st          1775–1650 cm-1      Aliphatic: ≈1715 cm-1
IR                                        Cyclic: ring size ≥6: ≈1715 cm-1
                                                   ring size <6: ≥1750 cm-1
                                          Conjugated: ≈1690–1665 cm-1

MS Molecular ion                          Aliphatic: moderate
                                          Aromatic: strong
      Fragments                           Ketone cleavages:
                                                                  +.
                                                         O


                                                    R1       R2         R 1 CO + , R 1 + , R 2 CO + , R 2 +




      Rearrange-      m/z 44              Aliphatic ketones
      ments           [M-44]+·
                                                   +.                            +.                    +.
                                 R1   H
                                          O          - R 1 CH=CH 2     OH                    O

                                              R2                            R2                   R2



      π   π*          <200 nm (log ε 3–4)           Saturated ketones
UV    n   π*          250–300 nm (log ε 1–2)        Saturated ketones
                      ≥215 nm (log ε ≈4)            α,β-Unsaturated ketones
                      ≥245 nm (log ε >3)            Aromatic ketones
     64        3 Combination Tables

     3.10.3 Carboxylic Acids

     Assignment        Range            Comments
13C COOH                170–185 ppm     For COO–, shift with respect to COOH: 0 to
                                          +8 ppm
     al C–(COOH)          25–70 ppm
     al C–(C–COOH)         5–50 ppm     Shift with respect to C–(C–CH3) ≈-6 ppm
     (C)=C–(COOH)       105–160 ppm
     C=(C–COOH)         105–160 ppm
     ar C–(COOH)        120–150 ppm
1H   COOH              10.0–13.0 ppm    Position and shape strongly depend on
                                          experimental conditions
     al CH–(COOH)        2.0–2.6 ppm
     CH=CH–(COOH)        5.2–7.5 ppm
     ar CH–(C–COOH)      7.2–8.0 ppm    Shift with respect to CH–(C–H):
                                          ortho ≈+0.8 ppm, meta ≈+0.2 ppm,
                                          para ≈+0.3 ppm
IR   COO–H st          3550–2500 cm-1 Broad
     C=O st            1800–1650 cm-1 Aliphatic: ≈1715 cm-1
                                      Conjugated: ≈1695 cm-1
                                      For COO–, two bands: 1580 and 1420 cm-1
     COO–H δ oop            ≈920 cm-1 For dimers

MS Molecular ion                        Aliphatic: moderate, strong for long chains,
                                          tendency to protonate
                                        Aromatic: strong
     Fragments         [M-17]+          Strong for aromatic acids
                       [M-45]+
     Rearrange-        m/z 60, 61       Aliphatic acids
     ments             [M-18]+·         Aromatic acids
                                        Ortho effect with aromatic acids:

                                             O        +.                     +.
                                                                         O
                                                                     C
                                                                                  for X : CH 2 ,
                                                 OH    - ROH                             O,
                                                 R                                       N,
                                             X                       X                   S, etc.


UV   n    π*           <220 nm (log ε 1–2)       Saturated acids
                       ≥193 nm (log ε ≈4)        α,β-Unsaturated acids
                       ≥230 nm (log ε >3)        Aromatic acids
                                       3.10 Carbonyl Compounds                65

     3.10.4 Esters and Lactones

     Assignment    Range           Comments
13C COOR           165–180 ppm     Shift with respect to COOH -5 to -10 ppm
     al C–(COOR)     20–70 ppm
     al C–(OCOR)    50–100 ppm     Shift with respect to C–(OH) +2 to +10 ppm
     (C)=C–(COOR) 105–160 ppm
     C=(C–COOR)    105–160 ppm
     (C)=C–(OCOR) 100–150 ppm
     C=(C–OCOR)     80–130 ppm
     ar C–(COOR)   120–150 ppm
     ar C–(OCOR)   130–160 ppm
     ar C=(C–OCOR) 105–130 ppm
1H   al CH–COOR      2.0–2.5 ppm   CH3COOR ≈2.0 ppm
                                   CH2COOR ≈2.3 ppm
                                   CHCOOR ≈2.5 ppm
     al CH–OCOR      3.5–5.3 ppm   CH3OCOR ≈3.5–3.9 ppm
                                   CH2COOR ≈4.0–4.5 ppm
                                   CHCOOR ≈4.8–5.3 ppm
     CH=CH–COOR      5.5–8.0 ppm   Shift with respect to CH=CH–H:
                                     gem ≈+0.8 ppm, cis ≈+1.1 ppm
                                     trans ≈+0.5 ppm
     CH=CH–OCOR      6.0–8.0 ppm   Shift with respect to CH=CH–H:
                                     gem ≈+2.1 ppm, cis ≈-0.4 ppm
                                     trans ≈-0.6 ppm
     ar CH–C–COOR    7.0–8.0 ppm   Shift with respect to CH–(C–H):
                                     ortho ≈+0.7 ppm, meta ≈+0.1 ppm,
                                     para ≈+0.2 ppm
     ar CH–C–OCOR    6.8–7.5 ppm   Shift with respect to CH–(C–H):
                                     ortho ≈-0.2 ppm, meta ≈0 ppm,
                                     para ≈-0.1 ppm
IR   C=O st         1745–1730 cm-1 Strong; range for aliphatic esters
                                   Higher wavenumbers for hal–C–COOR,
                                     COO–C=C, COO–C ar, and for small ring
                                     lactones
                                   Lower wavenumbers for C=C–COOR and
                                     ar C–COOR
     C–O st         1330–1050 cm-1 Mostly two bands, at least one of them
                                     strong
                                   For COO–, two bands: 1580 and 1420 cm-1
     66        3 Combination Tables

     Assignment        Range           Comments
MS   Molecular ion                     Aliphatic esters: weak, tendency to protonate
                                       Aliphatic lactones: medium to weak, ten-
                                        dency to protonate
                                       Aromatic esters and lactones: strong
     Fragments         [M - RO]+       Esters
                       [M - ROCO]+     Esters
                                       Lactones: loss of α-substituents (attached to
                                         ether carbon), decarbonylation, for aro-
                                         matic lactones also double decarbonylation
     Rearrange-                        Alkene elimination from the alcohol moiety:
     ments
                                                     +.                                               +.
                                  R1   H
                                           O
                                                                     R 1 CH=CH 2   + R 2 COOH
                                       O       R2



                                       Elimination of the alcohol side chain with
                                         double H transfer (for alcohols with Cn>2):
                                                                                             +
                                                                       +.                    OH
                                                      R1    COOR 2                 R1
                                                                                             OH

                                       Alcohol elimination from ortho-substituted
                                        aromatic esters:
                                           O         +.                                 +.
                                                                                   O
                                                                              C
                                                                                             for X : CH 2 ,
                                               OR          - ROH                                    O,
                                               H                                                    N,
                                           X                                  X                     S, etc.

                       [M-18]+·        Lactones
UV   n    π*           <220 nm (log ε 1–2)          Aliphatic esters
                       ≥193 nm (log ε ≈4)           α,β-Unsaturated esters
                       ≥230 nm (log ε >3)           Aromatic esters
                                          3.10 Carbonyl Compounds               67

     3.10.5 Amides and Lactams

     Assignment     Range             Comments
13C CONR2           165–180 ppm
     al C–(CONR2)     20–70 ppm
     al C–(C–CONR2)    5–50 ppm       Shift with respect to C–(C–CH3) ≈-6 ppm
     al C–(NCOR)      25–80 ppm       Shift with respect to C–(NH) ≈-1 to -2 ppm
     C=C–(CONR2)    105–160 ppm
     ar C–(CONR2)   120–150 ppm
     ar C–(NCOR)    110–150 ppm
1H   CONH                5–10 ppm     Frequently broad to very broad; splitting due
                                        to H–N–C–H coupling often recognizable
                                        only in the CH signal
     al CH–CONR2      2.0–2.5 ppm
     al CH–NCOR       2.7–4.8 ppm     CH3NCOR ≈2.7–3.0 ppm
                                      CH2NCOR ≈3.1–3.5 ppm
                                      CHNCOR ≈3.8–4.8 ppm
     CH=CH–CONR2      5.2–7.5 ppm     Shift with respect to CH=CH–(H):
                                        gem ≈+1.4 ppm, cis ≈+1.0 ppm
                                        trans ≈+0.5 ppm
     C=CH–NCOR        6.0–8.0 ppm     Shift with respect to CH=CH–(H):
     CH=C–NCOR        4.5–6.0 ppm       gem ≈+2.1 ppm, cis ≈-0.6 ppm
                                        trans ≈-0.7 ppm
     ar CH–C(CONR2) 7.5–8.5 ppm       Shift with respect to CH–C–(H):
                                        ortho ≈+0.6 ppm, meta ≈+0.1 ppm,
                                        para ≈+0.2 ppm
     ar CH–C(NCOR)    6.8–7.5 ppm     Shift with respect to CH–C–(H):
                                        ortho ≈0 ppm, meta ≈0 ppm,
                                        para ≈-0.2 ppm
IR   N–H st          3500–3100 cm-1 Position and shape depend on the extent
                                      of association, often different bands for
                                      H-bonded and free NH, always at least two
                                      bands for NH2
     C=O st          1700–1650 cm-1 Strong; range for amides as well as for δ-
     (amide I)                        and larger lactams, higher wavenumbers
                                      for β- and γ-lactams
     N–H δ and       1630–1510 cm-1 Often strong, missing in the case of tertiary
     N–C=O st sy                     amides and lactams
     (amide II)
     68        3 Combination Tables

     Assignment        Range          Comments
MS   Molecular ion                    Aliphatic amides: moderate, tendency to
                                       protonate
                                      Aromatic amides: strong
     Fragments                        Amides: cleavage on both sides of the
                                        carbonyl group followed by loss of CO;
                                        large number of fragments of even mass
                                      Lactams: loss of α-substituent, loss of CO
     Rearrange-                       Amides: elimination of the amine moiety,
     ments                              elimination of alkene from the amine or
                                        acid moiety in analogy to esters
                       [M-18]+·       Lactams
     n    π*           <220 nm        Aliphatic amides and lactams
UV                      (log ε 1–2)
4      13C    NMR Spectroscopy

                                                                                   C


                                                                                  C       C

4.1 Alkanes                                                                       C       C

4.1.1 Chemical Shifts

13C    Chemical Shifts (δ in ppm)


-2.3                    7.3                    15.9                        13.0
CH4                     CH3
                                                      15.4              24.8
                        CH3                                                           N

                                                                        31.3       Hal
 24.1                         22.8                 32.0   22.3
       25.0                                               30.1      27.7
                        34.8 14.2           11.8                                      O

                                                                                      N
         32.2    14.2                29.5   23.1                   32.1    14.1
                                                                                      S
              23.1                      32.4 14.1                29.5   22.8

                                                                                  C       X


                                                                                   P Si

                                                                                  Natural
                                                                                  Products

                                                                                  Solvents
              70       4 13C NMR

              13C   Chemical Shifts of Methyl Groups (δ in ppm)


      C              Substituent R         δCH3–R           Substituent R     δCH3–R
                     –H                     -2.3       C    –2-pyridyl         24.2
  C       C    C     –CH3                    7.3            –3-pyridyl         18.0
                     –CH2CH3                15.4            –4-pyridyl         20.6
                     –CH(CH3)2              24.1            –2-furyl           13.7
  C       C          –C(CH3)3               31.3            –2-thienyl         14.7
                     –(CH2)6CH3             14.1            –2-pyrrolyl        11.8
                     –CH2–phenyl            15.7            –2-indolyl         13.4
                     –CH2F                  15.8            –3-indolyl          9.8
                     –CH2Cl                 18.7            –4-indolyl         21.6
                     –CH2Br                 19.1            –5-indolyl         21.5
                     –CH2I                  20.4            –6-indolyl         21.7
                     –CHCl2                 31.6            –7-indolyl         16.6
                     –CHBr2                 31.8       X    –F                 71.6
      N              –CCl3                  46.3            –Cl                25.6
                     –CBr3                  49.4            –Br                 9.6
  Hal                –CH2OH                 18.2            –I                -24.0
                     –CH2OCH3               14.7       O    –OH                50.2
                     –CH2OCH2CH3            15.4            –OCH3              60.9
      O              –CH2OCH=CH2            14.6            –OCH2CH3           57.6
                     –CH2O–phenyl           14.9            –OCH(CH3)2         54.9
                     –CH2OCOCH3             14.4            –OC(CH3)3          49.4
      N              –CH2NH2                19.0            –OCH2CH=CH2        57.4
                     –CH2NHCH3              14.3            –O–cyclohexyl      55.1
                     –CH2N(CH3)2            12.8            –OCH=CH2           52.5
      S              –CH2NO2                12.3            –O–phenyl          54.8
                     –CH2SH                 19.7            –OCOCH3            51.5
                     –CH2S(O)2CH3            6.7            –OCO–cyclohexyl    51.2
  C       X          –CH2S(O)2OH             8.0            –OCOCH=CH2         51.5
                     –CH2CHO                 5.2            –OCO–phenyl        51.8
                     –CH2COCH3               7.0            –OCOOCH3           54.9
  P Si               –CH2COOH                9.6            –OS(O)2–4-tolyl    56.3
                     –cyclopentyl           20.5            –OS(O)2OCH3        59.1
Natural              –cyclohexyl            23.1            –OP(OCH3)2         48.8
Products             –CH=CH2                18.7            –NH2               28.3
                        –
                                                       N
                     –C – CH
                        –                    3.7            –NH3+              26.5
Solvents             –phenyl                21.4            –NHCH3             38.2
                     –1-naphthyl            19.1            –NH–cyclohexyl     33.5
                     –2-naphthyl            21.5            –NH–phenyl         30.2
                                                 4.1 Alkanes       71

     Substituent R        δCH3–R        Substituent R      δCH3–R

N    –N(CH3)2             47.5          –COCH=CH2           25.7
     –N-pyrrolidinyl      42.7
                                   O    –CO–cyclohexyl      27.6         C
     –N-piperidinyl       47.7     ||   –CO–phenyl          25.7
     –N(CH3)phenyl        39.9     C    –COOH               21.7
     –N-pyrrolyl          35.9          –COO–               24.4        C       C
     –N-imidazolyl        32.2          –COOCH3             20.6
     –N-pyrazolyl         38.4          –COOCOCH3           21.8
                                                                        C       C
     –N-indolyl           32.1          –CONH2              22.3
     –NHCOCH3             26.1          –CON(CH3)2          21.5
     –N(CH3)CHO           31.5,         –COSH               32.6
                          36.5          –COSCH3             30.2
     –N(CH3)COCH3         35.0,         –COCOCH3            23.2
                          38.0          –COCl               33.6
     –N(CH3)P[N(CH3)2]2   33.9          –COBr               39.1
     –NO2                 61.2          –COSi(CH3)3         35.7
     –C – N
        –
        –                  1.7
     –NC                  26.8
                                   M    –Li                -16.6
                                                                            N
                                        –B(CH3)2            14.8
     –NCS                 29.1          –B–(CH3)3 Li+        6.2
S    –SH                   6.5          –Si(CH3)2CH=CH2     -2.0         Hal
     –SCH3                19.3          –SiCl3               9.8
     –S–n-C8H17           15.5          –Ge(CH3)3           -3.6
     –S–phenyl            15.6          –Sn(CH3)3           -9.3            O
     –SSCH3               22.0          –Pb(CH3)3           -4.2
     –S(O)CH3             40.1          –P(CH3)(n-C4H9)     14.4
     –S(O)2CH3            42.6          –P+(CH3)3 I–        10.7
                                                                            N
     –S(O)2CH2CH3         39.3          –As(CH3)2           11.2
     –S(O)2Cl             52.6          –As+(CH3)3 I–
     –S(O)2OH             39.6
                                                             8.4            S
                                        –In(CH3)2           -6.3
     –S(O)2ONa            41.1
O    –CHO                 31.2
                                                                        C       X
     –COCH3               30.7
||   –COCH2CH3            27.5
C    –COCCl3              21.1                                           P Si

                                                                        Natural
                                                                        Products

                                                                        Solvents
              72       4 13C NMR

              13C   Chemical Shifts of Monosubstituted Alkanes (δ in ppm)

                     Substituent       Methyl        Ethyl                  1-Propyl
      C                                –CH3       –CH2 –CH3         –CH2     –CH2 –CH3
                     –H                 -2.3       7.3     7.3      15.4     15.9   15.4
                     –CH=CH2            18.7      27.4    13.4      36.2     22.4   13.6
  C       C   C      –C – CH
                        –                3.7      12.3    13.8      20.6     22.2   13.4
                        –
                     –phenyl            21.4      29.1    15.8      38.3     24.8   13.8
  C       C   X      –F                 71.6      80.1    15.8      85.2     23.6    9.2
                     –Cl                25.6      39.9    18.9      46.8     26.3   11.6
                     –Br                 9.6      27.6    19.4      35.6     26.4   13.0
                     –I                -24.0      -1.6    20.6       9.1     27.0   15.3
              O      –OH                50.2      57.8    18.2      64.2     25.9   10.3
                     –OCH3              60.9      67.7    14.7      74.5     23.2   10.5
                     –OCH2CH3           57.6      66.0    15.4      72.5     23.2   10.7
                     –OCH(CH3)2         54.9
                     –OC(CH3)3          49.4      56.8    16.4
      N              –O–phenyl          54.8      63.2    14.9      69.4     22.8   10.6
                     –OCOCH3            51.5      60.4    14.4      66.2     22.4   10.5
                     –OCO–phenyl        51.8      60.8    14.4      66.4     22.2   10.5
  Hal                –OS(O)2–4-tolyl    56.3      66.9    14.7      72.2     22.3   10.0
              N      –NH2               28.3      36.9    19.0      44.6     27.4   11.5
      O              –NHCH3             38.2      45.9    14.3      54.0     23.2   12.5
                     –N(CH3)2           47.6      53.6    12.8      61.8     20.6   11.9
                     –NHCOCH3           26.1      34.4    14.6      40.7     22.5   11.1
      N              –NO2               61.2      70.8    12.3      77.4     21.2   10.8
                        –
                     –C – N
                        –                1.7      10.8    10.6      19.3     19.0   13.3
                     –NC                26.8      36.4    15.3      43.4     22.9   11.0
      S       S      –SH                 6.5      19.1    19.7      26.4     27.6   12.6
                     –SCH3              19.3
                     –SSCH3             22.0      31.8    14.7
  C       X          –S(O)CH3           40.1
                     –S(O)2CH3          42.6      48.2     6.7      56.3     16.3   13.0
  P Si               –S(O)2Cl           52.6      60.2     9.1      67.1     18.4   12.1
                     –S(O)2OH           39.6      46.7     8.0      53.7     18.8   13.7
              O      –CHO               31.3      36.7     5.2      45.7     15.7   13.3
Natural
                     –COCH3             30.7      35.2     7.0      45.2     17.5   13.5
Products      ||     –CO–phenyl         25.7      31.7     8.3      40.4     17.7   13.8
              C      –COOH              21.7      28.5     9.6      36.2     18.7   13.7
Solvents             –COOCH3            20.6      27.2     9.2      35.6     18.9   13.8
                     –CONH2             22.3      29.0     9.7
                     –COCl              33.6      41.0     9.3      48.9     18.8   13.0
                                                          4.1 Alkanes   73

13C   Chemical Shifts of Monosubstituted Alkanes (δ in ppm, contd.)

                       2-Propyl           tert-Butyl
                                                                              C
                       –CH –CH3           –C       –CH3
       –H               15.9    15.4       25.0     24.1
 C     –CH=CH2
          –
                        32.3    22.1       33.8     29.4                     C       C
       –C – CH
          –             20.3    22.8       27.4     31.1
       –phenyl          34.3    24.0       34.6     31.4
                                                                             C       C
 X     –F               87.3    22.6       93.5     28.3
       –Cl              53.7    27.3       66.7     34.6
       –Br              44.8    28.5       62.1     36.4
       –I               20.9    31.2       43.0     40.4
 O     –OH              64.0    25.3       68.9     31.2
       –OCH3            72.6    21.4       72.7     27.0
       –OCH2CH3                            72.6     27.7
       –OCH(CH3)2       68.5    23.0       73.0     28.5
       –OC(CH3)3        63.5    25.2       76.3     33.8
       –O–phenyl        69.3    22.0                                             N
       –OCOCH3          67.5    21.9      79.9     28.1
       –OCO–phenyl      68.2    21.9      80.7     28.2                       Hal
 N     –NH2             43.0    26.5      47.2     32.9
       –NHCH3           50.5    22.5      50.4     28.2
       –N(CH3)2         55.5    18.7      53.6     25.4                          O
       –NHCOCH3         40.5    22.3      49.9     28.6
       –NO2             78.8    20.8      85.2     26.9
       –C – N
          –
          –             19.8    19.9      28.1     28.5                          N
       –NC              45.5    23.4      54.0     30.7
 S     –SH              29.9    27.4      41.1     35.0
                                                                                 S
       –SCH2CH3         34.4    23.4
       –S(O)2CH3        53.5    15.2      57.6     22.7
       –S(O)2Cl         67.6    17.1      74.2     24.5                      C       X
       –S(O)2OH         52.9    16.8      55.9     25.0
 O     –CHO             41.1    15.5      42.4     23.4
       –COCH3           41.6    18.2      44.3     26.5                       P Si
 ||    –CO–phenyl       35.2    19.1      43.5     27.9
 C     –COOH            34.1    18.8      38.7     27.1                      Natural
       –COOCH3          34.1    19.1      38.7     27.3                      Products
       –CONH2           34.9    19.5      38.6     27.6
       –COCl            46.5    19.0      49.4     27.1
                                                                             Solvents
              74       4 13C NMR

              13C   Chemical Shifts of 1-Substituted n-Octanes (δ in ppm)

                     Substituent        1    2    3    4    5    6    7    8
      C                                –CH2 –CH2 –CH2 –CH2 –CH2 –CH2 –CH2 –CH3
                     –H                14.1    22.8    32.1 29.5 29.5       32.1   22.8   14.1
  C       C    C     –CH=CH2           34.5   ~29.6   ~29.6 ~29.6 ~29.6     32.2   23.0   13.9
                     –phenyl           36.2    31.7   ~29.6 ~29.6 ~29.6     32.1   22.8   14.1
               X     –F                84.2    30.6    25.3 29.3 29.3       31.9   22.7   14.1
  C       C          –Cl               45.1    32.8    27.0 29.0 29.2       31.9   22.8   14.1
                     –Br               33.8    33.0    28.3 28.8 29.2       31.8   22.7   14.1
                     –I                 6.9    33.7    30.6 28.6 29.1       31.8   22.6   14.1
               O     –OH               63.1    32.9    25.9 29.5 29.4       31.9   22.8   14.1
                     –O–n-C8H17        71.1    30.0    26.3 29.6 29.4       32.0   22.8   14.1
                     –O–phenyl         68.0    26.2    29.3 29.4 29.4       31.9   22.7   14.1
                     –OCO–n-propyl     64.4    28.8    26.1 29.3 29.3       31.9   22.8   14.1
                     –OCO–phenyl       65.1    28.8    26.1 29.3 29.3       31.9   22.7   14.1
                     –ONO              68.3    29.2    26.0 29.3 29.3       31.9   22.7   14.0
      N        N     –NH2              42.4    34.1    27.0 29.6 29.4       31.9   22.7   14.1
                     –N(CH3)2          60.1   29.5*   ≈27.9* ≈27.7* 29.7*   32.0   22.8   14.4
                     –N+(CH3)3 Cl–     66.6    26.2    23.2 29.1* 29.0*     31.6   22.5   14.0
  Hal                –NO2              75.8    26.2    27.9 ≈29.6 ≈29.6     31.4   22.6   14.0
                     –C – N
                        –
                        –              17.2    25.5   ≈29.9 ≈29.9 ≈29.9     31.8   22.7   14.0
      O        S     –SH               24.7    34.2    28.5 29.2 29.1       31.9   22.7   14.1
                     –SCH3             34.5    29.0    29.4 29.4 29.4       31.9   22.8   14.1
                     –S(O)–n-C8H17     52.6   ≈29.1   ≈29.1 ≈29.1 ≈29.1     31.8   22.7   14.1
      N        O     –CHO              44.0    22.2   ≈29.3 ≈29.3 ≈29.3     31.9   22.7   14.1
                     –COCH3            43.7    24.1   ≈29.5 ≈29.5 ≈29.5     32.0   22.8   14.1
               ||    –CO–phenyl        38.6    24.4    29.5 29.5 29.5       31.9   22.7   14.0
      S        C     –COOH             34.2    24.8   ≈29.3 ≈29.3 ≈29.3     31.9   22.7   14.1
                     –COOCH3           34.2    25.1    29.3 29.3 29.3       31.9   22.8   14.1
                     –CONH2            35.5    25.4    29.1 29.1 29.1       31.6   22.3   14.0
  C       X          –COCl             47.2    25.1    28.5 29.1 29.1       31.8   22.7   14.1
              Si     –Si(OCH3)3         9.2    22.7    33.2 29.3 29.3       32.0   22.7   14.1

  P Si        * Assignment uncertain


Natural
Products

Solvents
                                                              4.1 Alkanes      75

Estimation of 13C Chemical Shifts of Aliphatic Compounds (δ in ppm)
The chemical shifts of sp3-hybridized carbon atoms can be estimated with the help
of an additivity rule using the shift value of methane (-2.3 ppm) and increments (Z) C
for substituents in α, β, γ, and δ position (see next pages). Some substituents occupy
two positions. Thus, the quaternary carbon atom c in the example given below is
in δ position relative to the carbon atom a since the sp3-hybridized oxygen of the C C
β-COO group occupies the γ position. This simple linear model needs corrections
in case of strong branching of the observed C atom and/or its neighbors (steric
corrections, S). Substituents for which such corrections are necessary are those with
varying branching, i.e., a varying number of directly bonded H atoms. They are
                                                                                       C C
marked with an asterisk (*) in the Table of Increments (next page). Further correction
terms are needed if γ substituents are in a sterically fixed position (conformational
corrections, K).
   The chemical shifts estimated with this additivity rule, in general, differ by less
than ca. 4 ppm from the experimental values. Larger discrepancies may be ex-
pected for highly branched systems (particularly for quaternary carbon atoms). For
carbon atoms bearing several halogen, oxygen, and/or other strongly deshielding
substituents, additional correction terms are needed [1]. Without such corrections,
deviations can be so large as to render the rule useless.
   Example: Estimation of chemical shifts for N-(tert-butoxycarbonyl)alanine            N

                                     O         b
                                                                                     Hal
                         d
                                                       OH
                               c O
                                                                                        O
                                         N a
                                         H         O


   a    base value           -2.3                      b    base value      -2.3
                                                                                        N
        1 α-C                 9.1                           1 α-C            9.1
        1 α-COOH             20.1                           1 β-COOH         2.0
        1 α-NH               28.3                           1 β-NH          11.3        S
        1 β-COO               2.0                           1 γ-COO         -2.8
        1 δ-C                 0.3                           1 S(prim,3)     -1.1
        1 S(tert,2)          -3.7                           estimated       16.2    C       X
        estimated            53.8                           exp             17.3
        exp                  49.0
                                                                                     P Si
   c    base value           -2.3                      d    base value      -2.3
        3 α-C                27.3                           1 α-C            9.1
        1 α-OCO              56.5                           2 β-C           18.8    Natural
        1 γ-NH               -5.1                           1 β-OCO          6.5    Products
        1 δ-C                 0.3                           1 δ-NH           0.0
        3 S(quat,1)          -4.5                           1 S(prim,4)     -3.4    Solvents
        estimated            72.2                           estimated       28.7
        exp                  78.1                           exp             28.1
              76     4 13C NMR

              Estimation of 13C Chemical Shifts of Aliphatic Compounds (δ in ppm)
                                     δ = -2.3 + ∑ Zi + ∑ Sj + ∑ Kk
                                                  i    j      k
      C
                   Substituent            Increment Zi for substituents in position
                                                α            β            γ             δ
  C       C
                   –H                          0.0          0.0          0.0           0.0
              C    –C*                         9.1          9.4         -2.5           0.3
  C       C        –C*=C                     19.5           6.9         -2.1           0.4
                      –
                   –C – C–
                      –                        4.4          5.6         -3.4          -0.6
                   –phenyl                   22.1           9.3         -2.6           0.3
              X    –F                        70.1           7.8         -6.8           0.0
                   –Cl                       31.0         10.0          -5.1          -0.5
                   –Br                       18.9         11.0          -3.8          -0.7
                   –I                        –7.2         10.9          -1.5          -0.9
              O    –O–*                      49.0         10.1          -6.2           0.3
                   –OCO–                     56.5           6.5         -6.0           0.0
      N            –ONO                      54.3           6.1         -6.5          -0.5
              N    –N*                       28.3         11.3          -5.1           0.0
  Hal              –N+,*                     30.7           5.4         -7.2          -1.4
                   –NH3+                     26.0           7.5         -4.6           0.0
                   –NO2                      61.6           3.1         -4.6          -1.0
      O               –
                   –C – N
                      –                        3.1          2.4         -3.3          -0.5
                   –NC                       31.5           7.6         -3.0           0.0
      N       S    –S*–                      10.6         11.4          -3.6          -0.4
                   –SCO–                     17.0           6.5         -3.1           0.0
                   –S*(O)–                   31.1           7.0         -3.5           0.5
      S            –S*(O)2–                  30.3           7.0         -3.7           0.3
                   –S(O)2Cl                  54.5           3.4         -3.0           0.0
                   –SCN                      23.0           9.7         -3.0           0.0
  C       X   O    –CHO                      29.9         -0.6          -2.7           0.0
                   –CO–                      22.5           3.0         -3.0           0.0
              ||   –COOH                     20.1           2.0         -2.8           0.0
  P Si        C    –COO–                     24.5           3.5         -2.5           0.0
                   –COO–                     22.6           2.0         -2.8           0.0
Natural            –CO–N                     22.0           2.6         -3.2          -0.4
Products           –COCl                     33.1           2.3         -3.6           0.0
                   –C=NOH syn                11.7           0.6         -1.8           0.0
Solvents           –C=NOH anti               16.1           4.3         -1.5           0.0
                   –CS–N                     33.1           7.7         -2.5           0.6
                   –Sn                        -5.2          4.0         -0.3           0.0
                                                                  4.1 Alkanes            77

Steric Corrections, Sj

Observed 13C center            S for number of substituents at the α atoma
                                                                                               C
                                     1            2             3            4
primary (CH3)                       0.0          0.0          -1.1         -3.4
secondary (CH2)                     0.0          0.0          -2.5         -6.0               C       C
tertiary (CH)                       0.0         -3.7          -8.5        -10.0
quaternary (C)                     -1.5         -8.0        -10.0         -12.5
a Tobe applied to each of the neighboring atoms that has an unspecified number of non-
                                                                                              C       C
hydrogen substituents (marked with an asterisk (*) in the Table of Increments, Zi).


Conformational Corrections, Kk, for γ Substituents

       Conformation                                          K
                                       CX
       synperiplanar (eclipsed)                            -4.0
                                                                                                  N
                                        C
       synclinal (gauche)
                                            X
                                                           -1.0
                                                                                               Hal

                                        C                                                         O
       anticlinal                                           0.0
                                             X
                                                                                                  N
                                        C
       antiperiplanar (anti)                                2.0
                                                                                                  S
                                        X
       not fixed                                            0.0
                                                                                              C       X
One can also use the chemical shifts of a reference compound as the base value if
its structure is closely related to that assumed for the unknown. The increments cor- P Si
responding to the structural elements missing in the reference compound are then
added to the base value, while those of structural elements present in the reference
but absent in the unknown are subtracted (see example on next page).                 Natural
                                                                                              Products

                                                                                              Solvents
              78          4 13C NMR

              Example: Estimation of the chemical shifts for the carbon atoms a and b in N-(tert-
              butoxycarbonyl)alanine using the chemical shifts of valine as base values (a', b'):
                       Target:                                          Reference:
      C
                                 O         b                                         b'
                   d
                                                   OH                                     OH
  C       C               c O        N a                                   H2 N a'
                                     H         O                                      O

  C       C   a        base value (a')      61.9                b       base value (b')       30.3
                       1 β-COO               2.0                        1 γ-COO               -2.8
                       1 δ-C                 0.3                        1 S(prim,3)           -1.1
                       1 S(tert,2)          -3.7                        - 2 α-C              -18.2
                       - 2 β-C             -18.8                        - 1 S(tert,3)          8.5
                       - 1 S(tert,3)         8.5                        estimated             16.6
                       estimated            50.2                        exp                   17.3
                       exp                  49.0

      N
              4.1.2 Coupling Constants
  Hal         13C-1H      Coupling Constants

              Coupling through one bond (1JCH in Hz)
      O
              The 13C-1H coupling constant of 125 Hz in methane increases in the presence of
              electronegative substituents and can be estimated by using the following additivity
      N       rule:
                                        JCHZ Z Z = 125.0 + ∑ Zi
                                                        1 2 3       i

      S       Substituent            Increment Zi                   Substituent           Increment Zi
              –H                           0.0                      –Br                       27.0
              –CH3                         1.0                      –I                        26.0
  C       X   –C(CH3)3                    -3.0                      –OH                       18.0
              –CH2Cl                       3.0                      –O–phenyl                 18.0
              –CH2Br                       3.0                      –NH2                        8.0
  P Si        –CH2I                        7.0                      –NHCH3                      7.0
              –CHCl2                       6.0                      –N(CH3)2                    6.0
              –CCl3                        9.0                      –C – N
                                                                       –
                                                                       –                       11.0
Natural       –C – C
                 –
                 –                         7.0                      –S(O)CH3                  13.0
Products      –phenyl                      1.0                      –CHO                        2.0
              –F                         24.0                       –COCH3                     -1.0
              –Cl                        27.0                       –COOH                       5.5
Solvents
              Example: Estimation of 13C-1H coupling constant of CHCl3:
              J = 125.0 + 3 × 27.0 = 206.0 Hz (exp: 209.0 Hz).
                                                                           4.1 Alkanes        79

Coupling through more than one bond (|JCH| in Hz)
The coupling constants can be estimated from the corresponding 1H-1H coupling
constants [2]: JCH ≈ 0.62 JHH
                                                                                                   C
                      Typical values:                     Examples:
                      2J                                  1H–CH –13CH
                         CH 1– 6                                2     3    4.5
                      3J
                         CH 0–10
                                                          1H–CH –CH –13CH 5.8
                                                                2   2    3                         C       C
   The 13C-1H   coupling constants for coupling across three bonds depend on the
dihedral angle in the same way as the vicinal 1H-1H coupling constants (see Chap-
ter 5.1.2):                                                                       C                        C
        13
           C                     13
                                    C                         13
                                                                 C
            H

                    ≈6                            H       ≈0                             ≈9


                                                                                   H

13C-13C    Coupling Constants (|JCC| in Hz)                                                            N


H 3 C CH 3     1J   34.6
                                   b
                                           1J
                                                                   b           d         2J 4.6
                                                                                           ac      Hal
                                                ab 34.6                            OH
                                                                                         3J 4.6
                                                                                           ad
                               a                               a           c             2J <1
                                                                                           bd
                                                                                                       O
                                       O                                   O
                                                                                   b
       O                                                               a                 2J 0.5
           CH3 2Jab                                                                                    N
                      2.4                                                          CH3     ab
H3 C                           H3 C        CH3 2Jab 16.1           H           N         2J 4.9
   a       b                       a       b                                               ac
                                                                               CH3
                                                                               c
                                                                                                       S
The 13C-13C coupling constants for coupling over three bonds depend on the di-
hedral angle in the same way as the vicinal 1H-1H (see Chapter 5.1.2) and 13C-1H
coupling constants. Maximum values of ca. 4–6 Hz are observed for dihedral angles
of 0o and 180o and minimal values around 0 Hz at 90o.                             C                        X


4.1.3 References                                                                                   P Si
[1] A. Fürst, E. Pretsch, W. Robien, A comprehensive parameter set for the predic- Natural
    tion of the 13C NMR chemical shifts of sp3-hybridized carbon atoms in organic Products
    compounds, Anal. Chim. Acta 1990, 233, 213.
[2] J.L. Marshall, Carbon-Carbon and Carbon-Proton NMR couplings, Verlag
    Chemie International, Deerfield Beach, FL, 1983.                               Solvents
              80        4 13C NMR

              4.2 Alkenes

              4.2.1 Chemical Shifts
      C
              13C   Chemical Shifts (δ in ppm)

  C       C   The 13C chemical shifts of the carbons of C=C double bonds typically range from ca.
              80–160 ppm; a wider range of 40–210 ppm is observed with O and N substituents.
              In unsaturated acyclic hydrocarbons, they can be predicted with high accuracy (see
  C       C   below). To estimate the 13C chemical shifts in all other substituted alkenes, one can
              use the substituent effects listed for chemical shifts in vinyl groups. However, since
              no configuration-dependent parameters are available, the values thus estimated are
              less accurate than those for unsaturated acyclic hydrocarbons.
                 The 13C chemical shifts of sp3-hybridized carbon atoms in the vicinity of double
              bonds can be estimated using the additivity rule given in Chapter 4.1.1. The con-
              formational correction factors, K, for γ substituents of cis- vs. trans-disubstituted
              alkenes differ by 6 ppm because the relative position of these substituents is fixed
              by the double bond.

      N
              Estimation of the 13C Chemical Shifts of sp2-Hybridized Carbon Atoms in
  Hal         Unsaturated Acyclic Hydrocarbons (δ in ppm)

                                               C–C–C'=C–C–C–C
      O                                        γ' β' α' α β γ
                                                         Base value: 123.3

      N       Increments for C substituents:

              at C atom under consideration (C)                 at neighboring C atom (C')
      S                  α            10.6                              α'           -7.9
                         β              4.9                             β'           -1.8
  C       X              γ             -1.5                             γ'            1.5

              Steric corrections:
  P Si
               •    for each pair of cis-α,α'-substituents       -1.1
               •    for a pair of geminal α,α-substituents       -4.8
Natural        •    for a pair of geminal α',α'-substituents      2.5
Products
               •    if one or more β-substituents are present     2.3

Solvents
                                                                    4.2 Alkenes       81

Example: Estimation of chemical shifts of cis-4-methyl-2-pentene


                                                                                           C
                                      a      b

a    base value          123.3                      b    base value        123.3           C   C
     1 α-C                10.6                           1 α-C              10.6
     1 α'-C               -7.9                           2 β-C               9.8
     2 β'-C               -3.6                           1 α'-C             -7.9           C       C
     cis-α,α'             -1.1                           cis-α,α'           -1.1
     estimated           121.3                           1 β-substituent     2.3
     exp                 121.8                           estimated         137.0
                                                         exp               138.8



Effect of Substituents on the        13C   Chemical Shifts of Vinyl Compounds (δ in
ppm)
                         1       2                                                             N
                     R   CH CH2                  δCi = 123.3 + Zi
                                                                                           Hal
     Substituent R  Z1                Z2                Substituent R    Z1         Z2
                                                                                            O
     –H              0.0               0.0        O     –OH              25.7      -35.3
 C   –CH3           12.9              -7.4              –OCH3            29.4      -38.9
     –CH2CH3        17.2              -9.8              –OCH2CH3         28.8      -37.1
     –CH2CH2CH3     15.7              -8.8              –O(CH2)3CH3      28.1      -40.4    N
     –CH(CH3)2      22.7             -12.0              –OCOCH3          18.4      -26.7
     –(CH2)3–       14.6              -8.9        N     –N(CH3)2         28.0*     -32.0*
     –C(CH3)3       26.0             -14.8              –N+(CH3)3        19.8      -10.6    S
     –CH2Cl         10.2              -6.0              –N-pyrrolidonyl   6.5      -29.2
     –CH2Br         10.9              -4.5              –NO2             22.3       -0.9
     –CH2I          14.2              -4.0                 –
                                                        –C – N
                                                           –            -15.1       14.2  C X
     –CH2OH         14.2              -8.4              –NC              -3.9       -2.7
     –CH2OCH2CH3 12.3                 -8.8        S     –SCH2CH3          9.0      -12.8
     –CH=CH2        13.6              -7.0              –S(O)2CH=CH2 14.3            7.9  P Si
     –C – CH
        –
        –           -6.0               5.9        O     –CHO             15.3       14.5
     –phenyl        12.5             -11.0              –COCH3           13.8        4.7 Natural
     –F             24.9             -34.3        ||    –COOH             5.0        9.8 Products
 X   –Cl             2.8              -6.1        C     –COOCH2CH3        6.3        7.0
     –Br            -8.6              -0.9              –COCl             8.1       14.0
     –I            -38.1               7.0        Si    –Si(CH3)3        16.9        6.7 Solvents
                                                        –SiCl3            8.7       16.1

* Estimated values
              82        4 13C NMR

              The values listed on the preceding page can also be used to estimate the 13C chemi-
              cal shifts of sp2-hybridized carbon atoms in alkenes with more than one substituent
              (note that the cis/trans configuration is not taken into account):
      C                                          δCi = 123.3 + ∑ Zi

              Example: Estimation of chemical shifts of 1-bromo-1-propene
  C       C
                                                    a        b
                                                 Br CH CH CH3
  C       C
              a     base value           123.3                   b    base value       123.3
                    Z1(Br)                -8.6                        Z2(Br)            -0.9
                    Z2(CH3)               -7.4                        Z1(CH3)           12.9
                    estimated            107.3                        estimated        135.3
                    exp                  108.9 (cis)                  exp              129.4 (cis)
                                         104.7 (trans)                                 132.7 (trans)
              The following examples show some larger deviations between measured and esti-
              mated (in parentheses) chemical shifts. This is usually to be expected when several
      N       substituents are present that strongly interact with the π electrons of the double
              bond:
  Hal         NC a        b N(CH3 )2                             Ha     b N(CH3 )2
                                        a 39.1 (29.1)                                  a 69.2 (59.3)
                C      C                                          C     C
                                        b 171.0 (207.7)                                b 163.0 (179.3)
      O       NC           N(CH3 )2                              H          N(CH3 )2

                       Ha       b NO2                            H a     b OCH3
                                        a 151.0 (150.4)                                a 54.7 (45.5)
      N                 C       C
                                        b 111.4 (113.6)
                                                                   C     C
                                                                                       b 167.9 (182.1)
              (CH3 )2 N             H                            H           OCH3

      S       13C   Chemical Shifts of cis- and trans-1,2-Disubstituted Alkenes (δ in ppm)


  C       X                 Substituent R
                                                         R       R                     R    H

                                                         H       H                     H    R

  P Si                      –CH3                          123.3                         124.5
                            –CH2CH3                       131.2                         131.3
                            –Cl                           118.1                         119.9
Natural
                            –Br                           116.4                         109.4
Products
                            –I                             96.5                          79.4
                            –C – N
                               –
                               –                          120.8                         120.2
Solvents                    –OCH3                         130.3                         135.2
                            –COOH                         130.4                         134.2
                            –COOCH3                       130.1                         133.5
                                                                            4.2 Alkenes          83

13C   Chemical Shifts of Enols (δ in ppm)
The carbon atom bonded to the enolic OH group is strongly deshielded so that its
shift is close to that of a carbonyl carbon. The other carbon atom of the double bond                  C
is strongly shielded.
       Enol:                                       Ketone:
                                                                                                      C       C
               H
           O           O        a 22.5                         O        O          a 28.5
                                b 190.5                                            b 201.1
                                c 99.0                         b                   c 56.6             C       C
           b                                           a            c
       a       c

           a                    a 28.3                     a                        a 28.3
           c       b            b 32.8                     c        b               b 31.0
                                c 46.2                                              c 54.2
                                d 191.1                                             d 203.6
      HO d
                   e
                           O    e 103.3                O d
                                                                    e
                                                                            O       e 57.3


13C   Chemical Shifts of Allenes (δ in ppm)
                                                                                                          N
                                           a   b   c           R3
                                      R1
                                           C C C                                                       Hal
                                      R2                   H

       R1                  R2         R3                               a           b        c             O
       –H                  –H         –H                             74.8       213.5     74.8
       –CH3                –H         –H                             84.4       210.4     74.1
       –CH3                –CH3       –H                             93.4       207.3     72.1            N
       –CH3                –H         –CH3                           85.4       207.1     85.4
       –CH2CH3             –H         –H                             91.7       208.9     75.3
       –C(CH3)3            –C(CH3)3   –H                            119.6       207.0     75.8
                                                                                                          S
       –CH=CH2             –H         –H                             93.9       211.4     75.1
       –C – CH
          –
          –                –H         –H                             74.8       217.7     77.3
                                                                                                      C       X
       –phenyl             –H         –H                             94.4       210.0     78.8
       –F                  –H         –H                            129.8       200.2     93.9
       –Cl                 –H         –H                             88.8       207.9     84.5         P Si
       –Br                 –H         –H                             72.7       207.6     83.8
       –I                  –H         –H                             35.3       208.0     78.3
                                                                                                      Natural
       –OCH3               –H         –H                            123.1       202.0     90.3
                                                                                                      Products
       –N(CH3)2            –H         –H                            113.1       204.2     85.5
       –C – N
          –
          –                –H         –H                             67.4       218.7     80.7
       –SCH3               –H         –H                             90.0       206.1     81.3        Solvents
       –COOH               –H         –H                             88.1       217.7     80.0
              84         4 13C NMR

              4.2.2 Coupling Constants

              13C-1H     Coupling Constants (|JCH| in Hz)
      C
              Coupling through one bond
                                    1J         156.4                                                                 1J            167.8
  C       C   CH2    CH2                 CH                                CH2            C        CH2                    CH

              Coupling through two bonds
  C       C
              H               H                                                       H                      H
                                          2J        -2.4                                                                  2J         6.9
                     13
                          C                    CH                                                   13
                                                                                                         C                     CH
              H               H                                                      Cl                      H
              Additivity rule for the estimation of             2J        of alkenes: see [2].
                                                                     CH

              Coupling through three bonds
              The trans-1H–C=C–13C coupling constant of alkenes is always larger than the cor-
              responding cis coupling constant so that an assignment is possible if both isomers
      N       are available: see [3].
                          c                                          c                                                         c
              Ha                                           Ha                                                Ha
   Hal
                     13                                         13                                                        13
                          CH3                                        CH3                                                       COOH
                                  3J       7.6                                3J          4.1                                              3J       7.6
               C     C               ac                     C   C                ac                           C           C                   ac
                                  3J      12.6                                3J          8.1                                              3J      14.1
              Hb          H          bc                    Hb        Cl          bc                          Hb                H              bc

      O                   c                                a         c                                                          c
              Ha     13
                          COOH                         H        13
                                                                     COOH                                H3 C              13
                                                                                                                                COOH
               C     C              3J         7.6                             3J             7.7                                          3J       6.9
                                       ac               C       C                 ab                              C        C                  ab
      N       Hb          CH3
                                    3J
                                       bc     14.1 H3 C         13
                                                                     CH3
                                                                               3J
                                                                                  ac          7.4             H            13
                                                                                                                                CH3
                                                                                                                                           3J
                                                                                                                                              ac   13.2
                                                                     b                                        a                 b

      S       13C-13C     Coupling Constants (|JCC| in Hz)
                                                                          a            b             c
                                          1J                                                                              1J         70.0
              CH2    CH2                       CC   67.6                  CH2         CH            CH3                      ab
                                                                                                                          1J         41.9
  C       X                                                                                                                  bc
                                          1J                                     b             d             1J       68.8           2J       <1
              CH2    C        CH2              CC   98.7                                                        ab                      ac
                                                                                                             1J       53.7           3J        9.0
   P Si                                                                   a               c                     bc                      ad

              4.2.3 References
Natural
Products [1] R.H.A.M. Janssen, R.J.J.Ch. Lousberg, M.J.A. de Bie, An additivity relation
                  for carbon-13 chemical shifts in substituted allenes, Recl. Trav. Chim. Pays-Bas
                  1981, 100, 85.
Solvents      [2] U. Vögeli, D. Herz, W. von Philipsborn, Geminal C,H spin coupling in substi-
                  tuted alkenes, Org. Magn. Reson. 1980, 13, 200.
              [3] U. Vögeli, W. von Philipsborn, Vicinal C,H spin coupling in substituted alkenes.
                  Org. Magn. Reson. 1975, 7, 617.
                                                                        4.3 Alkynes   85

4.3 Alkynes

4.3.1 Chemical Shifts
                                                                                            C
13C   Chemical Shifts of Alkynes (δ in ppm)
                                                a        b
                                                                                           C       C
                                          R C C H


                    Substituent R                                a           b             C       C
                    –H                                         71.9        71.9
        C           –CH3                                       80.4        68.3
                    –CH2CH3                                    85.5        67.1
                    –CH2CH2CH3                                 84.0        68.7
                    –CH2CH2CH2CH3                              83.0        66.0
                    –CH(CH3)2                                  89.2        67.6
                    –C(CH3)3                                   92.6        66.8
                    –cyclohexyl                                88.7        68.3
                    –CH2OH                                     83.0        73.8                N
                    –CH=CH2                                    82.8        80.0
                       –
                    –C – C–CH3
                       –                                       68.8        64.7             Hal
                    –phenyl                                    84.6        78.3
        O           –OCH2CH3                                   90.9        26.5
                                                                                               O
        S           –SCH2CH3                                   72.6        81.4
                    –CHO                                       81.8        83.1
        O           –COCH3                                     81.9        78.1
        ||          –COOH                                      74.0        78.6
                                                                                               N
        C           –COOCH3                                    74.8        75.6

Additivity rule for estimating the chemical shifts of sp-hybridized carbon atoms in
                                                                                               S
alkynes: see [1].
                                                                                           C       X
4.3.2 Coupling Constants

13C-1H      Coupling Constants (|JCH| in Hz) [2]                                            P Si
  a     b       c
                                1J      249.0
  H C           C       H          ab                                                      Natural
                                2J       49.3 (in substituted acetylenes: 40–60)
                                   ac                                                      Products
  a     b       c       d e
                                2J       50.1       3J        3.4
                                   ac                  ad
  H     C       C       CH3
                                2J      -10.4       3J        4.7                          Solvents
                                   ce                  be
  a         b       c
 H3 C       C       C       CH3 2Jab -10.3          3J
                                                         ac   4.3
              86      4 13C NMR

              With acetylenes, the results of multipulse experiments (such as DEPT, INEPT,
              SEFT, or APT) to determine the number of protons attached to the carbon atoms
              must be interpreted with care. As a consequence of the unusually large 13C-1H cou-
      C       pling constants through one and two bonds, the sign of the signals may be opposite
              to the expected one. For the same reasons, unexpected signals may occur in two-
              dimensional heteronuclear correlation spectra (HSQC, HMBC).
  C       C
              13C-13C   Coupling Constants (|1JCC| in Hz)

  C       C                                             a   b   c
                               1J        171.5                               1J      190.3
              H C     C   H         CC             H    C   C   C   C   H       ab
                                                                             1J      153.4
                                                                                bc



              4.3.3 References

              [1]   W. Höbold, R. Radeglia, D. Klose, Inkrementen-Berechnung von 13C-che-
                    mischen Verschiebungen in n-Alkinen, J. Prakt. Chem. 1976, 318, 519.
              [2]   K. Hayamizu, O. Yamamoto, 13C,1H Spin coupling constants of dimethylacet-
      N             ylene, Org. Magn. Reson. 1980, 13, 460.

  Hal

      O

      N

      S

  C       X


  P Si

Natural
Products

Solvents
                                                              4.4 Alicyclics          87

4.4 Alicyclics

4.4.1 Chemical Shifts
                                                                                            C
Saturated Monocyclic Alicyclics (δ in ppm)
                                                                     n          δ
                                                                                           C       C
        -2.8                27.1                                     9         26.0
                                                                    10         25.1
                                                                    11         26.3        C       C
                                                                    12         23.8
        22.9                28.8                 (CH 2 )n           13         26.2
                                                                    14         25.2
                                                                    15         27.0
                                                                    20         28.0
                                                                    30         29.3
         25.6               26.8                                    40         29.4
                                                                    72         29.7
13C   Chemical Shifts of Monosubstituted Cyclopropanes (δ in ppm)
                                       a
                                                                                               N
                                             b
                                   R
                                                                                            Hal
      Substituent R           a              b              other
      –H                    -2.8           -2.8
C     –CH3                   4.9            5.6             CH3 19.4                           O
      –CH2CH3               12.8            4.1             CH2 27.8, CH3 13.6
      –CH2CH2CH2CH3         10.9            4.4             1-CH2 34.7, 2-CH2 32.0
      –C(CH3)3              22.7            0.3             C 29.3, CH3 28.2                   N
      –CH2Cl                13.6            5.5             CH2 50.3
      –CH2OH                12.7            2.2             CH2 66.5
      –CH=CH2               14.7            6.6             CH 142.4, CH2 111.5                S
      –phenyl               15.3            9.2             C 143.9, CH 125.3–128.2
X     –Cl                   27.3            8.9
                                                                                           C       X
      –Br                   14.2            9.1
      –I                   -20.1           10.4
O     –OH                   45.7            6.8                                             P Si
N     –NH2                  24.0            7.4
      –NO2                  54.3           11.7
         –                                                                                 Natural
      –C – N
         –                  -4.5            6.2             CN 121.5
                                                                                           Products
O     –CHO                  22.7            7.4             CO 202.1
      –COCH3                20.1            9.6             CO 207.3, CH3 29.1
||    –CO–phenyl            17.1           11.5                                            Solvents
C     –COOH                 12.7            8.9             CO 181.6
      –COOCH3               12.2            7.7             CO 174.7, CH3 51.1
              88       4 13C NMR

              13C   Chemical Shifts of Monosubstituted Cyclopentanes (δ in ppm)
                                                       b
                                                            c
      C                                        R
                                                   a



  C       C
                     Substituent R     a      b      c     other
                     –H              26.0   26.0   26.0
  C       C   C      –CH3            34.8   34.8   25.4    CH3 21.4
                     –CH2CH3         42.3   32.6   25.4    CH2 29.2, CH3 13.2
                     –CH(CH3)2       47.4   30.0   24.7    CH 33.9, CH3 21.7
                     –C(CH3)3        50.3   26.5   25.1    C 32.5, CH3 27.6
                     –CH2OH          41.2   28.3   24.5    CH2 67.0
                     –F              95.5   32.8   22.5    1J          2         3
              X                                               CF 173.5, JCF 22.1, JCF <1.5 Hz
                     –Cl             62.0   37.2   23.1
                     –Br             53.5   37.9   23.3
                     –I              28.7   40.7   24.9
      N       O      –OH             73.7   35.4   23.4
                     –OCH3           82.2   31.4   23.1    CH3 56.0
  Hal                –OCOCH3         77.7   33.8   24.9    CO 170.8, CH3 21.7
              N      –NH2            53.4   36.4   24.0
                     –NO2            87.0   32.6   24.8
      O                 –
                     –C – N
                        –            27.0   30.5   24.2    CN 123.4
              S      –SH             38.3   37.7   24.6
              O      –CO–phenyl      46.4   30.0   26.3
      N        ||    –COOH           43.0   29.2   25.1    CO 183.8
                     –COOCH3         43.7   30.0   25.8    CO 177.0, CH3 51.4
              C
      S

  C       X


  P Si

Natural
Products

Solvents
                                                       4.4 Alicyclics                  89

13C Chemical Shifts of Equatorially and Axially Monosubstituted Cyclohexanes
(δ in ppm)                                                                   R
                                c       a
                                    b                              c     b
                                            R                                    a           C
                            d                                 d
     Substituent R        a      b       c       d      a    b    c    d
     –H                  27.1   27.1    27.1    27.1   27.1 27.1 27.1 27.1                  C       C
C    –CH3                33.2   36.0    27.1    27.0   28.4 32.4 20.6 26.9
     –CH2CH3             40.1   33.4    26.9    27.2   35.5 30.0 21.4 27.1
     –CH2CH2CH3          40.0   33.6    26.6    26.9
                                                                                            C       C
     –CH(CH3)2           44.6   30.0    26.8    27.3   41.1 30.2 21.6 27.1
     –CH2CH2CH2CH3       38.4   34.1    27.1    27.3
     –C(CH3)3            48.8   28.1    27.7    27.1
     –cyclohexyl         44.3   30.8    27.4    27.4
     –CH=CH2             42.1   32.3    26.0    27.1   37.0       30.0   21.2        27.1
        –
     –C – CH
        –                28.7   32.1    25.2    24.4   28.0       30.0   21.2        25.7
     –phenyl             45.1   34.9    27.4    26.7   35.2       30.1   21.9        27.7
X    –F                  91.0   32.8    23.6    25.3   88.1       30.1   19.8        25.0
     –Cl                 59.8   37.4    26.1    25.4   60.1       33.9   20.4        26.0       N
     –Br                 52.4   38.3    27.3    25.6   55.4       34.9   21.5        26.4
     –I                  31.2   40.1    28.3    25.4   38.3       36.0   22.8        26.1    Hal
     –OH                 70.4   35.8    25.1    26.3   65.5       33.2   20.5        27.1
O    –OCH3               79.2   32.2    24.5    26.4   74.9       30.0   21.1        26.6
     –OCOCH3             72.3   32.2    24.4    26.1                                            O
     –OCO–phenyl         72.8   31.5    24.1    24.7   69.0 29.3 20.3 24.7
     –OSi(CH3)3          70.5   36.0    24.7    25.0   66.1 33.1 19.8 25.0
     –NH2                51.1   37.6    25.8    26.3   47.4 33.8 20.0 27.1
                                                                                                N
N
     –NHCH3              58.7   32.7    25.7    26.8
     –N(CH3)2            64.3   29.2    26.5    26.9
                                                                                                S
     –NH3+Cl–            51.8   32.2    24.8    25.2
     –N=C=N–cyclohexyl   55.7   35.0    24.8    25.5
     –NO2                84.6   31.4    24.7    25.5                                        C       X
     –N3                 59.5   31.5    24.5    24.5   56.8       29.0   20.1        25.2
        –
     –C – N
        –                28.0   29.6    24.6    25.1   26.4       27.4   21.9        25.0
     –NC                 51.9   33.7    24.4    25.2   50.3       30.5   20.1        25.2    P Si
     –NCS                55.3   33.9    24.5    24.8   52.8       31.3   20.4        24.8
S    –SH                 38.3   38.1    26.6    25.3   35.9       33.1   19.4        25.7   Natural
     –CHO                50.1   26.0    25.2    26.1   46.4       24.7   22.7        27.1   Products
O    –COCH3              51.5   29.0    26.6    26.3
||   –COOH               43.7   29.6    26.2    26.6
C    –COO–               47.2   30.9    26.9    26.9                                        Solvents
     –COOCH3             43.4   29.6    26.0    26.4   39.1 27.7 24.1 26.7
     –COCl               55.4   29.7    25.5    25.9
              90          4 13C NMR

              Estimation of 13C Chemical Shifts of Alicyclic Compounds (δ in ppm)
              The 13C chemical shift of the parent compound (e.g., 22.9 for cyclobutane, 26.0
      C       for cyclopentane, and 27.1 ppm for cyclohexane) and the same increments as for
              alkanes (see Chapter 4.1) can be used to estimate the chemical shifts of sp3-hybrid-
              ized carbon atoms of alicyclic compounds. Appropriate use of the conformational
              correction terms, K, is especially important with axial and equatorial substituents in
  C       C   cyclohexanes. The additivity rule is, however, not suitable for estimating chemical
              shifts of substituted cyclopropanes.
  C       C
              13C   Chemical Shifts of Unsaturated Alicyclics (δ in ppm)


                          108.7              137.2                  130.8              132.7
                                              31.4                   32.8              132.7
                   2.3
                                                           23.3                 41.6

                          124.9
                                             127.4                                     126.1
      N                    134.3
                         152.6               25.4                   124.5              124.6
  Hal                    123.4       23.0                 26.0                  22.3


      O
                           130.4             28.8                   134.1
                            26.0              130.9                   129.8
      N                     27.0              128.2                 123.3
                   29.8              27.1                 28.8

      S
                           130.2        132.8                       128.5              131.5
                            25.7             34.3                    28.5
  C       X
                            26.4             34.4
                          29.5               28.7
  P Si          cis                  trans               cis, cis

Natural
Products

Solvents
                                                                     4.4 Alicyclics            91

13C    Chemical Shifts of Condensed Alicyclics (δ in ppm)

        27.6 16.7                         23.9                              28.1 H
                                                  9.4                                33.3            C
                                  21.5                               22.9                24.6
20.2                5.8                                 10.3

                                                                                 H                  C       C

                                                    39.9                               47.3
        31.8 H 45.4                      28.0 H                             32.4 H                  C       C
                                                        29.9                            31.7
26.5                   29.4      23.8                                27.1
                                                          22.6                            22.1

            H                                H                                  H

                 43.3                             36.8                               44.0
           H
                  34.3                       H       29.7                       H       34.6
                                                        24.5                               27.1
                       26.4
                                                                                                        N
           H                                 H                                  H
                                                                                                     Hal
   24.5 38.7 38.7                                37.6 22.0
                          24.1
26.8                                                          27.5                                      O

            42.6                             32.7
                                                                                                        N
         38.5                               33.2                              32.2
                36.5                               29.7                              23.2
                                                                                                        S
                       29.8                                                                 15.0
                                                        9.9
                                                                                                    C       X
         48.8                               75.2
                42.0                               50.4                               24.6           P Si
 24.8               135.8                                 143.2                          26.7
                                                                                                    Natural
                                                                                                    Products
                                                                                      24.4
                       37.9                              47.3                          28.4         Solvents
                       28.5                                                                  28.8
              92       4 13C NMR

                                143.9                   143.5                                  136.8
                      125.9       32.8             123.6    39.1                          125.5    29.5
              124.2                           124.5                                  129.0              23.6
      C                              25.3                               133.8
                                              126.1
                                                      120.9      132.1
  C       C                                                144.7


  C       C   4.4.2 Coupling Constants

              13C-1H   Coupling Constants

              Coupling through one bond (|1JCH| in Hz)


                        160                       134                          128                   125


      N       Coupling through two bonds (|2JCH| in Hz)

  Hal
                        2.6                       3.5                          3.0                   3.7

      O
              Coupling through three bonds (|3JCH| in Hz)

      N                                               H 2.1
                                         13
                                              C             H 8.1
      S

  C       X   13C-13C   Coupling Constants (|1JCC| in Hz)


  P Si                                        a
                                                  b     c       1J      13.4                      32.7
                         12.4                           CH3     1J
                                                                   ab
                                                                   bc   44.0
Natural
Products

Solvents
                                                  4.5 Aromatic Hydrocarbons              93

4.5 Aromatic Hydrocarbons

4.5.1 Chemical Shifts
                                                                                                C
13C   Chemical Shifts of Aromatic Hydrocarbons (δ in ppm) [1]

                                                                        131.8                  C       C
                                  133.7
                                             128.0                  126.2    128.1
                128.5                                126.0                            125.3    C       C


                                           125.5
             126.3                                                    135.2
                                                    124.6
   122.4                                            130.9                     119.7
                     126.3
131.9                                                  127.0
                     128.3                                                    140.1
                   130.1                                                       137.4
                   126.6                             124.6                    123.9
                                                                                                   N
                                                                      137.4

                  143.9                            143.5
                                                                                                Hal
        125.9                            123.6                        141.6    119.7
                    32.8                             39.1
124.2
                          25.3
                                 124.5
                                                           133.8
                                                                                       126.5       O
                                 126.1                                                 126.5
                                         120.9       132.1
                                                                      36.8    124.8
                                                  144.7
                                                                                                   N
                                                                        143.2

             136.8                           137.3                             134.7               S
                                                                      29.2
        125.5 29.5
129.0                                                                             127.5
                          23.6                              128.0
                                                                                               C       X
                                                                                       127.5
                                           37.7 128.0               137.3 123.9 127.5
                                                                                                P Si

139.7      30.3                    128.7         129.7                                 143.2 Natural
                                                                                               Products
                145.9                               140.0
                   119.5                               124.3
                                                                                               Solvents
                   128.2                               127.9
            122.7                                 127.4
   132.1                                 128.4
              94     4 13C NMR

              Effect of Substituents on    13C   Chemical Shifts of Monosubstituted Benzenes
              (δ in ppm)
                                   3   2
      C                                    1
                               4               R          δC = 128.5 + Zi
                                                            i

  C       C
                     Substituent R                  Z1            Z2         Z3      Z4

  C       C    C     –CH3                           9.2           0.7       -0.1    -3.0
                     –CH2CH3                       11.7          -0.6       -0.1    -2.8
                     –CH2CH2CH3                    10.3          -0.2        0.1    -2.7
                     –CH(CH3)2                     20.2          -2.2       -0.3    -2.8
                     –CH2CH2CH2CH3                 10.9          -0.2       -0.2    -2.8
                     –C(CH3)3                      18.6          -3.3       -0.4    -3.1
                     –cyclopropyl                  15.1          -3.3       -0.6    -3.6
                     –cyclopentyl                  17.8          -1.5       -0.4    -2.9
                     –cyclohexyl                   16.3          -1.8       -0.3    -2.8
                     –1-adamantyl                  22.2          -2.9       -0.5    -3.1
                     –CH2F                          8.5          -0.7        0.4     0.5
      N              –CF3                           2.5          -3.2        0.3     3.3
                     –CH2Cl                         9.3           0.3        0.2     0.0
  Hal                –CHCl2                        11.9          -2.4        0.1     1.2
                     –CCl3                         16.3          -1.7       -0.1     1.8
                     –CH2Br                         9.5           0.7        0.3     0.2
      O              –CH2I                         10.5           0.0        0.0    -0.9
                     –CH2OH                        12.4          -1.2        0.2    -1.1
                     –CH2OCH3                       8.7          -0.9       -0.1    -0.9
      N              –CH2NH2                       14.9          -1.4       -0.2    -2.0
                     –CH2NHCH3                     12.6          -0.3       -0.3    -1.8
                     –CH2N(CH3)2                    7.8           0.5       -0.3    -1.5
      S              –CH2NO2                        2.2           2.2        2.2     1.2
                     –CH2CN                         1.6           0.5       -0.8    -0.7
                     –CH2SH                        12.5          -0.6        0.0    -1.6
                     –CH2SCH3                       9.8           0.4       -0.1    -1.6
  C       X
                     –CH2S(O)CH3                    0.8           1.5        0.4    -0.2
                     –CH2S(O)2CH3                  -0.1           2.1        0.6     0.6
                     –CH2CHO                        7.4           1.3        0.5    -1.1
  P Si               –CH2COCH3                      5.8           0.8        0.1    -1.6
                     –CH2COOH                       6.5           1.4        0.4    -1.2
Natural              –CH2Li                        32.2         -22.0       -0.4   -24.3
Products             –CH=CH2                        8.9          -2.3       -0.1    -0.8
                     –C(CH3)=CH2                   12.6          -3.1       -0.4    -1.2
                     –C – CH
                        –
                        –                          -6.2           3.6       -0.4    -0.3
Solvents             –phenyl                        8.1          -1.1        0.5    -1.1
                     –2-pyridyl                    11.2          -1.4        0.5    -1.4
                     –4-pyridyl                     9.6          -1.6        0.5     0.5
                              4.5 Aromatic Hydrocarbons      95

    Substituent R       Z1           Z2       Z3       Z4
    –F                 33.6        -13.0      1.6     -4.4
X   –Cl                 5.3          0.4      1.4     -1.9         C
    –Br                -5.4          3.3      2.2     -1.0
    –I                -31.2          8.9      1.6     -1.1
O   –OH                28.8        -12.8      1.4     -7.4        C       C
    –ONa               39.6         -8.2      1.9    -13.6
    –OCH3              33.5        -14.4      1.0     -7.7
    –OCH=CH2           28.2        -11.5      0.7     -5.8        C       C
    –O–phenyl          27.6        -11.2     -0.3     -6.9
    –OCOCH3            22.4         -7.1      0.4     -3.2
    –OSi(CH3)3         26.8         -8.4      0.9     -7.1
    –OPO(O–phenyl)2    21.9         -8.4      1.2     -3.0
    –OCN               25.0        -12.7      2.6     -1.0
N   –NH2               18.2        -13.4      0.8    -10.0
    –NHCH3             15.0        -16.2      0.8    -11.6
    –N(CH3)2           16.0        -15.4      0.9    -10.5
    –NH–phenyl         14.7        -10.6      0.9    -10.5
    –N(phenyl)2        13.1         -7.0      0.9     -5.6            N
    –NH3+               0.1         -5.8      2.2      2.2
    –NH2+CH(CH3)2       5.5         -4.1      1.1      0.7
    –N+(CH3)3          19.5         -7.3      2.5      2.4         Hal
    –N(O)(CH3)2        26.2         -8.4      0.8      0.6
    –NHCOCH3            9.7         -8.1      0.2     -4.4
    –NHOH              21.5        -13.1     -2.2     -5.3            O
    –NHNH2             22.8        -16.5      0.5     -9.6
    –N=CH–phenyl       24.7         -6.5      1.3     -1.5
    –N=NCH3            22.2         -6.2      0.5     -3.0            N
    –NO                37.4         -7.6      0.8      7.1
    –NO2               19.9         -4.9      0.9      6.1
       –
    –C – N
       –              -16.0          3.5      0.7      4.3            S
    –NC                -1.8         -2.2      1.4      0.9
    –NCO                5.1         -3.7      1.1     -2.8
    –NCS                3.0         -2.7      1.3     -1.0        C       X
    –N+ – N
        –             -12.7          6.0      5.7     16.0
S   –SH                 4.0          0.7      0.3     -3.2
    –SCH3              10.0         -1.9      0.2     -3.6         P Si
    –SC(CH3)3           4.5          9.0     -0.3      0.0
    –S(CH3)2+          -1.0          3.1      2.2      6.3
    –SCH=CH2            5.8          2.0      0.2     -1.8        Natural
    –S–phenyl           7.3          2.5      0.6     -1.5        Products
    –S–S–phenyl         7.5         -1.3      0.8     -1.1
    –S(O)CH3           17.6         -5.0      1.1      2.4        Solvents
    –S(O)2CH3          12.3         -1.4      0.8      5.1
    –S(O)2OH           15.0         -2.2      1.3      3.8
    –S(O)2OCH3          6.4         -0.6      1.5      5.9
              96    4 13C NMR

                    Substituent R       Z1      Z2     Z3     Z4
                    –S(O)2F             4.6     0.0    1.5    7.5
               S    –S(O)2Cl           15.6    -1.7    1.2    6.8
      C
                    –S(O)2NH2          10.8    -3.0    0.3    3.2
                    –SCN               -3.7     2.5    2.2    2.2
                    –CHO                8.2     1.2    0.5    5.8
  C       C    O    –COCH3              8.9     0.1   -0.1    4.4
               ||   –COCF3             -5.6     1.8    0.7    6.7
               C    –COC – CH
                           –
                           –            7.4     1.0    0.0    5.9
  C       C         –CO–phenyl          9.3     1.6   -0.3    3.7
                    –COOH               2.1     1.6   -0.1    5.2
                    –COONa              9.7     4.6    2.2    4.6
                    –COOCH3             2.0     1.2   -0.1    4.3
                    –CONH2              5.0    -1.2    0.1    3.4
                    –CON(CH3)2          6.0    -1.5   -0.2    1.0
                    –COCl               4.7     2.7    0.3    6.6
                    –COSH               6.2    -0.6    0.2    5.4
                    –CH=NCH3            8.8     0.5    0.1    2.3
                    –CS–phenyl         18.7     1.0   -0.6    2.4
      N             –P(CH3)2           13.6     1.6   -0.6   -1.0
               P    –P(phenyl)2         8.9     5.2    0.0    0.1
  Hal               –P+(phenyl)2CH3    -9.7     5.2    2.0    6.7
                    –PO(CH3)2           2.5     1.1    0.1    3.0
                    –PO(phenyl)2        5.8     3.9   -0.1    3.0
      O             –PO(OH)2           -1.9     3.6    1.5    5.6
                    –PO(OCH2CH3)2       1.6     3.6   -0.2    3.4
                    –PS(CH3)2           6.7     2.0    0.2    2.9
      N             –PS(OCH2CH3)2       6.1     2.8   -0.4    3.4
               M    –Li               -43.2   -12.7    2.4    3.1
                    –MgBr             -35.8   -11.4    2.7    4.0
      S             –SiH3              -0.5     7.3   -0.4    1.3
                    –SiH2CH3            4.8     6.3   -0.5    1.0
                    –Si(CH3)3          11.6     4.9   -0.7    0.4
  C       X         –Si(phenyl)3        5.8     7.9   -0.6    1.1
                    –SiCl3              3.0     4.6    0.1    4.2
                    –Ge(CH3)3          13.7     4.5   -0.5   -0.2
  P Si              –Sn(CH3)3          13.2     7.2   -0.4   -0.4
                    –Pb(CH3)3          20.1     8.0   -0.1   -1.0
                    –AsH2               1.7     7.9    0.8    0.0
Natural             –As(phenyl)2       11.1     5.0    0.1   -0.1
Products            –As(O)(OH)2         3.8     1.6    0.8    4.5
                    –SeCH=CH2           0.7     4.7    0.4   -1.4
                    –SeCN              -5.3     5.1    2.9    2.1
Solvents
                    –Sb(phenyl)2        9.8     7.7    0.3    0.0
                    –Hg–phenyl         41.6     9.3   -0.9   -1.6
                    –HgCl              22.5     8.0   -0.6   -0.9
                                          4.5 Aromatic Hydrocarbons            97

Estimation of 13C Chemical Shifts of Multiply Substituted Benzenes
and Naphthalenes (δ in ppm)
The 13C chemical shifts of multiply substituted benzenes and naphthalenes (see       C
next pages) can be estimated using the substituent effects in the corresponding
monosubstituted hydrocarbons.
Example: Estimation of the chemical shifts for 3,5-dimethylnitrobenzene             C        C

                                CH3
                                      3   2                                         C        C
                                              1
                                 4                NO2

                                CH3


C-1    base value      128.5                      C-2   base value   128.5
       Z1(NO2)          19.9                            Z2(NO2)       -4.9
       2 Z3(CH3)        -0.2                            Z2(CH3)        0.7
                                                        Z4(CH3)       -3.0               N
       estimated       148.2
       exp             148.5                            estimated    121.3
                                                        exp          121.7           Hal

C-3    base value      128.5                      C-4   base value   128.5
       Z1(CH3)           9.2                            2 Z2(CH3)      1.4
                                                                                         O
       Z3(CH3)          -0.1                            Z4(NO2)        6.1
       Z3(NO2)           0.9                            estimated    136.0               N
       estimated       138.5                            exp          136.2
       exp             139.6
                                                                                         S

Larger discrepancies between estimated and experimental values are to be expected C          X
if the substituents are ortho to each other or if strongly electron-donating and elec-
tron-accepting groups occur simultaneously.
                                                                                     P Si

                                                                                    Natural
                                                                                    Products

                                                                                    Solvents
              98      4 13C NMR

              Effect of Substituents in Position 1 on 13C Chemical Shifts of Monosubstituted
              Naphthalenes (δ in ppm)

      C
                                      R               for R: H    δC1 = 128.0
                             8            1
                                 9                                δC2 = 125.9
  C       C              7                    2
                         6                    3
                                                                  δC9 = 133.6
                                 10
  C       C                  5        4




                    Substituent R C-1 C-2 C-3 C-4 C-5 C-6 C-7              C-8     C-9    C-10
               C    –CH3            6.0 0.5 0.6 -1.8 0.3 -0.7 -0.5         -4.1    -1.1    -0.2
                    –C(CH3)3       17.9 -2.8 -0.9 -0.6 1.6 -1.4 -1.4       -1.2    -1.6     2.2
                    –CH2Br          4.0 1.1 -0.9 1.3 0.5 -0.1 0.3          -4.6    -2.8     0.1
                    –CH2OH          8.2 -0.9 -0.6 0.1 0.5 -0.3 0.1         -4.5    -2.6     0.0
      N             –CF3           -1.9 -1.3 -1.8 5.0 1.0 0.8 2.0          -3.4     1.0    -3.9
               X    –F             31.5 -16.1 0.1 -3.8 0.1 1.4 0.7         -7.1    -9.3     2.1
  Hal               –Cl             3.9 0.2 -0.2 -0.9 0.2 3.1 0.8          -3.6    -2.8     1.0
                    –Br            -5.4 3.6 -0.2 -0.5 -0.1 0.4 1.0         -1.3    -2.0     0.6
                    –I            -28.4 12.3 1.7 1.7 1.4 1.6 2.6            4.4     1.3     1.3
      O        O    –OH            23.5 -17.2 -0.1 -7.3 -0.4 0.5 0.3       -6.6    -9.3     1.0
                    –OCH3          27.3 -22.3 -0.2 -7.9 -0.7 0.3 -0.9      -6.1    -8.1     0.8
                    –OCOCH3        18.6 -7.9 -0.6 -2.1 0.0 0.4 0.4         -6.9    -6.9     0.9
      N        N    –NH2           14.0 -16.5 0.3 -9.3 0.3 -0.3 -1.3       -7.3   -10.2     0.6
                    –N(CH3)2       23.7 -11.2 0.6 -4.6 1.0 0.4 -0.3        -3.2    -3.9     2.1
                    –NH3+          -3.8 -4.6 -0.9 3.4 1.4 2.1 2.8          -9.0    -7.4     1.2
      S             –NHCOCH3        5.7 -4.4 -0.5 -3.0 0.0 -0.1 -0.3       -5.3    -5.9     0.1
                    –NO2           18.5 -2.1 -2.0 6.5 0.5 1.3 3.4          -5.1    -8.7     0.6
                    –C – N
                       –
                       –          -19.2 5.1 -2.4 3.8 -0.7 0.2 1.2          -4.5    -2.8    -2.2
  C       X
               O    –CHO            2.9 10.8 -1.4 6.7 0.2 0.6 2.7          -3.5    -3.6    -0.3
                    –COCH3          6.9 2.9 -1.7 4.9 0.3 0.4 2.0           -2.0    -3.5     0.2
               ||
  P Si         C
                    –COOH          -1.5 3.6 -2.4 4.3 -0.6 -0.9 0.6         -3.2    -3.2    -0.8
                    –COOCH3        -0.9 4.5 -1.2 5.4 0.7 0.5 1.9           -1.8    -1.9     0.5
                    –CON(CH3)2      6.8 -2.1 -0.8 0.9 0.4 0.4 1.0           0.1    -4.1    -0.2
Natural             –COCl           1.2 10.6 -0.5 9.3 1.9 2.1 4.5          -2.1    -2.1     1.0
Products
                    –Si(CH3)3       9.8 5.1 -0.4 1.7 1.2 -0.8 -0.7          0.1     3.8     0.2

Solvents
                                                 4.5 Aromatic Hydrocarbons                      99

Effect of Substituents in Position 2 on 13C Chemical Shifts of Monosubstituted
Naphthalenes (δ in ppm)

                                                                                                      C
                8          1                       for R: H        δC1 = 128.0
                      9               R
           7                      2                                δC2 = 125.9                       C    C
           6                      3
                    10                                             δC9 = 133.6
                5          4
                                                                                                     C    C



      Substituent R        C-1     C-2     C-3    C-4     C-5     C-6     C-7     C-8     C-9 C-10
 C    –CH3                 -1.3     9.3    2.0   -0.8    -0.5    -1.1    -0.2    -0.6    -0.1 -2.0
      –C(CH3)3             -3.3    22.5   -3.0   -0.4     0.0    -0.7    -0.2    -0.6     0.4 -1.3
      –CH2Br               -1.7     9.0    1.9   -0.4    -0.5     0.7     0.3     0.6    -0.6 -0.7
      –CH2OH               -2.7    12.3   -4.4   -0.1    -0.4*   -0.2*    0.1*   -0.2*   -0.3 -0.8
      –CF3                 -2.0     1.9   -4.2    1.1*    0.1*    2.4*    1.5     1.1    -1.1  1.3   N
 X    –F                  -17.0    34.9   -9.6    2.4     0.0    -0.7     1.1    -0.6     0.7 -3.0
      –Cl                  -1.4     5.7    0.8    1.5    -0.2     0.2     1.1    -1.1     0.7 -1.9  Hal
      –Br                   1.8    -6.2    3.1    1.5    -0.3     0.2     0.8    -1.1    -2.0  0.7
      –I                    9.2   -34.1    9.0    2.3     0.5     1.3     1.5    -0.6     2.1 -0.8
 O    –OH                 -18.6    27.3   -8.3    1.8    -0.3    -2.4     0.5    -1.7     0.9 -4.7   O
      –OCH3               -22.2    31.8   -7.1    1.5    -0.3    -2.2     0.5    -1.2     1.0 -4.3
      –OCOCH3              -9.5    22.5   -4.8    1.3    -0.4    -0.3     0.6    -0.4     0.1 -2.2
 N    –NH2                -20.6    16.7   -8.9   -0.2    -1.6    -4.8    -0.9    -3.5    -0.1 -7.0   N
      –N(CH3)2            -21.1    23.6   -8.8    1.2     0.0    -3.4     0.7    -1.1     2.4 -5.9
      –NH3+                -5.9    -0.3   -6.5    3.2     0.2     2.3     2.0     0.2     0.1 -0.3
      –NHCOCH3            -11.0     9.6   -5.7    0.6    -0.4*   -0.9     1.6*   -1.6     0.2 -3.0
                                                                                                     S
      –NO2                 -3.4    20.0   -6.7    1.7     0.1     4.0     2.2     2.1    -1.1  2.4
      –C – N
         –
         –                  5.8   -16.7    0.1    1.0    -0.2     3.0     1.6     0.2    -1.6  0.7
                                                                                                   C X
 O    –CHO                  6.2     7.9   -3.6    0.8    -0.3     2.9     0.9     1.8     2.4 -1.4
      –COCH3                1.9     8.3   -2.2    0.2    -0.4     2.3     0.7     1.4     1.8 -1.3
 ||   –COOH                 2.7     2.4   -0.6    0.2    -0.3     2.4     0.9     1.3    -1.3  1.5  P Si
 C    –COOCH3               3.0     1.8   -0.5    0.2    -0.1     2.4     0.9     1.4    -1.0  1.9
      –COCl                 2.5     9.1   -0.7    0.2*   -0.4     2.2*    0.8     1.2         -1.4
                                                                                                   Natural
      –Si(CH3)3             5.8    11.9    3.9   -1.0     0.1     0.3    -0.2     0.1    -0.5 0.2
                                                                                                     Products
* Assignment uncertain
                                                                                                     Solvents
              100        4 13C NMR

              4.5.2 Coupling Constants

              13C-1H     Coupling Constants (|J| in Hz)
      C
                             Ha                         In benzene:          In derivatives:
                                                 1J13     159.0
  C       C             13
                             C    Hb                  CH
                                                 2J13 a
                                                      CH     1.0                  1–4
                                                 3J13 b      7.6                  7–10
                                                      CH
                                  Hc             4J13 c     -1.3
  C       C                                           CHd
                             Hd



              13C-13C        Coupling Constants (|J| in Hz)


                    a
                                  1J      57.0                   a                   1J      44.2
                         b           ab                              CH3                ab
                                  2J       2.5                           b           2J       3.1
                                     ac                                                 ac
      N                  c        3J      10.0                                c      3J       3.8
                                     ad                                                 ad
                    d                                                                4J       0.9
                                                                              d
  Hal
                                                                                        ae
                                                                     e


      O       4.5.3 References

              [1] P.E. Hansen, 13C NMR of polycyclic aromatic hydrocarbons. A review, Org.
                  Magn. Reson. 1979, 12, 109.
      N

      S

  C       X


  P Si

Natural
Products

Solvents
                                                                    4.6 Heteroaromatics                     101

4.6 Heteroaromatic Compounds

4.6.1 Chemical Shifts
                                                                                                                    C
13C   Chemical Shifts of Monocyclic Heteroaromatics (δ in ppm)
                                                                                                                   C       C
                 109.9                         107.7                           126.4                   128.8
                  143.0                         118.0                           124.9                   131.0
             O                            N                              S                        Se
                                          H                                                                        C       C


        N        125.4                N        122.3                 N        143.2                    137.6
150.6             138.1    136.2                122.3       152.7              118.6                    126.2
             O                            N                              S                       Te
                                          H


150.0            100.5        133.3            104.7         157.0            123.4          N         147.3
        N         158.9              N          133.3               N          147.8                    135.8
            O                             N                              S
                                                                                             N
                                                                                                  S                    N
                                          H

                                                                                                                    Hal
        N N                           N        147.4                          130.4          N         143.3

             N
                 147.9     147.4
                                          N
                                              N                     N
                                                                         N
                                                                              N              N
                                                                                                  N
                                                                                                       N               O
             H                            H                              H                        H

                                                                                                                       N
        HN       120.1                         109.0        N   126.8                                  103.4
             +                   HN +                         –                              N –        138.5
134.6
             N                            N
                                                135.0 145.1
                                                                         N                       N                     S
             H                            H

                                                                                                                   C       X
 135.9                   148.4                     146.0                     135.6               125.7
            123.7                129.0                      128.6                    128.0                 127.2
            149.8
                          +
                                 142.5
                                                    +
                                                            146.0
                                                                              +
                                                                                     139.6                 139.4    P Si
    N                     N                         N                         N                   N
                          H
                                              I–    CH3 49.8            Cl– OH
                                                                                                  O                Natural
                                              (in ethanol)           (in DMSO)                                     Products

                                                        N                     N                   N                Solvents
            126.5      N                 121.4                144.9                   166.5 N              160.9
N           151.4 158.0                  156.4                           N        N                    N
    N                            N                      N                                         N
              102     4 13C NMR

              Effect of Substituents in Position 2 on 13C Chemical Shifts of Monosubstituted
              Pyridines (δ in ppm)

      C                         4
                                    3
                                                      for R: H     δC2,6 = 149.8
                           5
                                    2                              δC3,5 = 123.7
                           6
  C       C                    N        R                          δC4 = 135.9


  C       C
              Substituent R                   C-2     C-3        C-4       C-5       C-6
               C    –CH3                      8.6    -0.5         0.3     -3.0      -0.7
                    –CH2CH3                  13.7    -1.7         0.4     -2.8      -0.6
                    –CH=CH2                   5.9    -1.3         1.1     -2.5      -0.3
                    –phenyl                   7.7    -1.6         0.8     -3.2       0.2
               X    –F                       13.9   -14.0         5.4     -2.5      -2.0
                    –Cl                       1.8     0.8         2.8     -1.4       0.0
                    –Br                      -7.5     4.6         2.6     -1.1       0.5
      N
                    –I                      -31.6    11.3         1.7     -0.8       1.0
               O    –OH*                     15.5    -3.6        -1.1    -17.0      -8.2
  Hal               –OCH3                    14.3   -12.7         2.6     -7.1      -2.9
                    –O–phenyl                13.9   -12.2         3.5     -5.3      -2.0
                    –OCOCH3                   7.6    -7.3         3.4     -1.8      -1.6
      O
               N    –NH2                      8.4   -15.1         1.8     -9.7      -1.6
                    –NHCH3                   10.9   -16.2         1.5    -11.3      -1.3
      N             –N(CH3)2                  9.6   -17.9         1.2    -12.3      -1.9
                    –NHCOCH3                  1.4    -9.8         2.6     -3.9      -2.1
                    –NO2                      6.9    -5.7         3.9      5.4      -0.8
      S                –
                    –C – N
                       –                    -15.8     4.8         1.1      3.2       1.4
               S    –SH                      30.4    10.7         2.1    -10.6     -12.1
                    –SCH3                    10.2    -4.6         0.0     -2.2      -0.5
  C       X         –S(O)CH3                 16.2    -4.4         2.2      0.9      -0.2
                    –S(O)2CH3                 8.5    -2.6         2.4      3.7       0.3
               O    –CHO                      3.0    -2.0         1.2      4.2       0.4
  P Si              –COCH3                    3.8    -2.1         0.9      3.4      -0.8
               ||   –COOH                    -3.7     0.0         2.5      4.2      -1.7
Natural        C    –COOCH3                  -1.7     1.5         1.1      3.3       0.0
Products            –CONH2                   -0.3    -1.2         1.4      2.8      -1.5
               M    –Si(CH3)3                18.6     5.0        -2.0     -1.1       0.3
                    –Sn(CH3)3                23.3     7.6        -2.7     -1.7       0.6
Solvents
                    –Pb(CH3)3                33.4     9.2        -2.6     -2.3       1.1
              * Keto form (2-pyridone)
                                               4.6 Heteroaromatics        103

Effect of Substituents in Position 3 on 13C Chemical Shifts of Monosubstituted
Pyridines (δ in ppm)

                  4                                                               C
                          R             for R: H      δC2,6 = 149.8
              5
                      3
                                                      δC3,5 = 123.7
              6       2
                  N                                   δC4 = 135.9                C       C


                                                                                 C       C

 Substituent R                  C-2      C-3         C-4      C-5       C-6
 C     –CH3                     1.3      8.9         0.0     -0.9      -2.3
       –CH2CH3                 -0.4     15.4        -0.8     -0.5      -2.7
       –phenyl                 -1.4     12.8        -1.8     -0.3      -1.3
  X    –F                     -11.5     36.1       -13.2      0.8      -3.9
       –Cl                     -0.3      8.1        -0.4      0.6      -1.4
       –Br                      2.1     -2.7         2.7      1.1      -0.9
       –I                       7.1    -28.5         8.9      2.3       0.3          N
 O     –OH                    -10.7     31.3       -12.4      1.2      -8.6
       –OCH3                  -12.5     31.5       -15.9      0.1      -8.4
       –OCOCH3                 -6.5     23.4        -7.0     -0.1      -3.2
                                                                                  Hal
 N     –NH2                   -11.9     21.4       -14.4      0.8     -10.8
       –NHCH3                 -13.6     23.1       -18.2      0.6     -11.9          O
       –N(CH3)2               -14.0     23.3       -17.1      0.1     -11.6
       –C – N
          –
          –                     3.6    -13.8         4.2      0.5       4.2
  S    –SH                    -12.8     26.1       -11.3      7.3      -2.8          N
       –SCH3                  -13.6     24.6       -11.7     10.6      -3.0
 O     –CHO                     2.4      7.8        -0.2      0.5       5.4
 ||    –COCH3                   3.5      8.5        -0.7     -0.2       0.0          S
       –COOH                   -6.4     13.0        11.1      4.3      -6.0
 C     –COOCH3                 -0.6      1.0        -0.5     -1.8       1.8
       –CONH2                   2.7      5.9         1.1      1.2      -1.5      C       X
 M     –Si(CH3)3                2.7      9.1         3.0     -2.3      -1.2
       –Ge(CH3)3                3.9     12.8         4.2     -0.4      -0.1
       –Sn(CH3)3                5.9     13.0         7.1      0.1      -0.3       P Si
       –Sn(n-C4H9)3             6.6     12.6         7.7      0.0      -0.4
       –Pb(n-C4H9)3             7.1     21.7         8.5      0.9      -1.8      Natural
                                                                                 Products

                                                                                 Solvents
              104     4 13C NMR

              Effect of Substituents in Position 4 on 13C Chemical Shifts of Monosubstituted
              Pyridines (δ in ppm)

      C                         R                     for R: H       δC2,6 = 149.8
                                 4
                            5        3
                                                                     δC3,5 = 123.7
  C       C                                                          δC4 = 135.9
                            6        2
                                N

  C       C
                        Substituent R                C-2          C-3       C-4
                         C    –CH3                    0.5          0.7      10.6
                              –CH2CH3                -0.1         -0.5      16.8
                              –CH(CH3)2               0.4         -1.9      21.2
                              –C(CH3)3                0.9         -2.6      23.9
                              –CH=CH2                 0.3         -3.0       8.4
                              –phenyl                 0.4         -2.2      12.2
      N                  X    –F                      2.7        -11.9      32.8
                              –Br                     3.0          3.3      -3.2
                              –I                      0.2          9.1     -30.8
  Hal
                         O    –OH*                   -9.8         -6.2      45.4
                              –OCH3                   0.9        -13.9      29.0
                              –OCOCH3                 1.7         -6.7      23.9
      O                       –NH2                    0.7        -13.8      19.3
                         N
                              –NHCH3                  0.5        -15.9      19.8
      N                       –N(CH3)2                0.6        -16.3      19.2
                              –C – N
                                 –
                                 –                    2.1          2.1     -15.9
                         S    –SH                   -16.9          5.9      54.3
      S                       –SCH3                   0.1         -3.3      14.6
                         O    –CHO                    1.7         -0.7       5.3
                              –COCH3                  1.6         -2.7       6.6
  C       X
                         ||   –COOCH3                 1.0         -0.8       1.4
                         C    –CONH2                  0.4         -0.9       6.2
                              –Si(CH3)3              -2.8          2.4      11.9
  P Si                   M    –Ge(CH3)3              -1.1          4.4      16.8
                              –Sn(CH3)3              -1.1          7.3      16.2
Natural                       –Pb(CH3)3              -0.5          9.1      24.6
Products               * Keto form (4-pyridone)

Solvents
                                                    4.6 Heteroaromatics            105

Estimation of 13C Chemical Shifts of Multiply Substituted Pyridines
(δ in ppm)
The 13C chemical shifts in multiply substituted pyridines can be estimated using the      C
substituent effects in the monosubstituted parent compound.
Example: Estimation of the chemical shifts for 2-amino-5-methylpyridine
                                                                                         C       C
                                          4
                               H3 C
                                              3
                                      5                                                  C       C
                                      6       2
                                          N       NH2



    C-2    base value     149.8                         C-3   base value   123.7
           2-NH2            8.4                               2-NH2        -15.1
           5-CH3           -2.3                               5-CH3         -0.9
           estimated      155.9                               estimated    107.7
           exp            156.9                               exp          108.4
                                                                                             N
    C-4    base value     135.9                         C-5   base value   123.7
           2-NH2            1.8                               2-NH2         -9.7          Hal
           5-CH3            0.0                               5-CH3          8.9
           estimated      137.7                               estimated    122.9             O
           exp            138.6                               exp          122.5

    C-6    base value     149.8                                                              N
           2-NH2           -1.6
           5-CH3            1.3
           estimated      149.5                                                              S
           exp            147.6
                                                                                         C       X

Larger discrepancies between estimated and experimental values are to be expected P Si
if the substituents are ortho to each other and if strongly electron-donating and -ac-
cepting groups occur simultaneously. Also, tautomerization and zwitterion forma-
tion have large effects on 13C chemical shifts.                                        Natural
                                                                                         Products

                                                                                         Solvents
              106      4 13C NMR

              13C   Chemical Shifts of Condensed Heteroaromatics (δ in ppm)


      C                       127.9                               127.6                               139.8
                      121.6                               120.5                               123.8
                                   106.9                               102.1                               124.0
              123.2                               119.6                               124.3
                                          145.0                               124.1                               126.4
  C       C   124.6
                                  O
                                                  121.7
                                                                     N
                                                                                      124.4               S
                      111.8                               111.0      H                        122.6
                              155.5                               135.5                               139.9
  C       C
                              140.1                               137.9                               155.4
                      120.5                               115.4                               125.1
                                  N                                  N                                    N
              125.4                               122.9                               127.5
                                       152.6                              141.5                                   155.7
              124.4                               122.9                               126.9
                                  O                                  N                                    S
                      110.8                               115.4      H                        123.5
                              150.0                               137.9                               135.7

                              122.2                               122.8
                      124.3                               120.4
      N                            147.1                               133.4
              123.0                               120.1
                                      N                                   N
              130.6                               125.8
  Hal                             O                                  N
                                                                     H
                      109.9                               110.0
                              162.7                               139.9
      O
                              118.4                                                                   134.5
                      124.4                                                                   122.1
                                   155.3                                                                   144.5
      N       120.0
                                      O
                                                                                      124.1
                                                                                                              S
              131.1                                                                   128.6               N
                                  N
                      114.7                                                                   121.6
      S                       156.1                                                                   161.5

                                                                  145.5
                              144.4                       119.3                                       155.2
  C       X           111.2                                          N                        121.6
                                  N               123.4                                                   N
              127.2                                                       N           129.0
                                      O           126.8                                                       S
  P Si
                                                                     N
                                  N                                                                       N
                                                          108.8      CH3 33.7
                                                             133.1
Natural
Products                      133.4                               120.7                               128.4
                      119.6                               129.0                               144.8
                                   99.5                                100.5                              N
              117.2                               115.6                                       N
Solvents 110.5                            114.1
                                                  142.1
                                                                              125.5
                                                                                      152.0
                                                                                                                  147.9
                              N
                                                                     N                                    N
                                      113.0                 N                                     N
                      125.6                                          H                                    H
                                                             148.9                                154.9
                                                4.6 Heteroaromatics           107

         128.0                       135.7                   126.9
     127.6   135.7               126.4   120.4           128.0 124.7
126.3             120.8     130.2             142.9 132.2            146.1           C
129.2             150.0     127.2           N       132.1          N
                N                                                     N
     129.2                      127.5   152.4              129.5
         148.1                      128.6                      151.0                C       C

         125.2                       142.8                     126.7
     127.4    155.9              129.6                     126.7    152.0           C       C
                                          N
127.9            N          129.4               144.8 133.1            N
134.1              160.7                                                  N
                N                           N
     128.6
         150.1

         124.2                      122.6                     134.9
                 120.6                      120.0                     121.9
                    122.6                       118.4                     124.6         N
                    127.0                       125.4                     127.0
        O                         N                          S
         156.2
                 111.6            H         110.8                     122.9          Hal
                                    139.6                     138.5

         142.7                      126.6                     116.8                     O
                 114.5          135.8     129.5                       126.7
        O                                                    S
                                                128.3                     121.3
                    120.0
                                                125.5                     125.6
                                                                                        N
                    123.0
        N                         N                          N
        H        112.8                      130.3            H        113.8
            131.8                   149.1                     145.7                     S
         142.2                      144.0                     119.9
                 116.2                      130.9                     127.4*        C       X
        O                          N                         S
                    123.6                       130.2                     124.2

        O                          N                         O
                                                                          126.5*     P Si
                                                                      117.5
                                                              151.9                 Natural
                                                                                    Products
* Assignment uncertain

                                                                                    Solvents
              108             4 13C NMR

              4.6.2 Coupling Constants

              13C-1H          Coupling Constants (|1J| in Hz)
      C
                          a 1J              175            a     1J            169    b           N       1J          206
                               CaHa                                 CaHa                                     C H
                          b 1JC H           202                b 1JC H         183                        1J a a      189
  C       C                     b b                                  b b
                                                                                      b
                                                                                                      a      CbHb
                      O                                N                                      N
                                                       H                                      H

  C       C       b       a     1J
                                   C H      186            a       1J
                                                                        CaHa   194        N       N       1J
                                                                                                               CaHa   209
              a                 1J a a      177
                          N        CbHb            N       N                                          a
                      N                                N                                      N
                      H                                H                                      H
                      a
                                1J          161
                              b 1 CaHa
                                 JC H       163
                              c 1 b b
                      N
                                 JCcHc      178


      N
              13C-13C         Coupling Constants (|1J| in Hz)
  Hal
                          a     1J          69.1           a       1J          65.6                   a   1J          64.2
                                     CaCb                               CaCb                                   CaCb
      O
                          b                                    b                                      b
                      O                                N                                      S
                                                       H

      N               a
                              b 1JC C       53.7
                                1J a b      54.3
                              c   CbCc
      S               N



  C       X


  P Si

Natural
Products

Solvents
                                                                4.7 Halogen Compounds                                109

4.7 Halogen Compounds
The additivity rules for estimating the 13C chemical shifts of various skeletons can
be applied to those haloalkanes that do not have more than one halogen atom at C
a given carbon atom. In all other cases, the simple linear models fail but correc-
tion terms for non-additivity are available for halomethanes and derivatives (see
[1, 2]).                                                                             C C


4.7.1 Fluoro Compounds                                                                                                     C       C
19F (natural abundance 100%) has a spin quantum number I of 1/2. The signals of
carbon atoms up to a distance of about four bonds are split by coupling to 19F.

13C  Chemical Shifts and 19F-13C Coupling Constants
(δ in ppm, |J| in Hz)



CH3 F 71.6                         CH2 F2 109.0                 CHF3 116.4                          CF4 118.5
                                                                                                                               N
          1J                                 1J                             1J                             1J
               CF 161.9                           CF 234.8                       CF 274.3                       CF 259.2
                                                                                                                            Hal
2J                                     2J                         2J     22.4                         28.3
        21.1                                  19.5                     CF
     CF
      16.4
                                            CF
                                            23.6                       23.0
                                                                                    F
                                                                                                                     F         O
                F                                      F                                                            93.5
                                                                                  87.8
          83.7                         9.2         85.2
      1J
         CF 160.1
                             3J
                                  CF   6.7        1J
                                                     CF 163.3
                                                                                  1J
                                                                                     CF 162.1                                  N

                 4J
                      CF ≈ 0 2JCF 18.3                                  116.2
                                                                                                     2J
                                                                                                          CF24.8               S
14.1      31.9        29.3 30.6                                  F3 C        CF3
                                                                                                          88.5
                                             F                                                                        F
                                                                1J          271
      22.7 29.3             25.3 84.2                              CF                                            147.7     C       X
                                                                2J           48.1
                      3J          1
                           CF 6.2 JCF 164.8
                                                                   CF                                      1J
                                                                                                                CF 267.2

                                                                                                                            P Si
1J     177                                   1J     239                                 1J         283.2
     CF                                           CF                                         CF
     78.9                                         108.1                                           115.0                    Natural
                                                                                                                           Products
FH2 C           OH                                F2 HC      OH                               F3 C             OH
            173.5                                            167.2                                              163.0
          O 2J 22                                          O 2J 28                                    O 2J                Solvents
              CF                                               CF                                                 CF 43.6
              110         4 13C NMR

                 F                                     F                              CH2 F 84.9; 1JCF 166.0
                               1J
                     91.0; CF 170.6                        163.3; 1J    245.1                 137.0; 2JCF 16.5
                                                                    CF
                       32.8; 2JCF 19.0                        115.5; 2JCF 21.0                127.8; 3JCF 6.1
      C                23.6; 3JCF 7.6                         130.1; 3JCF 7.8                 128.9; 4JCF 1
                 25.3; 4JCF 1.5                        124.1; 4JCF 3.2                129.0; 5JCF 3
  C       C

                 CHF2 114.8; 1JCF 238.6                CF3 124.5; 1JCF 272.2          F
  C       C            134.4; CF 22.2 2J                      131.0; 2JCF 36.6                168.7; 1JCF 261.8
                       125.5; 3JCF 5.6                        125.3; 3JCF 3.7                  111.8; 2JCF 16.1
                       128.6                                  128.8; 4JCF 1                    152.5; 3JCF 6.4
                                                                                      N
                 130.7                                  131.8; 5JCF ≈ 0


                                122.7; 2JCF 17.7                                 141.3; 3JCF 7.5
                                                F
              124.5; 3JCF 4.3                  159.8; 1JCF 255.1 121.2; 4JCF 4.2               109.7; 2JCF 37.6
      N       145.9; 4J   CF   3.7             138.3; 2JCF 22.5 147.8; 3JCF 14.9
                                           N                                            N        F

  Hal                                                                                     163.7; 1JCF236.3


      O       Estimation of 13C Chemical Shifts of Linear Perfluoroalkanes
              (δ in ppm)
      N                                                 δ = 124.8 + ∑ Zi


      S                             Increments Zi for the CF2 or CF3 substituent in position:
                                          α                    β                     γ
                                         -8.6                 1.8                   0.5
  C       X
              Example: Estimation of the chemical shifts in perfluorobutane

  P Si                                                        CF2         CF3
                                                       F3 C         CF2

Natural        CF3     base value              124.8                       CF2   base value       124.8
Products
                       1 α-CF2                  -8.6                             1 α-CF3           -8.6
                       1 β-CF2                   1.8                             1 α-CF2           -8.6
Solvents               1 γ-CF3                   0.5                             1 β-CF3            1.8
                       estimated               118.5                             estimated        109.4
                       exp                     118.5                             exp              109.3
                                                         4.7 Halogen Compounds                            111

4.7.2 Chloro Compounds

13C   Chemical Shifts of Chloro Compounds (δ in ppm)
                                                                                                                 C
  25.6                              54.0                        77.2                           96.1
  CH3 Cl                            CH2 Cl2                     CHCl3                          CCl4             C       C

                                                             27.3                       34.6
18.9                               26.3                                  Cl                          Cl         C       C
              Cl                            Cl
                                                                      53.7                         66.7
       39.9                  11.6     46.8

31.6                                51.7                     46.3                      105.3
             Cl                                 Cl                       Cl
                                                                                        Cl3 C CCl3
             69.3             Cl                             96.2        Cl
        Cl                                                          Cl

117.2                        113.3         Cl                 Cl           Cl            119.9
                                                                                                       Cl           N
              Cl                           127.1                                        Cl
      126.1                                                          118.1
                                                                                                                 Hal
                                           Cl

  Cl             Cl            Cl           Cl

  117.6
                   125.1                        121.3
                                                                                                                    O
                 Cl            Cl           Cl

40.7                                        63.7                                      88.9                          N
ClH2 C             OH                           Cl2 HC       OH                       Cl3 C        OH
                   173.7                                     170.4                                 167.0
             O                                           O                                     O                    S

  Cl                                  Cl                            CH2 Cl 46.2               CHCl2 71.9        C       X
       59.8                                133.8                         137.8                  140.4
          37.4                               128.9                         128.8                  126.1
             26.1                               129.9                         128.7                   128.6      P Si
 25.4                               126.6                          128.5                     129.7
                                                                                                                Natural
                                                                                                                Products
  CCl3 97.7
                                    135.5                          138.7
       144.8                                     Cl
         126.8             124.3                      122.3                   124.5                             Solvents
                                                131.8
                                                                              151.6
          128.4            148.4                149.5 149.8          N          Cl
                                      N
 130.3
              112          4 13C NMR

              4.7.3 Bromo Compounds

              13C   Chemical Shifts of Bromo Compounds (δ in ppm)
      C
                9.6                          21.4                        12.1                         -28.7
                CH3 Br                       CH2 Br2                     CHBr3                       CBr4
  C       C

                                                                      28.5                    36.4
              19.4                          26.4
  C       C                Br                        Br
                                                                                  Br                         Br
                                                                               44.8                      62.1
                     27.6          13.0        35.6

              31.8                          32.4                      49.4                     53.4
                           Br                            Br                       Br
                                                                                               Br3 C       CBr3
                        40.1           Br                             31.5        Br
                      Br                                                     Br

              122.4                127.2            Br                 Br          Br              109.4
      N                    Br                       97.0                                                      Br
                                                                                              Br
                    114.7                          Br                        116.4
  Hal                                                             25.9                       31.3
                Br          Br          Br           Br           BrH2 C            OH       Br2 HC           OH
                            95.0                      93.7                         172.0                     169.7
      O         112.4       Br          Br           Br                       O                          O


      N         Br                     Br                               CH2 Br 33.4                  CHBr2 41.2
                     52.4                   123.1                            138.0                     141.9
                        38.3                  131.8                            129.2                     126.5
      S                 27.3                  130.7                               128.8                      128.6
               25.6                127.5                              128.7                         129.8
  C       X
                CBr3 36.5              Br
                                                                      138.6                         138.5
                     147.0                  132.7
  P Si                 126.5                  127.0           124.8
                                                                                   Br
                                                                                  121.0
                                                                                           122.6             128.3
                                                                                                             142.3
                        128.1                 152.8           148.9               151.9    150.3     N            Br
Natural                                N                                N
Products       130.1


Solvents
                                                       4.7 Halogen Compounds                             113

4.7.4 Iodo Compounds

13C       Chemical Shifts of Iodo Compounds (δ in ppm)
                                                                                                                C
      -24.0                    -54.0                     -139.9                             -292.5
                                                             CHI3                              CI4
      CH3 I                     CH2 I2
                                                                                                               C       C

                                                       31.2                             40.4
 20.6                       27.0                                    I                                I         C       C
                 I                         I
                                                                20.9                                43.0
          -1.6           15.3      9.1


      3.0                130.3                           I              I                   79.4
                     I                 I                                                                 I
  I                                                                                     I
                               85.2                           96.5


      I                    I                                 CH2 I 5.8                        CHI2 -0.6            N
          31.2                  97.3                           139.2                               145.2
             40.1                  137.4                         128.7                               126.3
                                                                                                                Hal
              28.3                 130.1                            128.7                            128.2
 25.4                     127.4                          127.8                              129.0
                                                                                                                   O
      I
                                  144.8                                 137.6
          105.1
                         126.0
                                                I
                                                         122.9                  135.0                              N
            132.8                              95.2
                                                                                118.2
              150.0      150.1                 156.9     150.8              N    I
                                                                                                                   S
      N                               N




4.7.5 References                                                                                               C       X

[1] G.R. Somayajulu, J.R. Kennedy, T.M. Vickrey, B.J. Zwolinski, Carbon-13
    chemical shifts for 70 halomethanes, J. Magn. Reson. 1979, 33, 559.             P Si
[2] A. Fürst, W. Robien, E. Pretsch, A comprehensive parameter set for the predic-
    tion of the 13C NMR chemical shifts of sp3-hybridized carbon atoms in organic
    compounds, Anal. Chim. Acta 1990, 233, 213.                                    Natural
[3] D.W. Ovenall, J.J. Chang, Carbon-13 NMR of fluorinated compounds using Products
    wide-band fluorine decoupling, J. Magn. Reson. 1977, 25, 361.
                                                                                                               Solvents
              114          4 13C NMR

              4.8 Alcohols, Ethers, and Related Compounds

              4.8.1 Alcohols
      C
              13C    Chemical Shifts of Alcohols (δ in ppm)

  C       C          50.2                   18.2                                25.9                        25.3
                                                      OH                                 OH                            OH
                    CH3 OH
                                               57.8                        10.3    64.2                               64.0
  C       C

              15.2 36.0                     31.2                         23.8 33.6                      26.2
                                 OH                    OH                                   OH                   32.7
                                                                                                                        OH
                20.3 62.9                             68.9          15.3 29.4          63.2
                                                                                                                 73.3


              14.2 31.9 32.9                                               OH                    14.3    39.4 30.5
                                        OH             14.3 28.2            67.2
      N         23.0 25.8            62.1                                                           19.2       10.1
                                                             23.2 39.2      23.5
                                                                                                       72.2 OH
  Hal
                                                                                                         OH
                    63.4                                          36.4
                                OH                     HO                  OH            68.2 (72.7)               OH
      O       HO
                                                                     60.2                     18.7 (23.0) 67.7 (71.6)
                                                                                              in parentheses: in D2O
      N
                                                                                                76.1      72.9
                           OH                                                                          OH      OH
                    73.7                               HO                  OH
                                                                                         66.1
      S       HO                 OH                                                                                     OH
                                                       HO                  OH          HO
                             64.5                                   64.3                                         65.8
                                                             48.3                                OH       OH
  C       X                                                                                        74.3        74.5

                    66.0                                            OH
                                                             75.5                                   HO           OH
  P Si
                                OH
              HO                                       HO                  OH                                  83.3
                             91.2
                            OH                               63.4        91.2                               OH
                                                                     OH
Natural
Products      125.1
                                              99.1                              63.4
              F3 C          OH                                                          OH                            OH
                                              Cl3 C          OH
Solvents             61.4                                                                                             50.0
                                                      75.9           114.9 137.5                   73.8 83.0
              |1JCF|   278
              |2JCF|    35
                           4.8 Alcohols, Ethers, and Related Compounds                                         115

  OH                                   OH                         OH                            103.6
        70.4               65.1                                       157.3           HO                     OH
           35.8                    140.9                                115.7                             157.7
                                     127.3                                                                             C
            25.1                                                        129.9                             108.5
                                         128.7
 26.3                                                           121.1                             131.6
                              127.4
                                                                                                                      C       C
13C    Chemical Shifts of Enols (δ in ppm)

            OH                                       H                                                                C       C
                                                O          O                           O            O
                                       190.5                   190.5                                    201.1
88.0     149.0
                                        22.5        99.0       22.5                        56.6         28.5
            32.8                                    31.0
 28.3               28.3                                       28.3
 46.2               46.2                                       54.2
191.1                191.1                                      203.6
HO                   O                      O                   O
           103.3                                 57.3                                                                     N

4.8.2 Ethers                                                                                                           Hal
13C    Chemical Shifts of Ethers (δ in ppm)
                                                                                                                          O
             60.9           57.6       67.7                59.1       74.5   10.5          54.9
H3 C         CH3           H3 C                          H3 C                              H3 C           72.6
        O                          O
                                          14.7
                                                                  O
                                                                         23.2
                                                                                                    O
                                                                                                               21.4       N
                                                               27.0
59.1
H3 C
            73.4    20.5                  49.4
                                          H3 C
                                                                                58.4
                                                                                H3 C
                                                                                               72.3
                                                                                                         O
                                                                                                                          S
        O                                           O                                      O                   CH3
               32.9 15.0
                                                         72.7
                                                                                                                      C       X
                                                                                    14.2                90.9
52.5        152.7                         57.4       73.1 116.4                                 O
H3 C                                     H3 C
        O           84.4                         O
                                                         134.4
                                                                                       74.6                    26.5    P Si

            55.1                                        54.8                                                          Natural
            CH3                                          CH3                                                          Products
       O                                            O                                       O
           79.2                                         159.9                   156.1
              32.2                                         114.1                                      117.3           Solvents
              24.5                                         129.5                                      128.2
   26.4                                         120.8                                  121.6
              116            4 13C NMR

              13C     Chemical Shifts of Cyclic Ethers (δ in ppm)

                                                                                                                         O
      C           O
                                                 O                                       O                                    69.5
                                                        72.6                                    68.4
                         39.5                                                                                                 27.7
                                                                                               26.5
                                                22.9                                                                  24.9
  C       C
                  O                              O                                       O
                             67.6                          68.1                                  68.5
  C       C                                                46.7                                  27.0
                  O                              N                                       S
                                                 H


                             O                         O                                         O                    O
              145.6                  68.6                      75.3             144.1                   64.8                 141.1
                98.4                28.5                      126.3              99.4                   22.6                 101.1
                                                                                               19.4

              13C     Chemical Shifts of Acetals, Ketals, and Ortho Esters (δ in ppm)
      N
                                                      99.9
  Hal                            53.7          24.9               48.1                  95.0                   108.8 147.8
                             O CH3             H3 C         O CH3                                                        O
                                                                                                      121.8
                                                                                    O        O
              109.9                                                                                                          100.7
      O                      O CH3             H3 C         O CH3                              64.5                      O


      N           94.8                                                                         51.1
                                                                                         O CH3                           O
              O          O                  O          O
                                                                                O                                 O
      S                      67.5
                                                 O
                                                           93.7          H3 C            O CH3                           O
                                                                                                                             59.5
                  27.5                                                       115.0                               112.9
                                                                                                                              15.2
  C       X
                          121.0                                           119.7                14.8
                                        50.4
  P Si        H3 C O                O CH3                                O          O
                                                                                          58.3
              H3 C O                                                     O          O
                                    O CH3
Natural
Products

Solvents
                                                 4.9 Nitrogen Compounds                           117

4.9 Nitrogen Compounds

4.9.1 Amines
                                                                                                         C
13C   Chemical Shifts of Amines and Ammonium Salts (δ in ppm)

The protonation of amines causes a shielding of the carbon atoms in the vicinity of C                           C
the nitrogen. This shielding amounts to -2 ppm for an α carbon atom, -3 to -4 for a
β carbon, and -0.5 to -1.0 ppm for a γ carbon. The most frequent exceptions occur
in branched systems: Tertiary and quaternary carbon atoms in the α-position are C                               C
generally deshielded by protonation of the nitrogen (Δδ = +0.5 to +9 ppm) [1]. In
the following, shifts induced by protonation (δamine hydrochloride - δamine, measured
in D2O) are given in parentheses.
                        38.2 (-2.0)                  47.6 (-1.2)
28.3 (-1.8)             H3 C                         H3 C                          56.5
H3 C NH2                        NH                          N CH3                  (CH3 )4 N+ I–
                        H3 C                         H3 C

                       15.7 44.5                12.9 51.4                                                   N
19.0 (-5.0)            (-3.2) (-0.6)            (-1.7) (+1.3)                             55.4 9.5
           NH2                                                                                           Hal
                                 NH                           N                           N+ I-
   36.9 (-0.2)

                                                                                                            O
  27.4
  (-5.4)
               NH2     24.0          NH                                                   N+ I-             N
                                               21.3
                                                         N                  16.0
                       (-2.6)
11.5 44.6                                                                            60.4
                                 52.4                 56.8
(-0.4) (-1.8)
                        12.0     (-1.4)       12.0                          10.9                            S
                        (-0.5)

26.5                                                 32.9                                               C       X
(-4.9)                           H     22.8          (-4.7)
           NH2                   N                                NH2
         43.0                          45.7                       47.2                                   P Si
         (+2.2)                                                   (+5.7)
                            (in D2O)
                                                                                                        Natural
                                                                            57.4                        Products
                                     HO
      64.2                                    51.3                  HO      (-1.0)
      (-5.4)                         60.5                          60.3                     OH
                 NH2                           NH                                                       Solvents
 HO                                                                (-3.5)     N
           44.6
           (-1.9)                    HO                             HO
              118          4 13C NMR

              14.3                        23.2                    22.5                           28.2
              (-2.6)       H              (-2.9)    H             (-3.1)      H                  (-1.2)    H
                           N                        N                         N                            N
                                                        CH3
      C              45.9 35.2
                                 CH3
                                        12.5 54.0 36.1
                                                                                  CH3                           CH3
                                                                                  33.9                         28.5
                     (-0.4) (-1.8)      (-0.9) (-2.1) (-2.0)     50.5             (-2.5)     50.4              (-2.7)
                                                                 (+1.9)                      (+6.6)
  C       C
              12.8                        20.6                    18.7                           25.4
                            CH3                     CH3                       CH3                          CH3
              (-2.1)                      (-2.0)                  (-1.3)                         (-0.8)
  C       C                 N                       N                         N                            N
                                 CH3                    CH3                       CH3                           CH3
                 53.6   44.6            11.9 61.8 45.2                            40.9                       38.7
                 (+0.5) (-1.3)          (-0.8) (-1.6) (-1.2)     55.5             (-0.8)     53.6            (+0.2)
                                                                 (+3.8)                      (+8.9)
                                                                        CH3
                                    H                                                                 44.8
              H3 C                  N               H3 C                N                                      NH2
                       N                CH3                 N               CH3
                       H       51.2
                                36.6                             57.2 46.1
                               (-3.0;                       CH3 (-2.6;                       113.6 139.9
                                (-1.3;                                (-1.0;
      N                        -2.7*)
                                -0.5*)                        -2.3*) -0.2*)
              * doubly protonated form              * doubly protonated form
  Hal
                                                           CH3 33.5 (-1.5)          H3 C         CH3 41.1 (-0.7)
                     NH2                           HN                                       N
      O             51.1 (+0.7)                       58.7 (+0.6)                             64.3 (+2.4)
                        37.6 (-5.4)                       32.7 (-2.7)                             29.2 (-1.6)
                        25.8 (-1.0)                       25.7 (-0.3)                             26.5 (-0.9)
      N
                 26.3 (-1.1)                       26.8 (-0.7)                             26.9 (-1.2)

      S                                                    CH3 30.2                 H3 C         CH3 39.9
                     NH2                           HN                                        N
                       146.7                            149.9                                    151.0
  C       X              115.1                            112.3                                    113.1
                         129.3                            129.3                                    129.4
                118.5                              116.9                                   117.0
  P Si

Natural
Products 46.3              NH2
                                                     HN                                          N
                       143.4                               143.2                                     141.6
Solvents                 127.1                               117.9                                     121.5
                         128.3                               129.4                                     129.4
                126.5                               118.0                                    122.9
                                               4.9 Nitrogen Compounds                119

13C    Chemical Shifts of Cyclic Amines (δ in ppm)

                                     48.6                                        46.4
         H                                             H                                     C
         N                       N                     N                     N
               18.2                   28.5                   45.3                  57.7
                                                      19.3                  17.5            C       C
                                     42.7              H
                                                                                 47.7
         H
         N                       N                     N                     N
                47.1                   56.7                  47.9                  57.2     C       C
               25.7                   24.4                   27.8                  26.4
                                                      25.9                  26.4

             45.9                                      H
                                 H                                           H
         N                       N                     N                     N
51.7            54.2                   46.7                  47.9                  49.2
26.2            125.0                  68.1                                          31.3
                                 O                     N
        124.3                                          H                     27.2
                                                                                                N

                                                                                             Hal

4.9.2 Nitro and Nitroso Compounds                                                               O
13C    Chemical Shifts of Nitro and Nitroso Compounds (δ in ppm)
                                                                                                N
   61.2                   12.3                   21.2                20.8
                                                             NO2                 NO2
                                                                                                S
   CH3 NO2                            NO2
                                               10.8 77.4                      78.8
                             70.8

                                                                                            C       X
13.3    29.6                                                         26.9
                                      NO2                                        NO2
                    NO2   10.1          85.0    28.2
                                                                              85.2
                                                                                             P Si
                                                             NO2
   19.8 75.6
                             28.6       18.7   19.6     82.9

                                                                                            Natural
                                                                                            Products
        NO2                      NO2                   NO2                   NO
          87.0                       84.6                  148.4                 165.9
             32.6                       31.4                 123.6                 120.8 Solvents
             24.8                       24.7                 129.4                 129.3
                            25.5                  134.6                 135.5
              120         4 13C NMR

              4.9.3 Nitrosamines and Nitramines

              13C    Chemical Shifts of Nitrosamines (δ in ppm)
      C
                                                                   11.3
              32.1                  11.5 38.4                                                              45.4
              H3 C
                              O                            O                   45.2       O
                                                                                                   19.1
                                                                                                                            O
  C       C                                                        20.3
                     N    N                     N      N                      N       N                           N     N
                                                                   22.5
              H3 C                                                             54.2                23.7
  C       C   39.9                  14.5 47.0                                                              51.1
                                                                   11.8

              13C    Chemical Shifts of Nitramines (δ in ppm)

              32.5                           41.5   NO2            40.0 H3 C
              H3 C–NH–NO2                  H3 C N                                 N NO2
                                                    NO2                    H3 C



      N       4.9.4 Azo and Azoxy Compounds

              13C    Chemical Shifts of Azo and Azoxy Compounds (δ in ppm)
  Hal
                                   152.7                                                  144.0
               130.9                                                  129.5                                122.3
      O        129.0               N
                                         N
                                                                      128.7                   N+
                                                                                                   N
                                                                                                                      128.7
                          122.8                                                   125.5
                                                                                              O–                      131.5
                                                                                               148.3
      N
              4.9.5 Imines and Oximes
      S
              13C    Chemical Shifts of Imines and Oximes (δ in ppm)

  C       X      22.6                                                                                        41.3
                                                                                       169.2           N
                 H3 C                          29.3                                    128.5                128.1
              154.2           N   29.7         163.4           N
                                                                    23.6       128.1                                   127.7
  P Si                H
                          56.6                 17.8
                                                                   50.6        129.7                                   129.7
                                                                                              139.8 136.4
Natural
Products
                 128.8 128.8                                                 128.3 127.2 17.3
                                       H
                                           120.9 129.2                                        119.4 128.9
              131.4                                                       130.4
Solvents
                                       N               125.9                              N           123.2
                          136.3 160.4                                             139.5 165.3
                                     152.1                                                   151.7
                                                            4.9 Nitrogen Compounds                           121

11.2                                                 13.6
               OH            H           OH                    27.1                              H             OH
H3 C                                                                       OH
                                                                                                        N
          N                         N                  19.6                              20.2
                                                                       N                               152.3         C
  H 147.8                  H3 C 148.2
                                                               H 151.9                          31.5
                           15.0                                                     13.9
                                                                                                                    C       C
                                             OH             155.9 OH                       154.3
15.0 H3 C            OH                  N                  H3 C      N                   H3 C         N
                                             159.4                                                           OH     C       C
                 N                                      12.4                             21.4
                            32.3               27.5                 136.5                             134.0
21.7 H3 C 155.4
                                                                      126.0                             128.0
                            26.3               26.1
                                                                      128.5                             128.0
                                    24.6
                                                               129.1                            129.0


4.9.6 Hydrazones and Carbodiimides

13C    Chemical Shifts of Hydrazones and Carbodiimides (δ in ppm)
                                                                                                                        N

          30.6
                            25.1                             22.6
                                                                                  13.7
                                                                                                40.5
                                                                                                                     Hal
          40.9
                                                                                   20.1
 159.6         N       164.6        N                    167.2    N                    167.2           N
                                         N           19.7           N                                                   O
          37.2 NH2          18.0                             33.1                          16.2
                                                                                                           N

        29.3                         47.1            14.2              47.0                             46.5
                                                                                                                        N

                   112.8 128.9                                                      112.8 128.9                         S
            N                                                                N
            HN                   119.0                                       HN                      119.0
                                                                                                                    C       X
                   143.2                                                           140.7

                                                                                                                     P Si
                                                                                     35.0 24.8
               140.2           24.8                                       139.9
                                                                                                                    Natural
            N C N             49.0                                  N C N                            25.5           Products
                                                                                  55.7

                                                                                                                    Solvents
              122         4 13C NMR

              4.9.7 Nitriles and Isonitriles

              13C    Chemical Shifts of Nitriles (δ in ppm)
      C                                                                                                        123.7
                     1.7 117.4               10.6         120.8                19.0* 119.9           19.9
                     CH3 CN                                CN                           CN                      CN
                                                                                                       19.8
  C       C                                         10.8                 13.3 19.3*
                                                                         * assignment uncertain
                                              28.5        125.1                   110.5                           118.0
              13.2     21.9 119.8
  C       C                       CN                       CN               NC          CN                           CN
                   16.8 27.4                              28.1                    8.6
                                                                                                     NC
                                                                                                              14.6


                                             131.2         119.2                     CN 122.4                CN 118.7
               137.5      117.2
                            CN
                                                           CN                         28.3                     112.5
                                                          118.2                          30.1                    132.0
                      107.8                           CH3
                                                                                         24.6                    129.2
                                                     20.7
                                                                                 25.8                       132.8
      N       13C  Chemical Shifts and 13C–14N Couplings of Isonitriles (δ in ppm,
              |J| in Hz)
  Hal
              Because of the symmetrical electron distribution around the nitrogen atom, the 13C-
              14N coupling can be observed in the 13C NMR spectra of isonitriles, leading to trip-

      O       lets with intensities of 1:1:1 (spin quantum number of 14N: I = 1, natural abundance,
              99.6%).
              2J7.5 1J 5.8             3J≈0         1J5.3           3J≈0        1J5.0
      N        26.8 158.2              15.3         156.8           120.6       165.7
                                                                                                    NC 165.7; 1J 5.2
                                                                                                      126.7; 1J 13.2
                   CH3 NC                             NC                         NC                     126.3; 2J ≈ 0
      S                                       36.4                         119.4                       129.9; 3J ≈ 0
                                              2J
                                               6.5                        2J11.7
                                                                                                129.4; 4J ≈ 0
  C       X   4.9.8 Isocyanates, Thiocyanates, and Isothiocyanates

              13C    Chemical Shifts (δ in ppm)
  P Si                                                                                                       NCO 124.9
              26.3     121.5           13.6        34.2      125 (broad)        110.7     124.2                133.6
Natural         CH3 NCO                                      NCO                         NCO                     124.8
Products                                    20.4     43.3                            124.7                       129.6
                                                                                                          125.8
Solvents                  111.8             130.4                  29.3 128.7
              15.4                                                                      13.3    32.3        131 (broad)
                          SCN          SCN– NH4 +                   CH3 NCS                                 NCS
                   28.7                                                                      20.0    45.0
                                                             4.10 Sulfur Compounds                             123

4.10 Sulfur Compounds

4.10.1 Thiols
                                                                                                                      C
13C    Chemical Shifts (δ in ppm)

   6.5                                                                                      27.4                     C       C
                              19.7                               27.6                                     SH
       CH3 SH                           SH                                   SH
                                                                                                        29.9
                                     19.1                  12.6       26.4                                           C       C

12.0     35.7                 35.0                           22.2       33.9
                       SH                   SH                                      SH                  31.8 SH
                                        41.1
   21.0      23.7                                      14.0 30.6             24.6           28.1        38.8


14.0     31.4 34.1                                    28.7                                       64.2
                              SH                                  SH                                      SH
                                                 HS                                        HO
   22.6       28.1 24.7                                                                             27.3
                                                                                                                         N

                                                                                                                      Hal
                                                                          SH
        SH                            SH                         28.8                               SH
            38.3                        38.5                             141.0                          130.6
               37.7                        38.5                            127.9                          129.2
             24.6                         26.8                             128.5                          128.8          O
                                     25.9                            126.8                        125.3
                                                                                                                         N
4.10.2 Sulfides

13C    Chemical Shifts (δ in ppm)                                                                                        S
                                                                                                        23.6
            19.3                    25.5                             34.3 13.7
H3 C        CH3                                                                                               33.4   C       X
        S                       S                                S
                                       14.8                             23.2                        S


                                                                 33.2
                                                                                                                      P Si
                       34.1 22.0                                                    15.5        34.1 22.0
                                                      45.6                        H3 C
                   S
                            31.4 13.7                  S                                   S                         Natural
                                                                                                   31.4 13.7 Products

            54.8                                      28.0                                         59.2
                                                                  30.9               14.4 S               S          Solvents
        S          S                              S          S                           H3 C                  CH3
                       23.2                                43.1                                     S
        30.4                                                                                H3 C
              124            4 13C NMR

                    25.4 132.3                                                  141.8
                              S                                             S                                     72.6 81.4
              14.2                   110.5                                        106.9                       S
      C

                             CH3 15.6
  C       C          S
                         138.5                           S
                           126.6
                                                             135.8
  C       C                128.7                               131.0
               124.9                                           129.1
                                                    127.0

              13C    Chemical Shifts of Cyclic Sulfides (δ in ppm)


                                                   S                             S                                S
                S
                                                           26.0                            18.6                        31.7
      N                      18.7                                                S                                    31.2
                                                  28.0
  Hal
                S                                  S                             S                                S
                             39.1                            34.4                          29.3                           27.0
                                                                                           28.2                           68.5
      O                  128.8             38.1        S
                                                                                                                  O
                                                                                26.9

      N         S                                  S                             S                                S
                             29.1          27.9              69.2                          31.9                           33.9

      S         S
                                           26.4          O               26.6          S                  S           S
                                                  69.7                           29.8

  C       X

              4.10.3 Disulfides and Sulfonium Salts
  P Si
              13C    Chemical Shifts of Disulfides (δ in ppm)
Natural
Products                                                                                              136.0
                                    22.0                          32.8
                         S          CH3                  S                                        S
              H3 C            S                               S
                                                                     14.5                             S               127.4
Solvents
                                                                                                      127.2        129.3
                                                              4.10 Sulfur Compounds                      125

13C    Chemical Shifts of Sulfonium Salts (δ in ppm)

                                                                                   134.0        130.1
                                                                     22.4                                        C
       27.5
                                                                     CH3                            131.0
                                            I–                              I–                         7.1
       CH3                                                           S+
             I–                                  26.9 13.6                  37.8                                C       C
       S+                             S+                                            126.9          S+
H3 C        CH3                                                             20.5                    22.1
                                         39.8      21.8
                                                                    22.7                                BF4 –   C       C

4.10.4 Sulfoxides and Sulfones

13C    Chemical Shifts of Sulfoxides and Sulfones (δ in ppm)


                                                              O
                                                                                       O         CH3 43.9
       O                     O                                                              S
        S                    S                                S                                 146.1
                                                                    49.0                                            N
H3 C        CH3                       54.3                                                        123.5
            40.1                                                    19.3                          129.6
                                     25.4
                                                          25.3                             130.9
                                                                                                                 Hal


    O O                       O O                         O O                              O O
                                                                                                                    O
                                            6.7               16.3                                       15.2
     S                         S                           S                                S
                                                                                                                    N
H3 C   CH3                H3 C                        H3 C                             H3 C
                                     48.2                          56.3 13.0                            53.5
            42.6          39.3                        40.3                             37.1


                                                                                                                    S
    O O                      O       O               O        O                    O       O 127.6
                   22.7
     S                           S                        S
                                                                  52.6
                                                                                       S                        C       X
H3 C                                     51.1                                                           129.3
34.2          57.6                                                25.1                                  133.2
                                       22.7                                        141.6
                                                      24.3                                                       P Si

                                                                                                                Natural
                                                                                                                Products

                                                                                                                Solvents
              126         4 13C NMR

              4.10.5 Sulfonic and Sulfinic Acids and Derivatives

              13C Chemical Shifts of Sulfonic and Sulfinic Acids and Derivatives (δ
      C       in ppm)


              39.6                    8.0                          18.8                      16.8                          25.0
  C       C                                                                                                 SO3 H                      SO3 H
              CH3 SO3 H                        SO3 H                              SO3 H
                                        46.7                  13.7       53.7                           52.9                        55.9
  C       C
              52.6                    9.1                          18.4                      17.1                          24.5
                                               SO2 Cl                              SO2 Cl                   SO2 Cl                     SO2 Cl
              CH3 SO2 Cl
                                        60.2                  12.1       67.1                           67.6                        74.2


                                              O
                                                                                                   O        O                 O        O
                O                             S                    O         O                          S                          S
                      13.7 51.8                    S                             18.2       59.8                S      48.4              O
                S                                                        S
                      S    15.5                        25.5                  S              25.1                       22.9
      N       42.7                                              48.7                                            35.3                     74.6
                                            23.3                                                    26.2                          23.5
  Hal                                                   O
                                                              CH3 56.5

                 SO3 H                                  SO2                                SO2 Cl                          SO2 NH2
      O              143.5                                  135.2                           144.1                            139.3
                       126.3                                  128.0                           126.8                            125.5
                       129.8                                  129.4                           129.7                            128.8
      N        132.3                               134.0                                135.3                          131.7


      S
              4.10.6 Sulfurous and Sulfuric Acid Derivatives
  C       X   13CChemical Shifts of Sulfurous and Sulfuric Acid Derivatives (δ in
              ppm)
  P Si                        O
                                                                    O                                    O
                                                                                                            S
                                       58.3                          S                              O           O
                              S                                O         O
Natural               O           O                                                                                 57.1
Products                                    15.4
                                                                         67.6                           26.0

Solvents                  O       O     59.1
                                                                O        O
                                                                                 69.6
               H3 C           S         CH3                          S
                      O           O                            O             O
                                                                                    14.5
                                                                  4.10 Sulfur Compounds                                   127

4.10.7 Sulfur-Containing Carbonyl Derivatives

13C    Chemical Shifts (δ in ppm)
                                                                                                                                  C
The 13C chemical shifts of thiocarbonyl groups are higher by about 30 ppm than
those of the corresponding carbonyl groups:
                                         δC=S ≈ 1.5 × δC=O - 57.5                                                                C       C
Carbonyl groups of thiocarboxylic acids and their esters are deshielded by about 20
ppm with respect to the corresponding oxygen compounds.                             C                                                    C


        S                       S                                  O                              O
252.7                  278.4                            194.5                            194.1            28.4       22.2
H3 C         CH3                                        H3 C            SH               H3 C         S
41.8                                                    32.6                             30.1                 32.1        13.6
                   33.0
                               53.7

                                                                                                                                     N
        S                            S                                          S                                S        44.3
                                              20.6
232.8                     234.1                                   205.6                               199.4
H3 C         SH              H3 C         S
                                               CH3
                                                                   H3 C                 NH2           H3 C            N
                                                                                                                          CH3
                                                                                                                                  Hal
42.1                         39.2                                  33.3                               32.7            CH3
                                                                                                                     42.3
                                                                                                                                     O
  S         NH2                               206.7                                       196.5
                                                        S                                             S
202.1                                       49.6                                         41.3                 40.7 118.2
         140.1                                                                                                                       N
           128.1                                   N          S–
                                                                       Na   +
                                                                                                  N       S
                                      12.3                                                                           132.8
           128.8                                       49.6
   132.1                                    12.3
                                                                                              45.2                                   S
                                                   (in D2O)
                                                                                                                                 C       X

   226.2                            183.8                                194.0
20.2     S                                    S                        43.2
                                                                               S                                                  P Si
 H3 C                  CH3                                             H3 C                       CH3
         S         S                 H2 N          NH2                              N         N
                                                                                                                                 Natural
                                                                                    CH3       CH3
                                                                                43.2
                                                                                                                                 Products

                                                                                                                                 Solvents
              128      4 13C NMR

              4.11 Carbonyl Compounds

              4.11.1 Aldehydes
      C
              Additivity Rule for Estimating the 13C Chemical Shifts of Aldehyde
              Carbon Atoms (δ in ppm)
  C       C
                                                δC=O = 193.0 + ∑ Zi
  C       C
                                                    –Cβ–Cα–CHO

                              Substituent i               Zα                   Zβ
                              –C                          6.5                  2.6
                              –CH=CH2                    -0.8                  0.0
                              –CH=CH–CH3                  0.2                  0.0
                              –phenyl                    -1.2                  0.0

      N

  Hal         13C   Chemical Shifts of Aldehydes (δ in ppm)

      O         197.0                31.3 200.5                              202.7              201.6
                                                                5.2                    15.7
               H2 C O               H3 C CHO                                 CHO                 CHO

      N                                                               36.7           13.3 45.7


      S       15.5    204.6
                       CHO       13.8 24.3       201.3          23.4         205.6
                                                                             CHO        95.3 176.9
                                                 CHO                                   Cl3 C CHO
                     41.1                                               42.4
                                    22.4 43.6
  C       X

                                                                       CHO 204.7              CHO 192.0
  P Si                194.4                   176.8                      50.1                  136.7
                       CHO                    CHO                           26.1                  129.7
Natural 137.8 138.6               83.1 81.8                                 25.2                  129.0
Products
                                                                      25.2               134.3

Solvents
                                                      4.11 Carbonyl Compounds                          129

4.11.2 Ketones

Additivity Rule for Estimating the 13C Chemical Shifts of Ketone Car-
bon Atoms (δ in ppm)                                                                                           C

                                       δC=O = 193.0 + ∑ Zi
                                                                                                              C       C
                                              O
                                              ǁ
                                       –Cβ–Cα–C –Cα–Cβ–                                                       C       C

                   Substituent i                    Zα                Zβ
                   –C                               6.5               2.6
                   –CH=CH2                         -0.8               0.0
                   –CH=CH–CH3                       0.2               0.0
                   –phenyl                         -1.2               0.0


                                                                                                                  N
13C    Chemical Shifts of Ketones (δ in ppm)

                                                                                                               Hal
206.7                   207.6                         206.6                           211.8
        O                       O                             O                                  O
                                       7.0                           17.5                              18.2
H3 C         CH3        H3 C                          H3 C                            H3 C                        O
                                    35.2                          45.2 13.5                           41.6
30.7                    27.5                          29.3                                27.5

                                                                                                                  N
206.8                           213.5                        210.7                    215.1
        O                                  O                         O                           O
               31.9 14.0                           26.5                      8.0                       17.8
H3 C                            H3 C
                                                                                                                  S
            43.5 23.8                  44.3                              35.5                         38.0
29.4                            24.5
                                                                                                              C       X
218.0                  197.5                          183.6                           207.9
        O                       O                             O                                  O   21.1
                28.6                   128.0
                                                                     81.9                                      P Si
                        H3 C                          H3 C                            H3 C
        45.6                        137.1             32.4                  78.1      29.9
                       25.7
                                                                                                     10.3     Natural
                                                                                                              Products
209.4                               196.9                                     195.2
        O                                      O                                      O
               29.0                                 128.6                                    130.1            Solvents
H3 C                   26.6          H3 C                    128.4                                   128.2
27.6                   26.3         25.7                     132.9                                   132.2
       51.5                             137.4                                      137.8
              130         4 13C NMR

              13C    Chemical Shifts of Halogenated Aliphatic Ketones (δ in ppm)

              203.5                          197.4                        187.5          115.6          172.9          114.4
      C               O                              O                            O                              O
                                 F                            F                              F          F                  F
              H3 C                           H3 C                         H3 C
                          84.9                               109.8                           F          F                  F
  C       C   25.1                           23.4        F                23.1          F                   F         F


              200.1                          193.6                        186.3                         175.5
  C       C           O                              O                            O      96.5                    O     90.2
                                 Cl                           Cl                             Cl        Cl                  Cl
              H3 C                           H3 C                         H3 C
                          49.4                               70.2                            Cl        Cl                  Cl
              27.2                           22.1        Cl               21.1          Cl                  Cl        Cl


              199.0                          203.5                        187.5          115.6
                      O                              O                            O
                                 Br                           Br                             Br
              H3 C                           H3 C                         H3 C
                          35.5                               84.9                            Br
              27.0                           25.1                         23.1
      N                                                  Br                             Br


  Hal
              13C    Chemical Shifts of Cyclic Ketones and Quinones (δ in ppm)
      O
                O                             O                                   O                              O
                     208.9                        219.1                               209.7                          214.9
                                                                                                                        43.9
      N               47.8                          38.2                                41.5
                                                     23.4                               26.6                             24.5
               9.9
                                                                                 24.6                            30.6
      S
                O                             O                                   O                              O
  C       X          155.1                        209.8                               199.0                          185.8
                                      34.0          134.2               38.2            129.9                           127.3
                      158.3
                                      29.1           165.3              22.9                150.6                       156.7
  P Si                                                                           25.8                                   37.9
                                                                                                                     26.7
Natural
                                                                                                        131.8
Products        O                                                 O                                           O
                     187.0                                            180.4                         126.2       184.7
                                                         O
                        136.4                                            130.8               133.7                     138.5
Solvents
                                                                         139.7

                O                                                                                                O
                                               4.11 Carbonyl Compounds                           131

13C    Chemical Shifts of Diketones (δ in ppm)

197.7                            201.1                                 206.9
        O                                 O        O                           O                        C
                 CH3                                                                             CH3
H3 C                               H3 C                  CH3           H3 C
23.2                             28.5       56.6                       29.6      37.0
            O                                                                                O         C       C
                              Enol form: see Chapter 4.8.1

                                                                                                       C       C
4.11.3 Carboxylic Acids

Additivity Rule for Estimating the 13C Chemical Shifts of Carboxyl
Carbon Atoms (δ in ppm)

                                    δC=O = 166.0 + ∑ Zi

                                    –Cγ–Cβ–Cα–COOH
                                                                                                           N
              Substituent i               Zα                Zβ            Zγ
              –C                      12.0                 3.0           -1.0                           Hal
              –CH=CH2                  5.0                 0.5           -1.5
              –phenyl                  6.0                 1.0           -2.0
                                                                                                           O

13C    Chemical Shifts of Carboxylic Acids (δ in ppm)                                                      N
       166.3           20.8 178.1                  8.9         181.5               18.4      180.7
H COOH                 H3 C COOH                              COOH                           COOH          S
                                                       27.6                   13.6    36.2

                                                                        30.6                           C       X
18.8     184.1       14.2 27.7      180.6          27.0        185.9                         179.4
         COOH                       COOH                      COOH                           COOH
       34.1                                                38.7           29.6
                        22.7 34.8                                                     47.9              P Si

                                                                                                       Natural
            172.0                156.5                    182.1                      172.6             Products
            COOH                 COOH                     COOH                       COOH
                       78.6 74.0                           43.7                       130.6
133.2 128.1                                                   29.6                       130.1         Solvents
                                                              26.2                       128.4
                                                       26.6                        133.7
              132        4 13C NMR

              13C    Chemical Shifts of Halogenated Carboxylic Acids (δ in ppm)


      C       115.0 163.0                   40.7 173.7              63.7 170.4           88.9 167.1
              F3 C     COOH             ClH2 C COOH               Cl2 HC COOH            Cl3 C COOH

  C       C
              13C    Chemical Shifts of Dicarboxylic Acids (δ in ppm)
  C       C
              160.1                 169.2              173.9              166.1                 166.6
              COOH                  COOH               COOH               COOH                  COOH
                             40.9              28.9               130.4              134.2
              COOH
                                    COOH               COOH               COOH     HOOC




      N       13C    Chemical Shifts of Carboxylate Anions (δ in ppm)

              Measured in water unless indicated otherwise.
  Hal
                                     24.4 182.6                 11.1 185.1
      O             171.3            20.8* 177.6*               10.6* 181.3*      20.2     184.8
              H     COO–             H3 C    COO–                     COO–                 COO– Na+

                                     * in CDCl3                     31.5      14.2 40.5
      N                                                             28.4*       (in DMSO)
                                                              * in CDCl3/DMSO

      S
                     181.8                            188.6               174.5           COO– 185.4
                  COO– Na+                            COO–                COO–              47.2
  C       X       36.1                                                                         30.9
                                                                  126.7 134.3
               20.5                                                                            26.9
  P Si         (in DMSO)                                                                 26.9

Natural
Products
                  COO– 177.6
                     138.2                  45.0 175.9             65.6 171.8              96.2 167.6
Solvents                133.1           ClH2 C COO–               Cl2 HC COO–             Cl3 C COO–
                        130.7
               133.1
                                                     4.11 Carbonyl Compounds                              133

4.11.4 Esters and Lactones

Additivity Rule for Estimating the 13C Chemical Shifts of Ester Car-
bon Atoms (δ in ppm)                                                                                              C

                                          δC=O = 166.0 + ∑ Zi
                                                                                                                 C       C
                                      –Cγ–Cβ–Cα–COO–Cα' –
                                                                                                                 C       C
      Substituent i                   Zα             Zβ                 Zγ                 Zα'
      –C                             12.0            3.0               -1.0            -5.0
      –CH=CH2                         5.0                                              -9.0
      –phenyl                         6.0            1.0                               -8.0



13C    Chemical Shifts of Acetic Acid Esters (δ in ppm)
                                                                                                                     N
171.3 O                    170.7 O                   170.3 O                     170.2 O                  79.9
               51.5
               CH3
                                          60.4                           67.5                                     Hal
H3 C       O               H3 C       O              H3 C        O                H3 C           O
20.6                       20.9              14.4    21.3                 21.9 22.3                       28.1
                                                                                                                     O
                                                                                   150.9
168.0 O                            169.2 O 72.3             26.1         169.2 O                         125.3
               141.4                                                                                                 N
                                                            24.4                                         128.9
H3 C       O                       H3 C       O                          H3 C          O
20.6                97.5           21.0             32.2                 20.8                 121.4
                                                                                                                     S

13C    Chemical Shifts of Methyl Esters (δ in ppm)                                                               C       X

161.6 O
               49.1
                           171.3 O
                                          51.5
                                                      173.3 O
                                                                       51.5
                                                                                     172.2 O
                                                                                                         51.9     P Si
                                                    9.2                            18.9
                   CH3                      CH3                        CH3                                CH3
  H        O                H3 C      O                            O                                 O
                            20.6                        27.2                    13.8 35.6                        Natural
                                                                                                                 Products

 177.4 O                                    173.4 O                                    178.8 O
19.1               51.5               15.1 28.5                 51.6                                      51.5 Solvents
                    CH3                                         CH3                                       CH3
               O                                            O                   27.3                 O
        34.1                                23.9 34.9                                         38.7
               134          4 13C NMR

                167.8 O                       165.1 O                           162.5 O                    166.5 O
                                   53.0                           54.2                             55.7 130.4                      51.5
               Cl                     CH3     Cl                  CH3          Cl                    CH3                           CH3
                              O                               O                                O                              O
      C             40.7                                                       Cl                                  128.8
                                                   Cl     64.1                       Cl       89.6

  C       C
                    153.4 O                                    175.3 O                                         166.8 O
                                                              29.6                   51.2                    129.7                 51.8
                                       CH3                                              CH3                                        CH3
  C       C                       O                    26.0                     O                    128.4                    O
                           74.8
              75.6                                     26.4                   43.3                   132.8                 130.5


                     158.4                                        167.6                                173.1 O
                                                                  O           CH3 52.3
                O          O CH3 53.1                                     O                                                 CH3 51.3
                                                                                                       29.1            O
                                                         41.2
                                                                                                                       O
                O          O CH3                                          O                                                 CH3
                                                                  O           CH3
      N                                                                                                            O


  Hal           165.8 O                                           165.3 O                                     O        O
                                                                                                                            CH3 53.6
                                       CH3 52.1                                         CH3 52.2           152.3
               130.1              O                           133.5                 O                                  74.6
      O                           O                           O
                                       CH3             H3 C
                                                                                                                            CH3
                            O                                         O
      N
                                                                                                              O        O



      S        13C    Chemical Shifts of Lactones (δ in ppm)


  C       X    168.6 O                       178.1 O                           177.1 O                        174.4 O

                      O           39.1             O          27.8                      O          34.2                O        87.6
  P Si                                                                                                                         180.5
                          58.7                 68.8 22.3                         153.6 100.2                       67.9       OH
                                                                                  (in acetone)
Natural
Products 171.2                               163.8 O                           161.6 O                        176.0 O
               O

Solvents              O           29.2      O                 146.2                   O            117.0               O          34.6
               69.3               19.1 66.6                   121.4           152.1                142.9      69.2                 23.0
                          22.3                         24.0                               106.0                      29.3 29.0
                                                   4.11 Carbonyl Compounds                            135

4.11.5 Amides and Lactams

Additivity Rule for Estimating the 13C Chemical Shifts of Amide Car-
bon Atoms (δ in ppm)                                                                                          C

                                   δC=O = 166.0 + ∑ Zi
                                                                                                             C       C
                                                               Cα' –Cβ'
                                                           /
                                –Cγ–Cβ–Cα–CO–N                                                               C       C
                                                           \
                                                               Cα' –Cβ'

       Substituent i        Zα              Zβ                 Zγ          Zα'            Zβ'
       –C                   7.7             4.5            -0.7           -1.5           -0.3
       –CH=CH2              3.3
       –phenyl              4.7                                           -4.5


                                                                                                                 N
13C   Chemical Shifts of Amides (δ in ppm)
Formamides:                                                                                                   Hal

167.6 O                  163.3 O                       166.5 O                    162.6 O
                                       24.8                                                           31.5       O
                                        CH3                                                           CH3
   H       NH2              H      N                           H      NH                 H        N
                                   H
                                                                      CH3 28.2                    CH3            N
                                ≈ 90%                           ≈ 10%                             36.5


                                  164.9 O                                   162.6 O
                                                                                                                 S
161.8 O
               33.0                                                                           36.7
   H       N                           H          NH                             H        N           12.8 C         X
           H      14.6
                                           36.9        16.8                          41.9         14.9
       ≈ 90%                           ≈ 10%                                                                  P Si
Primary and Secondary Acetamides:                                                                            Natural
                                                                                                             Products
173.4* O                               171.7 O                                   171.0 O
                                                           26.1
                                                                                                  34.4
                                                           CH3                                               Solvents
 H3 C       NH2                            H3 C        N                          H3 C        N
 22.3                                   22.7           H                         22.8         H       14.6
* in water: 177.0
               136       4 13C NMR

               169.8 O                                   168.6 O                                   169.0 O               49.9
                               40.7      11.1                                  40.5
                H3 C       N                               H3 C         N                           H3 C         N
      C         22.5       H     22.5                      22.6         H      22.3                 23.6         H       28.6


  C       C                                                 47.5                                 138.2
               168.3 O                       168.1 O                           25.4       169.5 O                       124.1
                               128.6
                                                                               24.7                                     128.7
  C       C     H3 C       N                    H3 C        N
                                                                      32.6
                                                                                           H3 C       N
                                                                                                             120.4
                22.9       H      95.5          22.7        H                              24.1       H




               Tertiary Amides:

               170.0 O                            169.6 O                                  170.1 O
                                                                      40.0                                  47.4
                                CH3 35.0                                                                                 11.4
                H3 C       N                        H3 C          N          13.1           H3 C       N
                21.5                                21.4                                    21.5               21.0
      N                    CH3 38.0                        42.9                                    50.6          11.2
                                                                        14.2                                22.2
  Hal
                                                                              143.2
                   172.2 O                                             169.1 O                       126.7
                  18.9                40.1
      O                          N           13.2                 23.2 H3 C           N
                                                                                                     129.1
               14.0 35.1                                                                    127.6
                                                                       143.2
                       42.0                                                                 127.6
      N                                 14.4
                                                                                            129.1

      S        13C    Chemical Shifts of Lactams (δ in ppm)

               179.4 O                  175.5 O                         171.9 O                       169.4 O
  C       X
                                                                                                    34.4
                 HN            30.3          HN          127.6               HN           31.5               N          32.3
  P Si           42.4 20.8                   49.5 147.6
                                                                        42.0              20.9        49.9              21.6
                                                                                  22.3                           23.3
Natural
Products 171.9                          164.7 O                         165.0 O                       179.4 O
               O

                                                                                                                         36.8
Solvents         HN            30.5          HN          123.2     HN                     120.8            HN
              125.1            20.1     37.9             139.7 136.1                      142.0      42.5                23.4
                       105.1                      22.5                          106.6                      29.9 30.7
                                                              4.11 Carbonyl Compounds                              137

4.11.6 Miscellaneous Carbonyl Derivatives

13C    Chemical Shifts of Carboxylic Acid Halides (δ in ppm)
                                                                                                                             C
161.0 O                       170.4 O                            165.7 O                           156.1 O

 H3 C           F              H3 C           Cl                   H3 C          Br                 H3 C           I        C       C
                               33.6                                39.1                             47.3

                                                                                                                            C       C
 174.7 O                     165.6 O                                176.3O                           168.0 O
9.3                       137.3                                   29.7                             131.2
                Cl                            Cl          25.5                      Cl     128.8                       Cl
     41.0                      131.4
                                                          25.9                  55.4       135.1               133.2



13C    Chemical Shifts of Carboxylic Acid Anhydrides (δ in ppm)
                                                                                                                                N
158.5                                          166.6 O                                     170.9 O
         O           O                                             O                                       O
                                                                                          8.5                                Hal
     H          O        H                     H3 C           O         CH3                            O
                                                                                            27.4
                                                   22.1
                                                                                                                                O
      169.6 O             O                      172.8 O                O                  173.9 O         O
     18.2                                      18.3                                      26.5
                     O                                            O                                    O                        N
13.4 37.2                                          35.2                                        40.2

                                                                                                                                S
2J
  CF 48 Hz                                                                              162.4 O        O
150.1 O    O                          154.0 O             O                           130.5
                                                                                                                            C       X
                                                                            128.9                  O
F3 C         O           CF3          Cl3 C          O           CCl3
113.5                                 87.9                                  134.5             128.9
1J                                                                                                                           P Si
   CF 285 Hz

                                                                                                                            Natural
                                                                                                    131.1                   Products
         O                              O                                   O                  125.3     O
28.2                                                          30.1
             172.5                        165.9                             168.5                         163.1
                          137.4                                                          136.1                  Solvents
            O                            O            16.7                  O                             O


         O                              O                                   O                                  O
              138         4 13C NMR

              13C    Chemical Shifts of Carboxylic Acid Imides (δ in ppm)
                                                                                               O                               O
              171.6 O             O          173.0 O              O                                183.6                        177.6
      C                                                                         30.3                           27.9
                                                                                               NH                               N CH3
              H3 C        N           CH3     H3 C           N           CH3                                                           24.0
              24.1        H                   26.0           CH3 31.3
  C       C                                                                                    O                               O
                              O
                                                                                                          131.5
                                                                 O                                             O
                                                                                                     122.4
  C       C                   173.0                               170.8                                         167.5
              135.5                           134.3                                       133.7
                              NH                                  N CH3                                                N CH3
                                                                        23.6                                                   23.2
                              O                                  O                                                    O


              13C    Chemical Shifts of Carbonic Acid Derivatives (δ in ppm)
                                                                                                                               O
                 181.3                        124.2                                    192.8                                       168.2
                 C O                         O C O                                 S C         S                       –
                                                                                                                           O           O–
      N
                 156.5 O                         155.4 O                                        155.9 O
              54.9                                                                        19.1 67.3
  Hal         H3 C                    CH3
                                                63.8
                      O           O                      O           O                                     O        O
                                             14.4                                      13.6 30.9
      O                                                                        68.1
              65.0     O 155.9              131.7 O 153.4                                 O 148.7              226.2 S
                                                                                                            20.2
                           O                                  O             21.7              O
                                                                                                            H3 C                       CH3
      N                O                             O                                    O                           S            S

                                                                                                             206.7 S
      S       162.0 O
                                                27.4
                                                    157.8 O                                                 49.6
                                                                             60.7                                  N            S– Na+
                                                     H3 C
              H2 N        O– NH4 +                           N           O                              12.3
                                                             H                     14.7                               49.6
  C       X     (in D2O)                                                                                 12.3
                                                                                                                  (in D2O)
              163.5 O                        158.7 O                                 165.4 O                        194.0 S
  P Si                                                       34.0                  38.5                           43.2
              H2 N        NH2                H2 N        N                                N         N                      N           N
                                                        15.5
                                                         H
Natural                                                                            38.5                           43.2
Products                                        (in DMSO)
                                                       156.9 O
                      162.0 O
                                                         35.6                                                             140.3
Solvents      31.4                                                      N          N
                          N           N                                                                            N C N
                                                                 48.0                                                 49.0
                                  45.0                                      22.3                           24.7
                                              4.12 Miscellaneous Compounds                                    139

4.12 Miscellaneous Compounds

4.12.1 Compounds with Group IV Elements
                                                                                                                     C
13C    Chemical Shifts of Silicon Compounds (δ in ppm)
                                                                                                                    C       C
        CH3                       CH3                                  Cl                           Cl
                0.0                         3.3                              6.7                          9.8
H3 C Si CH3                    Cl Si CH3                       Cl Si CH3                      Cl Si CH3
        CH3                       CH3                                  CH3                          Cl              C       C


               7.4                      16.2 16.6                                                         136.3
                                  Cl
                                                             138.7            -2.0
        Si                     Cl Si                                    Si                          Si
               3.1                      26.6                                                              135.7
                                  Cl
                                                             129.6


               O                                                                                                        N
                   21.6                                 18.3
                                             O
 4.7
         Si          169.0        H3 C Si O                                                    Si                    Hal
                   O                                    58.3
5.0 O                              -7.1 O
                                                                                   134.3                136.4
                                                                                                        127.9           O
                                                                                              129.6
13CChemical Shifts and Coupling Constants of Germanium and Lead                                                         N
Compounds (δ in ppm, |J| in Hz)
               CH3                                     CH3                                         CH3
                                                                                                                        S
       H3 C Ge CH3 -3.6                      H3 C Sn CH3 -9.3                           H3 C Pb CH3 -4.2
               CH3                                     CH3                                         CH3
                                                                                                                    C       X
                                                  4J   11                                     4J   19
                                                             3J   52                                     3J   80
                                       1J   531              2J   38               1J   478              2J   67     P Si

              Ge                                   Sn                                              Pb               Natural
                                                                                                                    Products
 136.2                 135.4           137.9                 137.2                  150.1                137.6
                       128.3                          128.6                                       129.5             Solvents
             129.1                            129.1                                        128.5
                                       Couplings with 119Sn                        Couplings with 207Pb
                                       (8.58%, I = 1/2)                            (22.6%, I = 1/2)
              140         4 13C NMR

              4.12.2 Phosphorus Compounds
              31P (natural abundance, 100%) has a spin quantum number I of 1/2. Couplings to
      C       protons through up to 3–4 bonds are usually observed.

              Phosphines and Phosphonium Compounds (δ in ppm, |J31P13C| in Hz)
  C       C
                               1
                    3J11 1J 12 J 16                              3J12 1J 11                                          1J12
  C       C         24.5 32.6 14.4                               24.8 28.6                                           126.0
                                              CH3
                                      P                                         P                                              PH2
              13.9       28.3                               14.0       27.9
              4J 0       2J 14        CH3                   4J 0       2J 15                                   130.8
                                                                                                               2J 20


                                                                            20 3J 7
                                                                           2J
                                                                                      4
                                              1J
                                                                          133.6 128.4 J 0
                   3J10 2J 14                   15                    1J 12           128.5                                   1J55
                   27.0 28.9                  11.3                    137.2                                                   10.7
                                              CH3                                                                 H3 C         CH3
              4J0
      N                                   P                                     P                                         P+         I–
              26.0                                                                                                H3 C         CH3
                                              CH3
  Hal                                  39.3
                                       1J 8

                                                                                                  1J86 2J 10 3J 12
      O                                                                                           118.3 133.7 130.6 4J 2
              2J 5       1J49                        3J15 1J 48                                                     135.1
              6.3        12.3                        24.1 18.7
      N
                              P+                                      P+
                                               13.3       23.7                                    Br–        P+          23.8
                                               4J 0       2J 4                      I   –                                2J 15
      S
                                  –
                              I
                                                                                                             22.7                  13.8
                                                                                                             1J 50                 4J 0
                                                                                                                   24.6
                                                                                                                   3J 5
  C       X
                                      2J10 3J 12                                                   2J10 3J 13
                                      134.0 130.7           4J3                                    134.3 131.0           4J3
  P Si                                                      135.6                                                        135.9

Natural
                                                          117.3                                                     117.4
Products                      Br–             P+
                                                          1J 90
                                                                                            Cl–         P+
                                                                                                                    1J 89

                                              119.1 145.5
Solvents                                      1J 80 2J 0
                                                              4.12 Miscellaneous Compounds                                      141

Phosphine Oxides and Sulfides (δ in ppm, |J31P13C| in Hz)
         3J13                                                                                              3J16
                       2J5                                                                                            2J4
         24.4                                                                                              24.0                          C
 4J                    24.0                              3J16   54   1J
                                                                         54       1J              4J0                 24.6
   0                            1J66                                                                                           1J51
 13.6                           27.8                     23.9 34.6 CH3 20.8                       13.6                         30.9
                            P        O                                      P     S                                        P        S   C       C
                                                     13.6      24.8
                                                     4J 0      2J 4         CH3
                                                                                                                                        C       C
                            132.3;       4J    3                                         131.5;       4J 3
                                                128.8; 3J 12                                              128.5; 3J 13
                                                132.3; 2J 10                                              132.3; 2J 10
                                             135.6; 1J 104                                             133.1; 1J 85
                                     P O                                                          P        S




                                                                                                                                            N
Phosphinic and Phosphorous Acid Derivatives (δ in ppm, |J31P13C| in
Hz)                                                                                                                                      Hal
      3J11 1J 20                         2J                      3J11 1J 44
                                           12
      24.7 33.6
                                O
                                         53.4                    23.4 42.9
                                                                                                    H3 C
                                                                                                                O
                                                                                                                     P
                                                                                                                           O
                                                                                                                               CH3
                                                                                                                                            O
                            P            CH3                                          PCl2
14.0          24.8                                            13.7        25.1                                       O         48.8
                                                                                                                               2J 12
4J 0          2J 16         O
                                CH3
                                                              4J 0        2J 14                            H3 C
                                                                                                                                            N
5J0           3J5                                                                4J0 3J 7
13.7          33.4                                                               129.5 124.1                                                S
                            O            O                                                                      O
                                P                                           5J0
      19.1 61.9                                                             124.1
                                                                                                    O P
      4J 0 2J 11                O                                                                               O                       C       X
                                                                                                  151.5
                                                                                                  2J 4

                                                                                             2J
                                                                                                                                         P Si
                                                2J                                             5
                                                  7                                          62.1
                                                61.4                                                                                    Natural
                                 16.5                                             16.3
     N             N             3J 6                O           O
                                                                                  2J 6            O                 O 2J 10             Products
           P
                                                          P
                                                                                                           P          131.7
           N           33.9                                           6.6                         O                       128.5 Solvents
                       2J 19                         O                2
                                                               19.0 J 7
                                                                                                                          3J 15
                                                                                                  128.5
                                                               1J 143                             1J 187                 132.4
                                                                                                                         4J 3
              142         4 13C NMR

              Phosphoric Acid Derivatives (δ in ppm, |J31P13C| in Hz)

                     4J
                     0                                  125.1; 5J 0                          125.5; 5J 0
      C            18.9
                                3J7
                                                                   129.8; 4J 0                          129.7; 4J 0
                                32.6
              13.6                                                 120.5; 3J 4                          120.1; 3J 5
              5J 0                     67.2
  C       C                            2J 6                      150.4; 2J 8                          150.4; 2J 8
                                     O                       O                                    O
                                O
                                     P O       H3 C O P O                                      O P O
  C       C                          O                       O                                    O




              Phosphoranes and Phosphorus Ylides (δ in ppm, |J31P13C| in Hz)


                                                                               3J       2J
      N                                        1J56     1J 90                    11       9            1J
                            O                                                  128.5    132.9             111 2J 4
                      O                        19.7 CH3 -1.5                                           3.2 11.0
                           P O
  Hal                                            H3 C P          CH2           130.6              P    CH      CH3
                          O O                                                  4J 3
                                                          CH3

      O             24.1        68.5
                                                    (in benzene)                       133.3
                                                                                       1J 83
                    3J 6        2J 13

      N
              4.12.3 Miscellaneous Organometallic Compounds

      S       Lithium Compounds (δ in ppm)
                                                                                                        Li
              -15.3                      33.5 9.7                         183.4                             85.3
  C       X   H3 C    Li                             Li                         Li                             115.8
                                     18.9 33.9                         132.5                                   130.9
  P Si                                                                                                131.6


Natural Magnesium Compounds (δ in ppm)
Products                                                                                           MgBr
                                                          141.0
                    -14.6                        17.0                                                 93.2
                                                              102.0
                                                                                                         117.6
Solvents             H3 C MgI                                     MgBr
                                                      15.0                                               131.7
                                                                                                 133.0
                                               4.12 Miscellaneous Compounds                                   143

Boron Compounds (δ in ppm, |J| in Hz)

                                        CH3                            11.8
H3 C        14.8                                 6.2                                    109.9
                                           –                                                                         C
       B    CH3                    H3 C B        CH3 Li   +                        B–                     CH3
                                                                            15.3                 85.7
H3 C                                    CH3
                                                                                             Na+
                                                                                                                    C       C
                                                                              121.4;       4J    0
                                                       10.3                                      125.2; 3J 3 C              C
                    51.3                                      163.3;   1J   50                   135.5; 2J 1
                                               64.9
H3 C O              CH3                O
                                                       24.9                             B–
            B O                            B    O
H3 C O                                 O
                                                                                                      Na+


                                                                       Couplings with 11B
                                                                       (80.4%, I = 3/2)
                                                                                                                        N
Arsenic, Antimony, and Bismuth Compounds (δ in ppm)
                                                                                      134.8                          Hal
                                                                                                     131.3
       11.2                             CH3 8.4                        120.2                         132.8
                                                                                                                        O
H3 C
    As CH3                         H3 C As+ CH3 I–
                                                                                             +
H3 C                                                                                    As
                                       CH3
                                                                                                                        N
                                                                                                          –
                                                                                                       Cl

                                                                                                                        S
                133.7 128.6                         136.8 129.4                         138.1 131.0
                                                                                                                    C       X
           As              128.4               Sb             129.1                Bi                       128.3

                139.6                             139.3                                 131.1                        P Si

                                                                                                                    Natural
Mercury Compounds (δ in ppm, |J| in Hz)                                                                             Products
                                                                                      2J85    104    3J
                                                                                      137.4 128.3
  5.9                          3.5             165.5
 H3 C Hg Cl                   H3 C Hg          C N                               Hg                         128.0 Solvents
                                                                                                            4J 20


                        Couplings with 199Hg (16.8%, I = 1/2)                    170.3; 1J 1275
              144          4 13C NMR

              4.13 Natural Products

              4.13.1 Amino Acids
      C
              13C    Chemical Shifts (δ in ppm; solvent: water)

  C       C              41.5                                   42.8                             46.0
              +
                                     OH                                     O–                               O–
                  H3 N                               +
                                                         H3 N                             H2 N
                                    171.2                                  173.6                            182.7
  C       C                     O                                      O                                O
                     (pH 0.45)                              (pH 4.53)                          (pH 12.01)

                            36.6                                   38.8                          39.3
              +
                  H3 N                   OH      +
                                                     H3 N                      O–      H2 N                  O–
                         32.2            175.7              34.8               179.4          41.6          182.7
                                     O                                     O                            O
                         (pH 0.49)                              (pH 5.03)                      (pH 12.56)

                            16.5                                    17.5                             21.7
      N                     50.1 OH                                 51.9 O–                          52.7 O–
              +                                      +
                  H3 N              174.0                H3 N               177.0        H2 N             185.7
  Hal                           O                                      O                              O
                    (pH 0.43)                                   (pH 4.96)                      (pH 12.52)
                   17.9     18.5                         17.8      19.2                  17.9        20.3
      O
                   30.0                                   30.3                            32.9
                            59.6 OH                                 61.9 O–                          63.2 O–
      N
              +
                  H3 N              172.7
                                                     +
                                                         H3 N               175.4        H2 N             184.1
                                O                                      O                              O
                    (pH 1.34)                                   (pH 5.64)                      (pH 12.60)
      S
                           22.1                                    21.8                               22.5
                      25.1                                    25.1                               25.6
  C       X        40.1       22.7                         40.7       22.9                    45.5      23.7
                        52.8 OH                                 54.4 O–                            55.9 –
              +                                      +
                                                                                                            O
                  H3 N              174.0                H3 N              176.3         H2 N             185.4
  P Si                          O                                      O                              O
                    (pH 0.37)                                   (pH 7.00)                      (pH 13.00)
Natural                         12.1                                       12.4                           12.3
Products           15.3                                   15.9                            16.7
                                25.9                                       25.6                           25.2
                   37.1                                    37.1                           39.8
                           58.7 OH                                 60.9 O–                           62.3 O–
Solvents      +
                  H3 N                               +
                                                         H3 N                            H2 N
                                    172.8                                   175.0                         184.1
                                O                                      O                              O
                    (pH 0.28)                                   (pH 6.04)                      (pH 12.84)
                                                                4.13 Natural Products        145

                 OH                                       OH                            OH
     60.4                                  61.2                                62.9
                56.0 OH                                  57.5 O–                      57.8 O–
+
    H3 N
                     171.3
                                      +
                                          H3 N
                                                              173.2           H2 N          176.1    C
                 O                                        O                             O
       (pH 1.12)                             (pH 6.05)                           (pH 9.28)
                                                                                                    C       C

                20.2                                     20.6                         20.3
     HO                                   HO                                   HO
                                                                                                    C       C
     66.3                                  66.9                                68.6
                59.8 OH                                  61.5 O–                      62.1 O–
+                                     +
    H3 N             171.7                H3 N                173.6           H2 N          177.3
                 O                                        O                             O
       (pH 1.36)                             (pH 5.87)                           (pH 9.27)


                 SH                                       SH                            SH
     25.1                                  25.5                                32.0
                55.9                                     56.7 O–                      60.7 O–
                       OH
+
    H3 N             171.9
                                      +
                                          H3 N                173.1           H2 N          182.1
                                                                                                        N
                 O                                        O                             O
       (pH 1.75)                                 (pH 5.14)                       (pH 11.02)          Hal

                     14.8                                     14.8                          14.9        O
                 S                                        S                             S

     29.9
                     29.5
                                           30.6
                                                              29.8
                                                                               34.0
                                                                                        30.4            N
                53.2 OH                                  54.9 O–                      55.8 O–
+                                     +
    H3 N             172.9                H3 N                174.8           H2 N          181.3
                 O                                        O                             O
                                                                                                        S
       (pH 1.55)                                 (pH 5.83)                       (pH 9.80)
                                                                                                    C       X
                 O                                        O

                                                                                                     P Si
                                  +
                            NH3                                      NH3 +
           HO                –
                                                 –
                                                     O
                            Cl
                 S                                        S                                         Natural
                 S                                        S                                         Products
     37.4                                   44.1
                51.2 OH                                  55.8 O–
+
    H3 N             168.9
                                      +
                                          H3 N                180.7                                 Solvents
    Cl–          O                                        O
           (in DMSO)                         (in D2O)
              146          4 13C NMR

                           130.0                        116.8                                     118.6
                                                               OH                                        OH
                    130.2        128.5           131.7                                     133.5
                                                              155.8                                     157.7
                     136.0                        127.8                                     128.2
      C            37.2                         36.4                                      37.3
                        56.9 O–                      57.1 O–                                   56.7 OH
              +                            +                                         +
                  H3 N             174.7       H3 N                 174.9                H3 N          173.8
  C       C                    O                                O                                  O
                                                                                            (in D2O/DCl)
  C       C                    O                                        O                                   O
                                   174.4                                    178.7                               181.3
                   35.0             OH                     37.8              OH                  44.5            O–

              +
                                    OH                +
                                                                             O–                                  O–
                  H3 N             172.0                  H3 N              175.5               H2 N            183.4
                    50.6 O                                  53.5 O                                55.3 O
                     (pH 0.41)                                (pH 6.73)                             (pH 12.73)

                          O         OH                              O        OH                         O        O–
      N                        172.4                                        182.4                             184.0
                               30.7                                         34.7                              35.3
                   26.1                                    28.2                                  33.0
  Hal                                                                            –
              +
                                    OH                +
                                                                             O                                   O–
                  H3 N                                    H3 N                                  H2 N
                           172.6                                    175.8                                 183.9
      O             53.4 O                                  56.0 O                                57.2 O
                     (pH 0.32)                                (pH 6.95)                             (pH 12.51)

      N             +
                        H3 N                                +
                                                                H3 N                               H2 N
                               40.2                                         40.3                              41.9
                               24.0                                         24.0                              29.4
      S            28.1                                    28.7                                  33.3
                                    OH                                       O–                                  O–
              +                                                                                 H2 N
                  H3 N     172.8                          H2 N      175.3                                 184.6
  C       X         53.7 O                                  55.5 O                                57.2 O
                     (pH 0.46)                                (pH 5.02)                             (pH 13.53)

  P Si                    NH3 +                                     NH3 +                               NH2
                   40.5                                    40.5                                  41.8
Natural                        27.6                                         27.7                              33.0
Products                       22.6                                         22.6                              23.6
                   30.5                                    31.2                                  35.7
                                    OH                                       O–                                  O–
Solvents      +
                  H3 N             173.2                  H2 N
                                                                            175.8               H2 N            184.6
                    54.0 O                                  55.9 O                                57.3 O
                     (pH 0.50)                                (pH 6.03)                             (pH 13.85)
                                                                  4.13 Natural Products                    147

+                                           +
    H2 N           NH2                          H2 N           NH2                       HN          NH2
                157.8                                         157.9                                 157.8
           HN                                          HN                                      HN
                    41.5                                        41.6                                    42.1       C
                    24.9                                        25.0                                    25.6
     28.0                                        28.8                                     32.7
                     OH                                           O   –
                                                                                                          O–      C    C
+
    H3 N            172.8                       H2 N             175.4                  H2 N              183.9
      53.9 O                                      55.4 O                                   56.6 O
       (pH 1.33)                                   (pH 7.87)                              (pH 11.52)              C       C



  24.4 29.4                                 24.8 30.0                                24.8 30.0
         61.0 OH                                   62.3 O–                                  62.4 O–
47.4                                      47.2                                     47.2
      N      173.3                              N      175.4                             N      175.8
            H2 +      O                            H2 +          O                        H          O
           (pH 1.27)                               (pH 7.26)                              (pH 9.80)
                                                                                                                      N
    HO
       38.5
                                           HO
                                                       41.9                                                        Hal
 71.1                                      73.9
          61.0 O–                                         64.5 O–
54.0                                      57.7
               175.1                                           179.2
      N
            H2 +         O
                                                       N
                                                       H2 +      O
                                                                                                                      O

                                                                                                                      N
           118.9         NH3 +                  117.7          NH3 +                  118.2       NH2
     N                                     N                                      N
                 53.6 OH                  55.7 O–                   56.1 O–
                                                                               S
135.0 N             172.1 137.2 N             174.8 137.1 N             176.9
      H
           26.2                 H
                                     29.0                 H
                                                              30.1
                  O                         O                         O
        127.7                    133.1                     133.5
       (pH 1.74)                   (pH 7.82)                   (pH 9.21)      C X


                             NH3 +                                                                NH3 +
                                                                                                                   P Si
                         56.0 O                                                                56.1 O
                128.9                                                                 127.7
            124.5     28.2 174.7                                                  122.9     27.2 174.8 Natural
                                  OH                                                                 O–Products
121.8                            114.2                                    120.3                     108.7
120.5                             127.6                                   119.3                      125.8
                         N                                                                    N                   Solvents
            114.2        H                                                        112.7 H
                  138.6                                                                137.3
              (in D2O/DCl)                                                              (80 oC)
              148      4 13C NMR

              4.13.2 Carbohydrates

              13C   Chemical Shifts of Monosaccharides (δ in ppm)
      C
              Ribose
                           68.1 63.8                               68.2 63.8
  C       C           HO
                                     O
                                                              HO
                                                                             O

                                                 94.3                                 OH
                           70.1         OH                     69.7              OH 94.7
  C       C                       OH 70.8 OH                          OH 71.9




                             62.1                                     63.3
                       HO                                      HO                       OH
                                      O   97.1                                O
                           83.8                                     83.3              101.7
                                             OH
                            70.8                                     71.2            76.0
                                                71.7
                             HO           OH                           HO            OH

      N                    67.4 60.8                                61.9
                                     O                         HO            O
  Hal
                      HO
                                                                   84.6
                                                 100.4                                  O CH3 55.5
                           70.4         OH                          69.8
                                  OH 69.2 O                                             71.1
                                                                     HO             OH
                                                  CH3 56.7
      O
                                                                    62.9
                           68.6 63.9                           HO            O      O CH3 55.3
      N
                                     O
                      HO                                           83.0              108.0
                                               O                    70.9            74.3
                        68.6              OH 103.1 CH3 57.0
                                                                     HO           OH
                                  OH 71.0
      S
              Glucose
  C       X                       OH 61.6                             OH 61.7
                        70.6          72.3                     70.6          76.8
                                            O                                       O
                       HO                                     HO
  P Si                   HO                       92.9          HO                     OH
                               73.8       OH                          76.7        OH 96.7
                                      72.5 OH                                75.1
Natural
Products                          OH 61.6                             OH 61.8
                        70.6          72.5                     70.6          76.8
                                            O                                       O
Solvents               HO                                     HO
                         HO                       100.0         HO                      O
                               74.1       OH                          76.8        OH 104.0 CH3 58.1
                                      72.2 O                                 74.1
                                                   CH3 55.9
                                           4.13 Natural Products                      149

                   OAc 61.1                           OAc 61.7
           68.1           70.0                 69.4            72.8
                             O                                        O
         AcO
           AcO
                                            AcO                                              C
                                    89.2      AcO                              OAc
                  70.0      OAc                       72.8          OAc 91.8
                         69.4 OAc                              70.5
                                                                                            C       C
Fructose
                                                                                            C       C
                                                               99.1 OH
                     HO O                          64.1                          OH
    HO                           65.9
                                                               O               64.7
         71.3        70.9            OH
                                            70.0                          OH
                                                      70.5 68.4
                OH          OH                      HO
                                               HO
    traces in water and in DMSO              75% in water, 25% in DMSO




              61.9        105.5                       63.2         102.6                        N
         HO           O
                                  63.8         HO               O         OH
           82.2
                             OH
                                   OH               81.6                    OH               Hal
            77.0                                     75.4                 63.6
                HO          OH                         HO             OH
               82.9
    4% in water, 20% in DMSO
                                                        76.4
                                             21% in water, 55% in DMSO
                                                                                                O

13C-1H   Coupling Constants through One Bond (1JCH in Hz)                                       N

                  O
                            1
                                                        O
                                                                                                S
                     13
                        C H JCH 169–171                   13
                                                               C OR
                      OR                                       H 1JCH 158–162
                                                                                            C       X


                                                                                             P Si

                                                                                            Natural
                                                                                            Products

                                                                                            Solvents
              150       4 13C NMR

              4.13.3 Nucleotides and Nucleosides

              13C   Chemical Shifts of Nucleotides (δ in ppm)
      C
                                      NH2                                           .
                                                                              NH2 HCl                                O
                                          168.1a, 167.5b                          160.8                                  165.1
  C       C
                93.4b, 95.8a               N                                       N                101.0                 NH
                                               159.9a, 157.8b                          149.7                                152.3
              143.5b, 144.0a                                     146.9                              142.9
                                      N         O                             N         O                            N         O
  C       C                           H                                       H                                      H
                            (a in D2O, b in DMSO)                        (in D2O)                                (in DMSO)


               11.7b, 12.1a
                                      O                                                     119.1 NH2
                        H3 C              168.3a, 164.9b                                           156.4
                                                                                            N
              107.7b, 110.9a               NH                                                                N
                                               153.9a, 151.5b                  140.3
              137.6b, 139.8a                                                                                     153.4
                                      N         O                                           N            N
                                      H                                                     H
                                                                                             151.7
      N                      (a in D2O, b in DMSO)                                        (in DMSO)

  Hal
                        115.9 NH2 . HCl                    119.6 O                              108.4 O
                               151.4                                  168.8                                      155.7
      O       144.5
                      N
                                      N
                                                  150.1
                                                          N
                                                                       NH
                                                                                   137.9
                                                                                                N
                                                                                                                  NH

                      N               145.8               N       N         NH2                 N            N               .
                                                                                                                       NH2 HCl
                               N                          H                                     H
                      H
      N                   149.8                               162.2 160.0                           150.5 153.8
                       (in D2O)                            (in D2O)                             (in DMSO)

      S
              Nucleosides (δ in ppm)

  C       X
                                      NH2                                                           O
                                          166.9a, 165.5b                                                166.9a, 163.0b
  P Si           93.9b,   96.9a             N                          101.7b,     103.1a                NH
                                                158.2a, 155.4b                                               152.4a, 150.7b
              141.5b,   142.4a                                         140.6b,     142.6a
                                      N          O                                                  N            O
Natural          HO                                                               HO
Products 60.6b, 61.7a             O                                   60.8b,   61.6a        O
              84.1b, 84.6a                91.2a, 89.2b                84.8b, 85.0a                      90.2a, 87.7b

Solvents       73.9b, 70.2a           74.8a, 69.4b                     69.8b, 70.3a                 74.5a, 73.5b
                               OH OH                                                      OH OH

                      (a in D2O, b in DMSO)                                       (a in D2O, b in DMSO)
                                                                4.13 Natural Products                    151

                             O                                                       O
                 12.3                                           12.1b, 12.3a
                 H3 C          167.2                                   H3 C           167.2a, 163.6b
                 112.3             NH                         109.3b, 112.2a              NH
                                      152.6                                                 152.4a, 150.4b      C
                 138.2                                        136.0b, 138.3a
                              N          O                                           N         O
            HO                                                       HO
            61.6         O                                    61.3b, 62.0a      O                              C       C
            85.0                  89.9                        87.2b, 87.3a               85.9a, 83.7b
              70.2            74.2                            70.4b, 71.3a           39.4a, 39.5b
                     OH OH                                                    OH
                                                                                                               C       C
                     (in D2O)                                      (a in D2O, b in DMSO)


            120.1b, 119.6a NH2                                                        117.7 O
                            155.5a, 156.9b                                                         157.8
                         N                                                           N
                                         N                                                         NH
 140.7b, 141.4a                                                            136.7                     154.7
                         N                   152.1a, 153.2b                          N
         HO                         N                                 HO                       N        NH2
62.4b,   62.0a               149.0a,     149.8b                       62.5               152.3                     N
                    O                                                           O
86.6b,   86.3a               88.9a,   88.8b                           86.3               87.5
 71.4b, 71.1a            74.3a, 74.3b                                  71.4          74.8                       Hal
                  OH OH                                                        OH OH
     (a in D2O, b in DMSO)                                                     (in DMSO)                           O

                                                                                                                   N
            117.7b, 119.7a NH2                                                           117.4 O
                            156.1a, 157.9b                                                         159.7
                         N                                                           N
                                                                                                                   S
                                         N                                                          NH
 136.4b, 141.1a                                                              138.5                    154.6
                         N
                                             153.0a, 154.7b                          N
         HO                         N                                                          N         NH2
                                                                      HO
62.8b,   62.6a               149.0a,     151.9b                       62.5               152.0
                    O                                                           O                              C       X
88.7b, 88.3a                 85.5a, 83.8b                             88.0               84.8
 71.8b, 72.1a            40.0a, 39.7b                                  72.0           39.6
                  OH                                                           OH                               P Si
     (a in D2O, b in DMSO)                                                     (in D2O)
                                                                                                               Natural
                                                                                                               Products

                                                                                                               Solvents
              152       4 13C NMR

              4.13.4 Steroids

              13C    Chemical Shifts (δ in ppm)
      C
                                    18.3                                               17.3
                                40.7                                               40.3
  C       C                            40.7                                               40.6
                          24.1 20.7                  25.4                    12.0 20.7                 25.3
                      37.6     43.6 54.5                                 37.6     54.5 54.9
                                                     38.0                                              38.8
              21.2                                               22.0
  C       C                      27.2    36.1 20.4                              36.1       35.7 20.3
              26.8     40.3              27.4                    26.6    46.9              32.3
                      26.9        26.9                                  28.9        28.9
                              H                                                 H


                                    11.0                                              13.0               O
                                36.8                                              36.0                        197.8
                                       42.9          OH                                  43.7
                          17.0 21.0                  81.0                   17.0 21.2                  63.3 24.4
                      35.8     54.3 50.8                                35.7     54.7 56.2
                                                     30.4                                              38.8
              33.8                                               32.6
      N               170.1
                                 38.7    35.8 23.5
                                                                        169.3
                                                                                38.3       33.9 23.0
                                         31.9                                              30.7
               O                                                  O
  Hal         197.7 123.9 32.5                                   197.4 124.0 32.3



      O                             12.6
                                                     19.1
                                                                                      12.0
                                                                                                       18.8
                                40.7                     36.3                     40.0                     35.4
                                       43.0                                              42.4
      N                   12.5 21.3                  56.8 36.7              19.4 21.2                  56.5 36.4
                      39.2     55.3 57.1                                37.5     50.5 56.9
                                                    28.7 24.4                            28.3 24.1
              22.7            36.7       36.0 24.6      40.0  31.6       36.5 32.3 24.3      39.6
                      47.6                                    71.3 141.2
      S       27.3                       32.6           28.5
                                                              HO
                                                                              32.0           28.0

                      29.2        29.2           23.1    23.8      42.4 121.3         22.5    22.8
                             H

  C       X


  P Si

Natural
Products

Solvents
                          4.14 Spectra of Solvents and References                               153

4.14 Spectra of Solvents and Reference Compounds

4.14.1 13C NMR Spectra of Common Deuterated Solvents (125 MHz,
                                                                                                       C
δ in ppm)

                                                                                                      C       C
Acetone-d6
    206.0
                                                                                   29.8               C       C

                                                     31    30        29

   200      180    160    140     120        100     80         60        40              20     0
Acetonitrile-d3
                                        118.3
                                                                                               1.3

                                                                          2         1                     N
   200      180    160    140     120        100     80         60        40              20     0
                                                                                                       Hal
Benzene-d6
                                  128.0
                                                                                                          O

             129   128   127
                                                                                                          N
   200      180    160     140    120        100     80         60        40              20     0
Bromoform-d
                                                                                                          S
                                                                                               10.3

                                                                                                      C       X
                                                                     11       10

   200      180    160    140     120        100     80         60        40              20     0
Chloroform-d
                                                                                                       P Si
                                                          77.0
                                                                                                      Natural
                                                                                                      Products
                                 78     77      76
                                                                                                      Solvents
   200      180    160    140     120        100     80         60        40              20     0
              154         4 13C NMR


              Cyclohexane-d12

      C                                                                                                  26.4


                                                                        27       26
  C       C
                    200     180     160    140     120      100        80        60          40          20     0
              Dimethyl sulfoxide-d6
  C       C
                                                                                                  39.5


                                                                  40        39

                    200     180     160    140     120      100        80        60          40          20     0
              Methanol-d1

                                                                                            49.9
      N
                                                         51       50        49
  Hal
                    200     180     160    140     120      100        80        60          40          20     0
              Methanol-d4
      O
                                                                                            49.0

      N
                                                         50       49        48

                    200     180     160    140     120      100        80        60          40          20     0
      S       Pyridine-d5

                                   149.9            123.5
  C       X                                135.5

                    151    150    149                       136.0 135.0                    124.0 123.0
  P Si
                    200     180     160    140     120      100        80        60          40          20     0

Natural       Tetrahydrofuran-d8
Products                                                                         67.4
                                                                                                         25.3
Solvents
                                                    68      67                        26      25

                    200     180     160    140     120      100        80        60          40          20     0
                            4.14 Spectra of Solvents and References                              155

4.14.2    13C   NMR Spectra of Secondary Reference Compounds

Chemical shifts in 13C NMR spectra are usually reported relative to the peak posi-
tion of tetramethylsilane (TMS), which is added as an internal reference. If TMS is C
not sufficiently soluble in the sample, the use of a capillary with TMS as external
reference is recommended. In this case, owing to the difference in volume sus-
ceptibilities, the local magnetic fields in the solvent and reference are different. C C
Therefore, the position of the reference must be corrected. For a D2O solution in
a cylindrical sample with TMS in a capillary, the correction amounts to +0.68 and
-0.34 ppm for superconducting and electromagnets, respectively. These values must C C
be subtracted from the 13C chemical shifts relative to the external TMS signal if its
position is set to 0.00 ppm. Alternatively, secondary references with (CH3)3SiCH2
groups may be used. The following spectra of two secondary reference compounds
in D2O were measured at 125 MHz with a superconducting magnet and TMS as
external reference. Chemical shifts are reported in ppm relative to TMS upon cor-
rection for the difference in the volume susceptibilities of D2O. As a result, the peak
for the external TMS appears at 0.68 ppm.

 3-(Trimethylsilyl)-1-propanesulfonic acid sodium salt (sodium 4,4-dimethyl-4-
 silapentane-1-sulfonate; DSS)                                                                              N
                                                                              0.68 TMS
                                                                    (external reference)
     H3C     CH3
            Si     SO3Na
                                                                                                 -1.9    Hal
      H3C
                                                               55.1
                                                                             19.8     15.8


    200      180    160     140   120    100        80        60        40       20          0
                                                                                                            O
 2,2,3,3-D4-3-(Trimethylsilyl)-propionic acid sodium salt
       H3C D D
                                                                                                 -2.0       N
    H3C Si                                                                    0.68 TMS
              COONa                                                 (external reference)
    H3C D D
           186.3      187   186 33      32     31        13        12     31.9      12.7
                                                                                                            S
    200      180    160     140   120    100        80        60        40       20          0
                                                                                                        C       X


                                                                                                         P Si

                                                                                                        Natural
                                                                                                        Products

                                                                                                        Solvents
              156       4 13C NMR

              4.14.3 13C NMR Spectrum of a Mixture of Common Nondeuterated
              Solvents

      C       The broad-band-decoupled 13C NMR spectrum (125 MHz, δ in ppm relative to
              TMS) of a CDCl3 sample with 20 common solvents (0.05–0.4 vol%) shown below
              serves as a guide to identify possible solvent impurities. Chemical shifts of signals
  C       C   marked with an asterisk (*) may change up to a few ppm if the sample contains
              solutes having functional groups that can form hydrogen bonds.
                 DMF: dimethyl formamide; THF: tetrahydrofuran; EGDME: ethylene glycol
  C       C   dimethyl ether.

                                                                                                  149.9* pyridine
                                                          ethyl acetate         DMF
                    206.8* acetone    192.6 CS2                  171.1          162.5


              210 205       200 195 190 185           180 175 170              165 160 155 150           145 140
                pyridine    129.1 toluene                                               CDCl3 77.1*      (top part
                  136.0       128.4, 128.3 toluene, benzene                                              of signal
                                                                                        CHCl3 77.3*
                                125.3 toluene                                                            not
              toluene                 123.8 pyridine                                                     drawn)
      N       137.9
                                               116.3* acetonitrile             96.2* CCl4

  Hal         140 135 130 125 120 115 110 105 100                              95   90      85     80     75

                                                                                                  53.4 CH2Cl2
      O                 71.9 EGDME
                                        67.1 dioxane           60.4 ethyl acetate
                                                                                                        methanol
                                            65.9 diethyl ether      59.1* ethanol
                                THF 68.0                                                                   50.7*
                                                                       58.4 EGDME
      N
              75                 70                  65                   60                 55                 50
                                                                               DMF 31.3   27.0 cyclohexane
      S                    dimethyl sulfoxide 41.1                        hexane 31.6 30.9 acetone
                                                                                                      25.6
                                                          DMF 36.4                                    THF
  C       X
              50                 45                  40                   35                 30                 25
                       22.7 hexane               15.3 diethyl ether
  P Si                      21.4 toluene             14.2 ethyl acetate                            1.8 acetonitrile
                              21.0 ethyl acetate         14.1 hexane
                                      18.5 ethanol                                                             TMS
Natural
Products
              25                 20                  15                   10                 5                   0

Solvents
5    1H      NMR Spectroscopy

                                                                                                       C


                                                                                                      C       C

5.1 Alkanes                                                                                           C       C

5.1.1 Chemical Shifts

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)


CH4 0.23                        CH3 0.86          CH3 0.91     3J
                                                                    vic   7.4 CH3 a 0.91 3Jab 7.3
       2J         -12.4                                                                  2J -12.4
            gem                 CH3               CH2 1.33                    CH2 b 1.31 3 bb'
                                                                                          Jbc 5.7
                                                                                         3J               N
                                                                                            bc' 8.5
                                                  CH3                         CH2

                                                                                                       Hal
                                                                              CH3

       CH3 0.89           3J                            CH3 0.90              CH3 0.88
                               vic
                          6.8
       CH 1.74                             H3 C          CH3                  CH2 1.27                    O
H3 C         CH3                                        CH3                   CH2 1.27
                                                                              CH2                         N
                                                                              CH3

                                                                                                          S

In long-chain alkanes, the methyl groups at δ ca. 0.8                                                 C       X
ppm typically show distorted triplets due to second-
order effects:
                                                                                                       P Si

                                                                                                      Natural
                                                                                                      Products

                                                                                                      Solvents
              158      5 1H NMR

              1H   Chemical Shifts of Monosubstituted Alkanes (δ in ppm)

                      Substituent       Methyl          Ethyl              1-Propyl
      C                                 –CH3     –CH2      –CH3   –CH2      –CH2 –CH3
                      –H                 0.23    0.86     0.86    0.91     1.33   0.91
               C      –CH=CH2            1.71    2.00     1.00    2.02     1.43   0.91
  C       C
                      – C – CH
                          –
                          –              1.80    2.16     1.15    2.10     1.50   0.97
                      –phenyl            2.35    2.63     1.21    2.59     1.65   0.95
  C       C    X      –F                 4.27    4.55     1.35    4.30     1.68   0.97
                      –Cl                3.06    3.47     1.33    3.47     1.81   1.06
                      –Br                2.69    3.37     1.66    3.35     1.89   1.06
                      –I                 2.16    3.16     1.88    3.16     1.88   1.03
               O      –OH                3.48    3.71     1.24    3.59     1.59   0.94
                      –O–alkyl           3.24    3.37     1.15    3.27     1.55   0.93
                      –OCH=CH2           3.16    3.66     1.21
                      –O–phenyl          3.73    3.98     1.38    3.86     1.70   1.05
                      –OCOCH3            3.67    4.12     1.26    4.02     1.65   0.95
      N
                      –OCO–phenyl        3.88    4.37     1.38    4.25     1.76   1.07
                      –OS(O)2–4-tolyl    3.70    4.07     1.30    3.94     1.60   0.95
  Hal
               N      –NH2               2.47    2.66     1.11    2.65     1.46   0.91
                      –NHCH3             2.30
      O               –N(CH3)2           2.22    2.32     1.06
                      –NHCOCH3           2.79    3.26     1.14    3.18     1.55   0.96
                      –NO2               4.29    4.37     1.58    4.28     2.01   1.03
      N                  –
                      –C– N
                         –               1.98    2.35     1.31    2.34     1.70   1.08
                      –NC                2.85    3.39     1.28
      S        S      –SH                2.00    2.44     1.31    2.50     1.63   0.99
                      –S–alkyl           2.09    2.49     1.25    2.43     1.59   0.98
                      –SS–alkyl          2.30    2.67     1.35    2.63     1.71   1.03
  C       X           –S(O)CH3           2.50
                      –S(O)2CH3          2.84    2.94     2.80
               O      –CHO               2.20    2.46     1.13    2.37     1.64   0.97
  P Si                –COCH3             2.17    2.44     1.06    2.40     1.60   0.93
               ||
                      –CO–phenyl         2.55    2.92     1.18    2.86     1.72   1.02
Natural        C      –COOH              2.10    2.36     1.16    2.31     1.68   1.00
Products              –COOCH3            2.01    2.32     1.15    2.22     1.65   0.98
                      –CONH2             2.02    2.23     1.13    2.19     1.68   0.99
Solvents              –COCl              2.66    2.93     1.24    2.87     1.74   1.00
                                                         5.1 Alkanes          159

1H   Chemical Shifts of Monosubstituted Alkanes (δ in ppm, contd.)

        Substituent       2-Propyl                 n-Butyl           tert-Butyl
                          –CH –CH3      –CH2    –CH2 –CH2     –CH3     –CH3          C
        –H                1.33 0.91      0.91   1.31 1.31     0.91     0.89
 C      –CH=CH2                          2.06   ≈1.5 ≈1.2     0.90     1.02
                                                                                    C       C
        –C – C–
           –
           –              2.59   1.15    2.18   1.52 1.41     0.92     1.24
        –phenyl           2.89   1.25    2.61   1.60 1.34     0.93     1.32
 X      –F                4.84   1.34    4.34   1.65          0.95     1.34         C       C
        –Cl               4.14   1.55    3.42   1.68 1.41     0.92     1.60
        –Br               4.21   1.73    3.42   1.84 1.46     0.93     1.76
        –I                4.24   1.89    3.20   1.80 1.42     0.93     1.95
 O      –OH               4.02   1.21    3.64   1.56 1.39     0.94     1.26
        –O–alkyl          3.55   1.08    3.40   1.54 1.38     0.92     1.24
        –OCH=CH2          4.06   1.23    3.68   1.61 1.39     0.94
        –O–phenyl         4.51   1.31    3.94   1.76 1.47     0.97
        –OCOCH3           4.99   1.23    4.06   1.60 1.39     0.94     1.45
        –OCO–phenyl       5.22   1.37                                  1.58             N
        –OS(O)2–4-tolyl   4.70   1.25    4.03   1.62   1.36   0.88
 N      –NH2              3.07   1.03    2.69   1.43   1.35   0.92     1.15          Hal
        –NHCOCH3          4.01   1.13    3.21   1.49   1.35   0.92     1.28
        –NO2              4.44   1.53    4.47   2.07   1.50   1.07     1.59
        –C – N
           –
           –              2.67   1.35    2.34   1.63   1.50   0.96     1.37             O
        –NC               3.87   1.45                                  1.44
 S      –SH               3.16   1.34    2.52 1.59     1.43   0.92     1.43
                                                                                        N
        –S–alkyl          2.93   1.25    2.49 1.56     1.42   0.92     1.39
        –SS–alkyl                        2.69 1.64     1.42   0.93     1.32
        –S(O)2CH3         3.13   1.41                                  1.44             S
 O      –CHO              2.39   1.13    2.42 1.59     1.35   0.93     1.08
        –COCH3            2.58   1.11                                  1.13
 ||                                                                                 C       X
        –CO–phenyl        3.58   1.22    2.95   1.72   1.41   0.96
 C      –COOH             2.56   1.21    2.35   1.62   1.39   0.93     1.23
        –COOCH3           2.56   1.17    2.31   1.61   1.33   0.92     1.20
                                                                                     P Si
        –CONH2            2.44   1.18    2.22   1.60   1.37   0.93     1.22
        –COCl             2.97   1.31   2.88    1.67   1.40   0.93
                                                                                    Natural
                                                                                    Products

                                                                                    Solvents
              160    5 1H NMR

              Estimation of 1H Chemical Shifts of Substituted Alkanes (δ in ppm)


      C               CH3                                  CH2                                CH
              δCH3R1 = 0.86 + Zα       δCH2 = 1.37 + ∑ Zα + ∑ Zβ                 δCH = 1.50 + ∑ Zα + ∑ Zβ
                                                             i   i    j     j                   i    i      j   j
  C       C   δCH3CR1R2R3 = 0.86 + ∑ Zβ
                                   i      i


  C       C         Substituent               CH3                     CH2                     CH
                    (R1, R2, R3)       Zα           Zβ           Zα         Zβ           Zα         Zβ
               C    –C                 0.00         0.05         0.00       -0.06        0.17       -0.01
                    –C=C               0.85         0.20         0.63        0.00        0.68       0.03
                       –
                    –C – C–
                       –               0.94         0.32         0.70        0.13        1.04
                    –phenyl            1.51         0.38         1.22        0.29        1.28       0.38
               X    –F                 3.41         0.41         2.76        0.16        1.83       0.27
                    –Cl                2.20         0.63         2.05        0.24        1.98       0.31
                    –Br                1.83         0.83         1.97        0.46        2.44       0.41
      N             –I                 1.30         1.02         1.80        0.53        2.46       0.15
               O    –OH                2.53         0.25         2.20        0.15        1.73       0.08
  Hal               –O–C               2.38         0.25         2.04        0.13        1.85       0.32
                    –OC=C              2.64         0.36         2.63        0.33        2.00       0.30
                    –O–phenyl          2.87         0.47         2.61        0.38        2.20       0.50
      O             –O–CO–             2.81         0.44         2.83        0.24        2.47       0.59
               N    –N                 1.61         0.14         1.32        0.22        1.13       0.23
                    –N+                2.44         0.39         1.91        0.40        1.78       0.56
      N             –N–CO–             1.88         0.34         1.63        0.22        2.10       0.62
                    –NO2               3.43         0.65         3.08        0.58        2.31
                       –
                    –C – N
                       –               1.12         0.45         1.08        0.33        1.00
      S             –NCS               2.51         0.54         2.20        0.36        1.94       0.60
               S    –S–                1.14         0.45         1.23        0.26        1.06       0.31
                    –S–CO–             1.41         0.37         1.54        0.63        1.31       0.19
  C       X         –S(O)–             1.64         0.36         1.24        0.30        1.25
                    –S(O)2–            1.98         0.42         2.08        0.52        1.50       0.40
                    –SCN               1.75         0.66         1.62                    1.64
  P Si
               O    –CHO               1.34         0.21         1.07           0.29     0.86       0.22
                    –CO–               1.23         0.20         1.12           0.24
Natural        ||   –COOH              1.22         0.23         0.90           0.23     0.87       0.32
Products       C    –COO–              1.15         0.28         0.92           0.35     0.83       0.63
                    –CO–N              1.16         0.28         0.85           0.24     0.94       0.30
Solvents            –COCl              1.94         0.22         1.51           0.25
                                                                        5.1 Alkanes             161

1H   Chemical Shifts of Aromatically Substituted Alkanes (δ in ppm)

                                                           2.89 1.25                           1.32
                                                                                               CH3     C
               2.35             2.63 1.21                              CH3
              CH3              CH2          CH3                CH                      C        CH3
                                                                       CH3
                                                                                               CH3    C       C

                                                        3.10 1.38
             CH3 2.65                   2.46               CH2 CH3                  2.81 1.32         C       C
                                        CH3                                         CH2 CH3




                                   CH3 1.94


     O
              CH3 2.17                                 N
                                                                             N     CH3 2.16
                            O                          CH3 3.50              H
                                                                                                          N
         CH3 2.05                                      H3 C 2.27
                                                                                                       Hal
                               N
                                                               N
                                                                                           N
                           N           CH3 2.42                                     N
 N                         H                                       N
 H                                                                 H                CH3 3.83
                                                                                                          O
         CH3 2.34        H3 C 2.05                                               H3 C 2.18
                                                               N                         N
                                                                                                          N
         N                              N                           CH3 2.44
 N                                 N                       O                               O
 H                                 H                                                                      S
                                       CH3 2.21                N                 H3 C 2.33
                                                                                         N            C       X
     S       CH3 2.41                                      S        CH3 2.74
                               S                                                           S
                                                                                                       P Si
                                                           CH3 2.35
                                        CH3 2.32
                                                                                                      Natural
             CH3 2.55
 N
                               N
                                                                                                      Products
                                                           N
                                                                                    CH3 2.31
                                                                                                      Solvents
                                                   CH3 2.40
             N
                                              N                                    N
              CH3 3.58                        H                                    H
              162     5 1H NMR

              5.1.2 Coupling Constants

              Geminal Coupling Constants (2J in Hz)
      C
                                   H
                               C                  2J         -8 to -18
                                                       HCH
  C       C                        H


              Electronegative substituents cause a decrease in |J|gem while a double or triple bond
  C       C   next to the CH2 group causes an increase. The latter effect is strongest if one of the
              C–H bonds is parallel to the π orbitals:

                                                             H

                                                        H


              Influence of Substituents on the Geminal Coupling Constant

              Compound                    Jgem                   Compound              Jgem
      N
              CH4                        -12.4                   CH3COCH3           -14.9
  Hal         CH3Cl                      -10.8                   CH3COOH            -14.5
              CH2Cl2                      -7.5                   CH3CN              -16.9
              CH3OH                      -10.8                   CH2(CN)2           -20.3
      O               CH3                                                CH2 CN
                                         -14.3                                      -18.5

      N
              Vicinal Coupling Constants (3J in Hz)

      S                       H          H
                                                  conformation not fixed: 3JHCCH ≈ 7
                                                               fixed:     3J
                                                                             HCCH ≈ 0–18
  C       X
              Influence of Substituents on the Vicinal Coupling Constant

  P Si        Compound            Jvic       Compound                Jvic   Compound          Jvic
              CH3CHF2             4.5        CH3CH2OH                6.9    CH3CH2CN          7.6
Natural       CH3CHCl2            6.1        (CH3CH2)3O+ BF4–        7.2    (CH3CH2)2S        7.4
Products      CH3CH2F             6.9        (CH3CH2)3N              7.1    (CH3CH2)4Si       8.0
              CH3CH2Cl            7.2        (CH3CH2)4N+ I–          7.3    CH3CH2Li          8.4
Solvents
                                                                 5.1 Alkanes      163

Vicinal coupling constants strongly depend on the dihedral angle, φ (Kar-
plus equation):
                3J   = J0 cos2 φ - 0.3          0o ≤ φ ≤ 90o                             C
                3J   = J180 cos2 φ - 0.3        90o ≤ φ ≤ 180o

The same relationship between torsional angle and vicinal coupling con- C C
stant holds for substituted alkanes if appropriate values are used for J0 and
J180. These limiting values depend on the electronegativity and orientation
of substituents, the hybridization of carbon atoms, bond lengths, and bond
angles.                                                                       C C

      J / Hz
      15



      10



       5                                                                                  N

                                                                                         Hal
       0

           0         30        60          90              120     150      180
                                                                    φ / degrees
                                                                                          O

                                                                                          N
Long-Range Coupling Constants (|J| in Hz)

Coupling constants through more than three bonds (long-range coupling) in alkanes     S
are generally much smaller than 1 Hz and, thus, not visible in routine 1D NMR
spectra. They are, however, much larger than 1 Hz for fixed conformations (e.g., in
condensed alicyclic systems, see Chapter 5.4) and in unsaturated compounds (see C X
Chapter 5.2). They are also significant when electronegative substituents are present
between the coupling partners, as e.g.:
                                                                                         P Si
                                 CH3       4J        0.7
                          RO                    HH                                      Natural
                          RO     CH3                                                    Products

                                                                                        Solvents
              164        5 1H NMR

              5.2 Alkenes

              5.2.1 Substituted Ethylenes
      C
              1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)

  C       C                      2J                                                                3J
              H         H           gem      2.5                           4.88 H b     H a 5.73      ab   10.0
                                 3J         11.6                                                   3J      16.8
                                    cis                                                    d          ac
                                 3J         19.1                                                   3J       6.4
  C       C   H         H           trans                                  4.97 H c     CH3 1.72      ad
                                                                                                   2J       2.1
                                                                                                      bc
                                                                                                   4J      -1.3
                                                                                                      bd
                                                                                                   4J      -1.8
                                                                                                      cd
              b
                                            4J       -1.7                                          3J      10.9
              H3 C          Ha 5.55            ab                               Hb    H a 5.37        ab
                                            3J       15.1                                          4J      -1.8
                             d                 ac                                                     ac
                                            3J        6.5                                          3J       6.8
                   Hc       CH3 1.58        5J
                                               ad                           H3 C      CH3 1.54        ad
                                                      1.6                   c          d           5J       1.2
                                               bd                                                     cd

      N
                                                    3J      10.3   4J      -1.3
              4.87 H b        H a 5.78
  Hal                                               3J
                                                       ab
                                                            17.2   4J
                                                                      bd
                                                                           -1.7
                                  d         e          ac             cd
                                                    3J       6.2
              4.94 H c        CH2 CH3                  ad
                                                    2J       2.0
      O                       2.00 1.00                bc



      N
              Geminal and Vicinal Couplings of Alkenes (J in Hz)

              The values of the coupling constants strongly depend on the electronegativity
      S       of the substituents (see Table on pp 166, 167). They decrease with increasing
              electronegativity and number of electronegative substituents. The same trend holds
              for the signed values of geminal coupling constants but not for the absolute values
  C       X
              because Jgem can be positive or negative. Although the total ranges of cis and trans
              vicinal coupling constants overlap, Jtrans > Jcis always holds for given substituents.
  P Si                                  Typical ranges:            Jgem -4 to 4
                                                                   Jcis    4 to 12
Natural                                                            Jtrans 14 to 19
Products

Solvents
                                                                              5.2 Alkenes            165

Coupling Over More than Three Bonds in Alkenes (Long-Range
Coupling, J in Hz)

Allylic Coupling                                 φ                                                          C
                                                 Ha
                                                             cisoid:          4J -3.0 to +2.0
                                Hb          C                                   ab
                                                                              4J -3.5 to +2.5
                                                                                                           C       C
                                                             transoid:          ac
                                Hc
                                                                                                           C       C
In acyclic systems, the coupling constants range from ca. -0.8 to -1.8 Hz and, usually,
|J|cisoid is larger than |J|transoid. The magnitudes of the coupling constants depend
on the conformation. Largest absolute values are observed if the C–H bond of the
substituents overlaps with the π electrons of the double bond (φ = 0 or 180o):

                           φ                     4J                 4J
                                                      ab                 ac
                           0o                -3.0                  -3.5
                          90o                +1.8                  +2.2
                         180o                -3.0                  -3.5                                        N
                         270o                 0.0                   0.8
                                                                                                            Hal
Homoallylic Coupling
                                    Hb       Ha                                                                O
                                                             cisoid:   |5Jab| 0–3
                                                             transoid: |5Jac| 0–3                              N
                                    Hc
The values of homoallylic coupling constants between methyl groups and of allylic                              S
ones are comparable:
                         5J                4
                            H C–C=C–CH ≈ JH–C=C–CH
                                3                 3                     3
                                                                                                           C       X
In acyclic systems, |Jcisoid| < |Jtransoid| usually holds. Large homoallylic coupling
constants are occasionally observed in cyclic systems with fixed conformation
between the protons:                                                                                        P Si
               a H       R                                                                                 Natural
                                                             R      X          R                           Products
                                5J        5–11                                       4J        0–7
                  X      X           ab                                                   ab
                                                              Ha               Hb
               b H       R                                                                                 Solvents
              X: CH, N                                     X: O, NH
              R: any substituent                           R: any substituent
              166     5 1H NMR

              1H  Chemical Shifts and Coupling Constants of Monosubstituted Ethylenes
              (δ in ppm, J in Hz)
                                                Hb      Ha
      C
                                                Hc      R

  C       C         Substituent R      Ha      Hb      Hc       Jab   Jac     Jbc   Other
                    –H                 5.28    5.28    5.28    11.6   19.1   2.5
                    –CH3               5.73    4.88    4.97    10.0   16.8   2.1    CH3 1.72
  C       C   C     –CH2CH=CH2         5.71    4.92    4.95    10.3   16.9   2.2    CH2 2.72
                    –CH2–phenyl        5.89    5.00    5.01    10.0   17.0   1.9    CH2 3.19
                    –cyclopropyl       5.32    4.84    5.04    10.4   17.1   1.8
                    –cyclohexyl        5.79    4.88    4.95    10.5   17.6   1.9
                    –CF3               5.90    5.56    5.85    11.1   17.5   0.2
                    –CH=C=CH2          6.31    4.99    5.19    10.1   17.2   1.6
                    –C – C–CH3
                       –
                       –               5.62    5.24    5.39    11.1   17.0   2.3
                    –phenyl            6.72    5.20    5.72    11.1   17.9   1.0
                    –2-naphthyl        6.87    5.32    5.86
      N             –2-nitrophenyl     7.19    5.45    5.68    10.7   17.4    1.1
                    –3-nitrophenyl     6.74    5.42    5.86    10.9   17.5    0.4
  Hal               –4-nitrophenyl     6.77    5.48    5.90    10.9   17.4    0.8
                    –2-pyridyl         6.84    5.45    6.22    11.3   18.5    1.4
                    –4-pyridyl         6.61    5.42    5.91    10.8   17.6    0.7
      O
               X    –F                 6.17    4.03    4.37     4.7   12.8   -3.2
                    –Cl                6.26    5.39    5.48     7.5   14.5   -1.4
                    –Br                6.44    5.97    5.84     7.1   14.9   -1.9
      N             –I                 6.53    6.23    6.57     7.8   15.9   -1.5
              O     –OH                6.45    3.82    4.18     6.4   14.2   -1.0
      S             –OCH3              6.44    3.88    4.03     7.0   14.1   -2.0   CH3 3.16
                    –OCH=CH2           6.49    4.21    4.52     6.4   14.0   -1.8
                    –O–phenyl          6.64    4.40    4.74     6.1   13.7   -1.6
  C       X         –OCHO              7.33    4.66    4.96     6.4   13.9   -1.7   CHO 8.07
                    –OCOCH3            7.28    4.56    4.88     6.3   14.1   -1.6   CH3 2.13
                    –OCOCH=CH2         7.39    4.62    4.96     6.4   14.2   -1.6
  P Si              –OCO–phenyl        7.52    4.67    5.04     6.3   13.8   -1.7
                    –OP(O)(O–ethyl)2   6.58    4.59    4.91     6.0   13.8   -2.1
Natural       N     –NH2               ≈6.05   ≈3.99   ≈4.04
Products            –N+(CH3)3Br–       6.50    5.54    5.76     8.2 15.1     -4.3
                    –NHCOCH3           ≈7.33   ≈4.68   ≈4.53
                    –NO2               7.12    5.87    6.55     7.0   14.6    1.4
Solvents            –C – N
                       –
                       –               5.69    6.11    6.24    11.8   17.9    0.9
                    –NC                5.90    5.35    5.58     8.6   15.6   -0.5
                    –NCO               6.12    4.77    5.01     7.6   15.2   -0.1
                                                         5.2 Alkenes      167

     Substituent R     Ha     Hb     Hc      Jab   Jac      Jbc   Other

S    –SCH3             6.43   5.18   4.95   10.3   16.4    -0.3   CH3 2.25
     –S–phenyl         6.53   5.32   5.32    9.6   16.7    -0.2                  C
     –S(O)CH3          6.77   5.92   6.08    9.8   16.7    -0.6   CH3 2.61
     –S(O)2CH3         6.76   6.14   6.43   10.0   16.5    -0.5   CH3 2.96
     –S(O)2CH=CH2      6.67   6.17   6.41   10.0   16.4    -0.6                 C       C
     –S(O)2OH          6.73   6.13   6.41   10.2   16.8    -1.2
     –S(O)2OCH3        6.57   6.22   6.43   10.1   16.9    -0.6   CH3 3.85
     –S(O)2NH2         6.93   5.98   6.17   10.0   16.3     0     NH2 6.7       C       C
     –S(O)2NH–phenyl   6.56   5.86   6.18   10.1   16.7    -0.3   NH 9.07
     –SF5              6.63   5.64   5.96    9.8   16.6     0.4
     –SCN              6.19   5.70   5.66
O    –CHO              6.37   6.52   6.35   10.0   17.4     1.0   CHO 9.59
     –COCH3            6.30   5.91   6.21   10.7   18.7     1.3   CH3 2.29
||   –COCH=CH2         6.67   5.82   6.28   11.0   17.9     1.4
C    –CO–phenyl        7.20   5.81   6.52    9.9   17.7     2.3
     –COOH             6.15   5.95   6.53   10.5   17.2     1.8   COOH 12.8
     –COOCH3           6.12   5.83   6.41   10.6   17.4     1.5   CH3 3.77          N
     –CONH2            6.48   5.71   6.17    7.9   17.3     5.0   NH2 7.55
     –CON(CH3)2        6.64   5.55   6.12    9.8   17.0     3.4                  Hal
     –COF              6.14   6.25   6.60   10.7   17.3     0.8
     –COCl             6.35   6.16   6.63   10.6   17.4     0.2
P    –P(CH3)2          6.23   5.51   5.39   11.8   18.3     2.0   CH3 0.95          O
     –P(CH=CH2)2       6.16   5.64   5.59   11.8   18.4     2.0
     –P(phenyl)2       7.38   6.31   7.07   12.5   18.2     0
     –PCl2             7.48   6.68   6.64   11.7   18.6     0.4                     N
     –P(O)(phenyl)2    6.72   6.21   6.25   12.9   18.9     1.8
     –PSCl2            6.42   5.90   6.13   11.0   17.5     0.3
     –P(S)(CH3)2       6.60   6.14   6.26   11.8   17.9     1.8                     S
     –P(S)(phenyl)2    6.82   6.17   6.34   11.7   17.9     1.6
M    –Li               7.29   6.65   5.91   19.3   23.9     7.1
                                                                                C       X
     –MgBr             6.66   6.15   5.51   17.7   23.3     7.6
     –Si(CH3)3         6.11   5.88   5.63   14.6   20.2     3.8   CH3 0.06
     –Sn(CH=CH2)3      6.39   6.21   5.75   13.4   20.7     3.1                  P Si
     –Pb(CH=CH2)3      6.70   6.19   5.46   12.2   19.8     2.1
     –HgBr             6.45   5.92   5.52   11.9   18.7     3.1
                                                                                Natural
                                                                                Products

                                                                                Solvents
              168     5 1H NMR

              Estimation of 1H Chemical Shifts of Substituted Ethylenes (δ in ppm)

                                                 R cis    H
      C
                                               R trans    R gem

  C       C                          δ C=CH = 5.25 + Zgem + Zcis + Ztrans


  C       C
                    Substituent R                        Zgem          Zcis   Ztrans
                    –H                                    0.00         0.00    0.00
                    –alkyl                                0.45        -0.22   -0.28
              C     –alkyl ring1                          0.69        -0.25   -0.28
                    –CH2–aromatic                         1.05        -0.29   -0.32
                    –CH2X, X: F, Cl, Br                   0.70         0.11   -0.04
                    –CHF2                                 0.66         0.32    0.21
                    –CF3                                  0.66         0.61    0.32
      N             –CH2O–                                0.64        -0.01   -0.02
                    –CH2N                                 0.58        -0.10   -0.08
                    –CH2CN                                0.69        -0.08   -0.06
  Hal               –CH2S–                                0.71        -0.13   -0.22
                    –CH2CO–                               0.69        -0.08   -0.06
      O             –C=C                                  1.00        -0.09   -0.23
                    –C=C conjugated2                      1.24         0.02   -0.05
                       –
                    –C – C–
                       –                                  0.47         0.38    0.12
      N             –aromatic                             1.38         0.36   -0.07
                    –aromatic, fixed3                     1.60            –   -0.05
                    –aromatic, o-substituted              1.65         0.19    0.09
      S        X    –F                                    1.54        -0.40   -1.02
                    –Cl                                   1.08         0.18    0.13
                    –Br                                   1.07         0.45    0.55
  C       X         –I                                    1.14         0.81    0.88
                    –OC (sp3)                             1.22        -1.07   -1.21
              O     –OC= (sp2)                            1.21        -0.60   -1.00
  P Si              –OCO–                                 2.11        -0.35   -0.64
                    –OP(O)(OCH2CH3)2                      1.33        -0.34   -0.66
Natural       N     –NR2; R: H, C (sp3)                   0.80        -1.26   -1.21
Products            –NR–; R: C= (sp2 )                    1.17        -0.53   -0.99
                    –NCO–R                                2.08        -0.57   -0.72
Solvents            –N=N–phenyl                           2.39         1.11    0.67
                    –NO2                                  1.87         1.30    0.62
                       –
                    –C – N
                       –                                  0.27         0.75    0.55
                                                                    5.2 Alkenes           169

      Substituent R                               Zgem            Zcis          Ztrans
      –S–                                         1.11           -0.29         -0.13
 S    –S(O)–                                      1.27            0.67          0.41              C
      –S(O)2–                                     1.55            1.16          0.93
      –SCO–                                       1.41            0.06          0.02
      –SCN                                        0.94            0.45          0.41             C       C
      –SF                                         1.68            0.61          0.49
 O    –CHO                                        1.02            0.95          1.17
                                                                                                 C       C
      –CO–                                        1.10            1.12          0.87
 ||   –CO– conjugated2                            1.06            0.91          0.74
 C    –COOH                                       0.97            1.41          0.71
      –COOH conjugated2                           0.80            0.98          0.32
      –COOR                                       0.80            1.18          0.55
      –COOR conjugated2                           0.78            1.01          0.46
      –CON                                        1.37            0.98          0.46
      –COCl                                       1.11            1.46          1.01
      –P(O)(OCH2CH3)2                             0.66            0.88          0.67
1) The increment "alkyl ring" is to be used if the substituent and the double bond are part of
                                                                                                     N
   a cyclic structure.
2) The increment "conjugated" is to be used if either the double bond or the substituent is
   conjugated to other substituents.
                                                                                                  Hal
3) The increment "aromatic, fixed" is to be used if the double bond conjugated to an aro-
   matic ring is part of a fused ring (such as in 1,2-dihydronaphthalene).
                                                                                                     O

Influence of cis- and trans-Substituents on the 1H Chemical Shift of
                                                                                                     N
Methyl Groups at the Double Bond in Isobutenes (δ in ppm)
                                                                                                     S
1.70 H3 C        H 4.63         1.68 H3 C         H 5.13           1.80 H3 C           H 5.17

      H3 C       H              1.62 H3 C                          1.88 H3 C                     C       X


1.75 H3 C         H 5.78        1.65 H3 C         H 6.79           1.91 H3 C         H 5.63       P Si

1.75 H3 C         Br            1.65 H3 C         OCOCH3           2.11 H3 C         CHO         Natural
                                                                                                 Products
1.86 H3 C         H 5.97        1.84 H3 C         H 5.62           1.97 H3 C         H 6.01
                                                                                                 Solvents
2.06 H3 C         COCH3         2.12 H3 C         COOCH3           2.12 H3 C         COCl
              170        5 1H NMR

              1H  Chemical Shifts and Coupling Constants of Enols (δ in ppm,
              J in Hz)
                       ≈16                             ≈16
      C                         H                                                      H
                          O          O                    3J 9.7                   O        O              3J        5.1
                                                            ab                                                  ab
                                                          3 J ≈8
                                          H c ≈9.3           bc          7.90 Ha
              8.40 H a                                                                          CH3 2.11
  C       C
                                Hb                                                     Hb
                               5.04                                                    5.60
  C       C


              5.2.2 Conjugated Dienes

              1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)


                                               3J      10.2      2J      1.8
                     6.27                         ab                bc
                        Ha         Hf          3J      17.1      5J      1.3
      N       5.06                                ac                be
                                               3J      10.4      5J      0.6
              H                                   ad                bf
              b                         He     4J      -0.9      5J      0.7
  Hal              Hc         Hd               4J
                                                  ae
                                                  af   -0.8
                                                                    cf

                  5.16

      O              6.21 5.61                    3J      10.2      2J       1.9   6J      -0.7
                        Ha         Hf                ab                bc             ce
              4.86                                3J      16.9      4J      -0.8   5J       0.7
                                          e          ac                bd             cf
              H                                   3J                6J             4J
      N       b                         CH3
                                                  5J
                                                     ad   10.3
                                                                    5J
                                                                       be   -0.7
                                                                                   3J
                                                                                      de   -1.6
                                        1.71         ae    0.4         bf    0.7      df   15.1
                   Hc         Hd                  4J                4J             3J
                                                     af   -0.8         cd   -0.8      ef    6.6
                  4.98        5.98
      S
                     6.59          1.72           3J      10.2      2J       2.1   5J       0.7
                         Ha        CH3 f             ab                bc             ce
              5.03                                3J      16.9      4J      -0.8   6J      -0.6
  C       X   H                                   3J
                                                     ac
                                                                    5J
                                                                       bd
                                                                                   3J
                                                                                      cf
              b                         He           ad   10.9         be   -0.7      de   10.8
                                                  4J      -1.1      6J       0.7   4J      -1.8
                   Hc         Hd        5.45      5J
                                                     ae
                                                                    4J
                                                                       bf
                                                                                   3J
                                                                                      df
                                                           0.2              -0.8            7.0
  P Si            5.11        5.92
                                                     af                cd             ef


Natural
Products

Solvents
                                                                       5.2 Alkenes         171

5.2.3 Allenes

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
                                                                                                  C
            4.67                                                         5J
H            Ha                                   Hb           CH3 a        ab    3.2
                                                                         6J       0
     C C C
                   2J
                      ab   -9
                                                   C C C                    ac                   C       C
                   4J      -6                                            3J       6.8
                      ac                                                    ad
             Hb                             H3 C               Hd        4J
Hc
                                                                            bd   -6.4
                                            c
                                                                                                 C       C

1H  Chemical Shifts and Coupling Constants of Monosubstituted Allenes
(δ in ppm, J in Hz)
                                       Hb               Ha
                                           C C C
                                       H                R

Substituent R         Ha         Hb         Jab        Other                                         N
–H                  4.67        4.67       -9.0
–CH3                4.94        4.50       -6.7        CH3 (c) 1.59, 3Jac 7.2, 5Jbc 3.4
                                                                                                  Hal
–CH2CH3             5.03        4.55       -6.8        CH2 (c) 1.95, 3Jac 6.2, 5Jbc 3.5
–CH2Cl              5.4.3       4.92       -6.6        CH2 (c) 4.11, 3Jac 7.7, 5Jbc 2.2              O
–CH=CH2             5.96        4.92       -6.6        CH (c) 6.31, 3Jac 10.4, 5Jbc 1.1a
–Cl                 5.76        5.17       -6.1
–Br                 5.85        4.83       -6.1                                                      N
–I                  5.63        4.48       -6.3
–phenyl             5.91        4.92
–OCH3               6.77        5.48       -5.9                                                      S
–COCH3              5.77        5.25       -6.4
   –
–C – N
   –                4.97        5.04
–Si(CH3)3           4.92        4.31                                                             C       X
–SiCl3              5.35        4.92       -5.9
–SnCl3              4.98        4.11       -7.2
                                                                                                  P Si
a =CH , H (d) 5.19, 4J -0.8, 6J        -1.5, 3Jcd 17.2; CH2, Htrans (e) 4.99, 4Jae -0.9,
     2    cis          ad       bd
6J -1.8, 3J 10.1, 2J 1.6
  be        ce      de                                                                           Natural
                                                                                                 Products

                                                                                                 Solvents
              172      5 1H NMR

              5.3 Alkynes
              1H   Chemical Shifts of Substituted Alkynes (δ in ppm)
      C
                                                                R   C C Ha
  C       C
                     Substituent R                         Ha                Substituent R              Ha

  C       C
                     –H                                    1.91        S     –SCH2CH3                   2.79
              C      –CH3                                  1.91              –SCH=CH2                   3.26
                     –CH2CH3                               1.97              –S–phenyl                  3.28
                     –C(CH3)3                              2.07              –S(O)2–n-butyl             3.95
                     –CF3                                  2.95        O     –COCH3                     3.65
                     –CH=CH2                               3.07              –CO–phenyl                 3.48
                     –C – CH
                        –                                  2.16
                                                                       ||    –COOH                      3.17
                        –
                     –phenyl                               3.07        C     –COOCH2CH3                 2.90
                     –1-naphthyl                           3.43              –CONH2                     3.05

      N       X      –F                                    1.74        Si    –Si(CH3)3                  2.34
                     –Cl                                   2.05              –Si(phenyl)3               2.47
                     –Br                                   2.32        P     –P(CH2CH3)2                2.85
  Hal                –I                                    2.34              –P(phenyl)2                3.22
                     –OCH2CH3                              1.48              –P(O)(CH2CH3)2             3.33
              O                                                              –P(O)(phenyl)2             3.48
                     –OCH=CH2                              2.04
      O              –O–phenyl                             2.07
                     –N(CH2CH3)2                           2.30
              N      –N(phenyl)2                           2.86
      N                 –
                     –C – N                                2.63
                        –

      S       1H,1H   Coupling Constants of Substituted Alkynes (J in Hz)

              a               b                                       a           b    c
                                          4J        2.9                                        4J      2.6
              H            CH3
  C       X                                    ab                     H          CH 2 CH 3
                                                                                               5J
                                                                                                  ab
                                                                                                  ac   0
                                                                                               3J      7.4
                                                                                                  bc
  P Si        a
              H3 C            CH3
                                  b
                                          |5Jab| 2.7
                                                                      a
                                                                      H 3C
                                                                                    b
                                                                                   CH 2 CH 3   |5Jab| 2.5

Natural
                              b           4J                                       b
Products                                             2.0                               c
                                                                                               5J
                                                                                                  ab 0.3
                              H              ab                       a
              a                           5J         1.0
                                      c      ac                       H                    d   6J -0.1
              H                           6J         0.6                                          ac
                                                                                               7J
                                                                                                  ad 0.2
                                      H      ad
Solvents                                  3J        10.5
                                             bc
                          H3 C            4J         1.6
                          d                  bd
                                          3J         6.5
                                             cd
                                                                                                  5.4 Alicyclics                173

5.4 Alicyclics
1HChemical Shifts and Coupling Constants of Saturated Alicyclic
Hydrocarbons (δ in ppm, J in Hz)
                                                                                                                                       C

                 0.20 2Jgem -4.3 In derivatives:                                         1.94 In derivatives:
                      3J           2                                                          2J                                      C       C
                         cis 9.0 Jgem -3 to -9                                                   gem -10 to -17
                      3J       5.6 3Jcis 6 to 12                                              3J          4 to 12
                         trans                                                                   cis
                                   3J                                                         3J
                                      trans 2 to 9                                               trans    2 to 10                     C       C
                                   Throughout:                                                4J
                                                                                                 cis ≈ 0
                                   Jcis > Jtrans                                              4J
                                                                                                 trans ≈ -1


                 1.51 In derivatives:                                      1.44 In derivatives:
                      2J                                                        2J
                         gem-8 to -18                                              gem -11 to -14
                      3J                                                        3J
                         cis 5 to 10                                               ax,ax 8 to 13
                      3J                                                        3J
                         trans 5 to 10                             At -100 °C      eq,ax 2 to 6
                                                                                3J
                                                                   Hax 1.12        eq,eq 2 to 5
                                                                   Heq 1.60     Generally:
                                                                                                                                          N
                                                                                Jeq,ax ≈ Jeq,eq +1

                                                                                    5.95                                               Hal
    c        b   7.01                                                              b 2J                           3J
                          In derivatives:                              c
                                                                                        gem-13.7                     ad,cis 1.8
                          3J 1.5 to 2.0                                              3J      1.0                  3J
                                                                                                                     ad,trans 4.6
         a   0.92           ab
                          3J 0.5 to 1.5
                            bc
                                                                       d           a
                                                                                     4J
                                                                                2.57 ac
                                                                                        ab
                                                                                            -0.3                  3J
                                                                                                                     bc       2.8         O

    d        c   5.66        2J
                                gem,a -12.8
                                                 4J
                                                    bd      -2.3       d             c   6.43           3J
                                                                                                           ab 1.3
                                                                                                                        4J
                                                                                                                           bd   1.1       N
                             3J          9.3     5J
                                                    be,cis 2.1
                 b 2.27                                                                                 4J -1.5         5J      2.0
e                               ab,cis                             e                     b   6.28          ac              be
                             3J                  5J
                                ab,trans 5.7        be,trans 3.0
                                                                                                        3J              3J
                                                                                                           bc 5.0               1.9
         a
        1.79                 2J
                                gem,b -16.1
                                                 3J
                                                    cd       5.8           2.80
                                                                                a                                          cd
                                                                                                                                          S
                             3J          2.3
                                bc

                                                                                                                                      C       X
    f            a   6.533J        5.1         4J      -0.2                     a
                            ab                    bc                                                     3J      ≈10
                         5                     4J                                                           ab
                   b 6.23 Jac      0.5                 -0.4                                      5.69
                                                                                         b               3J
    e                                             bd                                                              1.5
                         5J
                            ad     1.4         4J
                                                  be    2.0                             1.99
                                                                                         c
                                                                                                            bc
                                                                                                                                       P Si
                         4J        1.3         2J       0.1
    d            c          ae                    cd                           d    1.60
                 H 5.89 3Jaf       2.0
    H
                                                                                                                                      Natural
                                                                                                                                      Products
                 a   5.67       3J
                                                                           a        b    5.79            3J      ≈10
                                   ab    9.7                                                             3J
                                                                                                            ab
2.08                   b 5.79   4J                                                           c   2.12             3.7
                                   ac    1.0                                                                bc
                                                                                                                                      Solvents
                      c         5J       1.1
                                   ad                                                    d       1.50
                                3J       5.1                                    e
                 d                 bc
                                                                               1.75
              174              5 1H NMR

                   a        b      6.50           3J               5J                      a   b   5.56         3J ≈10
                                                     ab 11.2          cg -0.6                                      ab
                                                  4J               3J                                           3J    3.7
              g                    c       6.09      ac 0.8           de 6.7                        c    2.11      bc
                                                  3J               2J -13.0
      C                                              bc 5.5           ee'
               f                   d 5.26         3J                                                d    1.5
                       e, e'                         cd 8.9
                                                  5J = 4J       = 5Jdg = 0
                                                                                               e   1.5
                       2.22                         cf     df
  C       C                                                                                                        7.90
                       a'      a   5.79            3J
                                                      ab    11.3                                                           7.38
                                                                                       1.76
  C       C
              b'                       b   5.59    3J
                                                      aa'    4.1
                                                   4J       -0.6                       1.87
                                      2.14
                                       c              ab'                                                                   8.31
                                                   5J        0.5
                               d   1.47               bb'
                                                                                                                           7.12
                                                                                                                   7.52

                   1.18                                                                                           2.00
                   H        H                                         1.34 H        H 1.12                             H
                                                                                                                  H


                                 H 1.47                                                H 1.63
      N                H       H 1.16                           6.02 H          H
                                                                                     H 0.98                        H       H 6.75
                   2.19                                                      2.87                                 3.58
  Hal

      O
                                                                                      H 1.50
                                                                6.25 H
                    1.50 1.50                                                 H     H 1.23                        4.60      6.63
                                                                             2.48
      N

              In condensed alicyclics, couplings over four bonds are often observed. Such long-
      S
              range couplings are particularly large if the arrangement of the bonds between the
              two protons is W-shaped (cf. Jac vs. Jad and Jbd below left and Jac vs. Jbc below
  C       X   right). Owing to the rigid arrangement, vicinal coupling constants (3J) may assume
              unusually small values when the torsional angles are close to 90° (Jce below right).

  P Si
                                                                                               a
                                   b                                                  b        H 1.73
Natural            a
                                   H          4J                                1.55 H                                   4J       2.3
                   H                                  ≈7                                           2.67                     ac
Products                                      4J
                                                 ac                                                                      4J      -0.1
                                                 ad   ≈0                      1.82 H                H                       bc
                                                                                                           H 2.06        3J       0.1
                                              4J      ≈0                                                                    ce
                                                 bd                           1.47                                       3J
Solvents                                     Hd                                                                             de    4.7
                                                                         1.82 Hd       H                 H 1.84
                                   Hc                                                 e    H
                                                                             1.50 Hc 2.59            O
                                                                       5.4 Alicyclics                 175

1H Chemical Shifts and Coupling Constants of Monosubstituted Cyclopro-
panes (δ in ppm, J in Hz)
                                       c
                                       H                                                                        C
                                  e Hb
                                                    R
                                  H
                                                    Ha                                                         C       C
                                      Hd

      Substituent R        Ha Hb;d Hc;e            3J        3J        2J        3J        3J        3J
                                                        ab        ac        bc        bd        be        ce   C       C
      –H                   0.20   0.20      0.20    9.0       5.6 -4.3            9.0       5.6       9.0
 C    –CH3                 1.00   0.35      0.15
      –CH2OH               1.14   0.40      0.30
      –CH=CH2              1.35   0.64      0.34    8.2       4.9      -4.5       9.3       6.2       9.0
      –phenyl              1.83   0.89      0.65    9.5       6.3      -4.5       9.5       5.2       8.9
      –F                   4.32   0.69      0.27    5.9       2.4      -6.7      10.8       7.7      12.0
 X
      –Cl                  2.55   0.87      0.74    7.0       3.6      -6.0      10.3       7.1      10.6
      –Br                  2.83   0.96      0.81    7.1       3.8      -6.1      10.2       7.0      10.5
      –I                   2.31   1.04      0.76    7.5       4.4      -5.9       9.9       6.6      10.0          N
 O    –OH                  3.35   0.40      0.48    6.2       2.9      -5.4      10.3       6.8      10.9
 N    –NH2                 2.23   0.32      0.20    6.6       3.6      -4.3       9.7       6.2       9.9       Hal
      –NH3+                1.06   0.52      0.34
      –NO2                 4.21   1.13      1.60    7.0       3.4      -5.5 10.1            8.3 11.3
         –
      –C – N
         –                 1.29   0.96      1.04    8.4       5.1      -4.7 9.2             7.1 9.5                O
 O    –CHO                 1.79   0.99      1.03    8.0       4.6      -4.5 8.8             7.0 9.6
      –COCH3               1.83   0.77      0.93    7.9       4.6      -3.5 9.2             7.0 9.5
 ||   –CO–cyclopropyl      1.70   0.56      1.02    7.9       4.6      -3.5 9.1             7.0 9.5                N
 C    –CO–phenyl           2.65   1.01      1.23
      –COOH                1.59   0.91      1.05    8.0       4.6 -4.0            9.3       7.1       9.7
      –COOCH3              1.61   0.86      0.98    8.0       4.6 -3.4            8.8       6.9       9.6          S
      –CONH2               1.39   0.70      0.95
      –COF                 1.66   1.11      1.20    8.0       4.6      -4.5 10.1            7.5 9.3
      –COCl                2.11   1.18      1.28    7.9       4.4      -4.5 9.2             7.6 10.0           C       X
 M    –Li                 -2.53   0.43     -0.12   10.3       9.1      -1.6 7.7             3.2 6.5
      –MgBr               -2.04   0.25     -0.13   11.0       8.5      -1.7 7.8             3.5 6.6
      –B(cyclopropyl)2    -0.25   0.61      0.66    8.9       5.8      -3.3 8.2             5.9 8.4
                                                                                                                P Si
      –Si(cyclopropyl)3   -0.67   0.49      0.36    9.7       6.9      -3.4 8.4             5.1 8.1
      –P+(phenyl)3         3.28   1.82      0.63                                                               Natural
      –Hg–cyclopropyl      0.00   0.75      0.47    9.6       6.9 -3.7            8.5       4.8       7.9      Products

                                                                                                               Solvents
              176     5 1H NMR

              1H  Chemical Shifts and Coupling Constants of Equatorially and Axially Sub-
              stituted Cyclohexanes (δ in ppm, J in Hz)
                                                        H                                             R
      C                                        H          1                                  H           1
                                                                R                                             H
                              R'                            H                   R'                        H
                                   4           3     2                               4       3      2
                                           H                                             H
  C       C                            H            H                                H            H
                     Eq. substituent R H1,ax                    H2,ax   H2,eq    H3,ax           H3,eq        H4,ax   H4,eq
  C       C          –D*                           1.12         1.12    1.60     1.12            1.60         1.12    1.60
               C     –C*                           1.27         0.81    1.57     1.15            1.60         1.06    1.58
                        –
                     –C – C*
                        –                          2.25         1.36    1.98     1.20            1.73         1.17    1.67
                     –phenyl*                      2.46
               X     –F*                           4.49         1.42    2.15     1.28            1.86         1.12    1.65
                     –Cl*                          3.88         1.58    2.22     1.33            1.84         1.18    1.68
                     –Br*                          4.09         1.75    2.33     1.35            1.80         1.22    1.72
                     –I*                           4.18         1.97    2.45     1.36            1.67         1.30    1.80
               O     –OH**                         3.52         1.22    2.01     1.05            1.78         0.97
      N              –OCOCH3*                      4.74         1.72    1.85     1.35            1.41         1.25    1.55
               N     –NH2**                        2.55         1.03    1.89     1.03            1.76         0.96
                     –NHCOCH3**                    3.67         1.07    2.01     1.11            1.78         1.01
  Hal                –NO2*                         4.38         2.23    1.85     1.38            1.85         1.28    1.67
                        –
                     –C – N**
                        –                          2.31         1.53    2.16     0.98            1.86         1.03
      O        S     –SH*                          2.79         1.34    2.01     1.31            1.75         1.22    1.61
                     –COOCH3*                      2.30         1.44    1.90     1.27            1.75         1.24    1.64

      N              Ax. substituent R H1,eq                    H2,ax   H2,eq    H3,ax           H3,eq        H4,ax   H4,eq
                     –D*                 1.60                   1.12    1.60     1.12            1.60         1.12    1.60
               C     –C*                 1.93                   1.37    1.40     1.39            1.34         1.06    1.58
      S                 –
                     –C – C*             2.87                   1.48    1.78
                        –
                     –phenyl*            3.16                           2.42
  C       X    X     –F*                 4.94                   1.43    2.03     1.63            1.75         1.28    1.58
                     –Cl*                4.59                   1.76    2.00     1.77            1.75         1.26    1.75
                     –Br*                4.80                   1.81    2.08     1.79            1.60         1.24    1.78
  P Si               –I*                 4.96                   1.53    2.06     1.72            1.62         1.26    1.73
               O     –OH**               4.03                   1.49    1.83     1.35            1.54         0.99
                     –OCOCH3*            5.31                   1.49    2.51
Natural
Products       N     –NH2**              3.15                   1.54    1.65     1.27            1.53         0.96
                     –NHCOCH3**          4.11                   1.51    1.85     1.03            1.66         1.04
                     –NO2**              4.43                   1.6     2.6
Solvents                –
                     –C – N**
                        –                2.96                   1.54    2.00     1.50            1.70         1.20
               S     –SH**               3.43                   1.5     1.9
              * R': –H; ** R': –tert-butyl
                                                      5.5 Aromatic Hydrocarbons                          177

5.5 Aromatic Hydrocarbons
1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
                                                                                                                 C
                                                               7.84               In derivatives:
              7.34 In derivatives:                       h       a                3J
                                                                                     ab 8–9 6Jaf ≈-0.1
                   3J
                      ortho 6.5–8.5              g                     b   7.48   4J    1–2 5Jag ≈0.2
                                                                                                       C                C
                   4J                                                                ac
                      meta 1.0–3.0               f                     c          5J     ≈1 ah4J ≈-0.5
                   5J                                                                ad
                      para 0.0–1.0                       e      d                 3J    5–7 7Jbf ≈0.3
                                                                                  5J
                                                                                     bc                C                C
                                                                                     ae≈0.9 6Jbg ≈0.1

                        8.01             In derivatives:                                         8.00
                         a
                                         3J      8.5–9.5
                               b    7.47 4Jab 0.8–1.5                                                    7.39
                                            ac
                               c         5J
                                            ad   0.6–0.9
              e          d               5J         ≈0.8                                  8.67
                                            ae
         8.43                            3J      6.5–8.0
                                            bc
                                         4J         ≈0.4
                                            de
                                                                                                                    N
                  7.67                  3J8.4                                                    7.68
                   b                       ab
                                        4J1.2
     8.70 a              c 7.61         5J
                                           ac
                                          0.7                              8.13 9.17
                                                                                    8.84                 7.65    Hal
                         d 7.90         3J
                                           ad                                                            7.85
                                          7.2
                                           bc                       7.56
                                        4J
                        7.75            3J
                                          1.3
                                           bd                       7.54                            7.62            O
                    e                     8.1
                                           cd
              f                In derivatives:                             8.05   8.37 7.80
                                   3J
                                      ef ≈9                                                                         N
                                                              7.66                                8.90
      8.08 8.19                                                        7.47                                         S
                             8.01                                      8.20

                                                                                                                C       X


                                                                                                                 P Si

                                                                                                                Natural
Weak long-range couplings                            CH3 a     4J
                                                                  ab   -0.7          CH3 a 5Jab ≈0.8            Products
between aromatic protons and                                   5J       0.3
                                                                  ac
aliphatic substituents are usually                           b 6Jad    -0.6
                                                                                     O
not resolved but lead to a char-                                                                                Solvents
                                                             c                               b
acteristic broadening of the cor-
responding lines.                                    d
              178    5 1H NMR

              Effect of Substituents on 1H Chemical Shifts of Monosubstituted Benzenes (in
              ppm)
                                   3   2
      C                                    1
                               4               R   δH = 7.34 + Zi
                                                     i

  C       C

                          Substituent R                   Z2         Z3        Z4
  C       C               –CH3                           -0.17      -0.09     -0.17
                     C    –CH2CH3                        -0.14      -0.05     -0.18
                          –CH(CH3)2                      -0.13      -0.08     -0.18
                          –C(CH3)3                        0.05      -0.04     -0.18
                          –CF3                            0.19      -0.07      0.00
                          –CCl3                           0.55      -0.07     -0.09
                          –CH2OH                         -0.07      -0.07     -0.07
                          –CH=CH2                         0.08      -0.02     -0.09
                          –CH=CH–phenyl (trans)           0.16       0.00     -0.15
      N                      –
                          –C – CH
                             –                            0.16      -0.01     -0.01
                          –C – C–phenyl
                             –
                             –                            0.20      -0.04     -0.07
  Hal                     –phenyl                         0.22       0.06     -0.04
                          –2-pyridyl                      0.73       0.09      0.02
                          –F                             -0.31      -0.03     -0.21
      O              X    –Cl                            -0.01      -0.06     -0.12
                          –Br                             0.15      -0.12     -0.06
                          –I                              0.36      -0.24     -0.02
      N                   –OH                            -0.51      -0.10     -0.41
                    O     –OCH3                          -0.44      -0.05     -0.40
                          –OCH2CH=CH2                    -0.45      -0.13     -0.43
      S                   –O–phenyl                      -0.33      -0.02     -0.25
                          –OCOCH3                        -0.26       0.03     -0.12
                          –OCO–phenyl                    -0.12       0.10     -0.06
  C       X
                          –OS(O)2CH3                     -0.05       0.07     -0.01
                          –NH2                           -0.67      -0.20     -0.59
                     N
  P Si                    –NHCH3                         -0.73      -0.16     -0.64
                          –N(CH3)2                       -0.60      -0.10     -0.62
                          –N(phenyl)2                    -0.26      -0.10     -0.34
Natural
                          –N+(CH3)3 I–                    0.72       0.40      0.34
Products
                          –NHCHO (trans to O)            -0.25       0.03     -0.13
                          –NHCHO (cis to O)              -0.20       0.21     -0.01
Solvents                  –N(CH3)CHO                     -0.16       0.07     -0.05
                          –NHCOCH3                        0.15      -0.02     -0.23
                          –NHCSNH2                        0.14       0.07     -0.14
                        5.5 Aromatic Hydrocarbons     179

     Substituent R          Z2       Z3        Z4
     –NHNH2                -0.60    -0.08     -0.55
     –N=N–phenyl            0.67     0.20      0.20          C
     –NO                    0.55     0.29      0.35
     –NO2                   0.93     0.26      0.39
        –
     –C – N
        –                   0.32     0.14      0.28         C       C
     –NCS                  -0.11     0.04     -0.02
S    –SH                   -0.08    -0.16     -0.22
     –SCH3                 -0.08    -0.10     -0.24         C       C
     –S–phenyl             -0.06    -0.20     -0.26
     –S–S–phenyl            0.13    -0.05     -0.10
     –S(O)–CH=CH2           0.28     0.15      0.15
     –S(O)–phenyl           0.29     0.09      0.13
     –S(O)2CH3              0.70     0.37      0.41
     –S(O)2OCH3             0.60     0.26      0.28
     –S(O)2Cl               0.68     0.27      0.37
     –S(O)2NH2              0.51     0.28      0.24
     –CHO                   0.54     0.19      0.29             N
O    –COCH3                 0.62     0.12      0.22
||   –COCH2CH3              0.61     0.11      0.21          Hal
C    –CO–phenyl             0.56     0.12      0.23
     –CO–(2-pyridyl)        0.86     0.11      0.20
     –COOH                  0.79     0.14      0.28             O
     –COOCH3                0.70     0.09      0.21
     –COOCH(CH3)2           0.73     0.11      0.20
     –COO–phenyl            0.87     0.18      0.30             N
     –CONH2                 0.48     0.11      0.19
     –COF                   0.71     0.21      0.38
     –COCl                  0.77     0.15      0.35             S
     –COBr                  0.70     0.15      0.32
     –CH=N–phenyl           0.64     0.24      0.24
                                                            C       X
M    –Li                    0.77     0.26     -0.29
     –MgBr                  0.40    -0.19     -0.26
     –Mg–phenyl            -0.49     0.18      0.25          P Si
     –Si(CH3)3              0.19     0.00      0.00
     –Si(phenyl)2Cl         0.32     0.07      0.12
                                                            Natural
     –SiCl3                 0.52     0.20      0.20
                                                            Products
     –P(phenyl)2            0.0      0.0       0.0
     –P(O)(OCH3)2           0.46     0.14      0.22
     –Pb+(phenyl) Cl–       0.30     0.49      0.61         Solvents
     –Zn–phenyl            -0.36     0.02      0.05
     –Hg–phenyl             0.06     0.10     -0.10
              180      5 1H NMR

              1H-1H   Coupling Constants in Selected Monosubstituted Benzenes (|J| in Hz)
                                                   3   2
      C                                      4
                                                           1
                                                               R

                                                   5   6
  C       C
                      Substituent R              J23       J24     J25   J26   J34   J35

               C      –CH3                       7.7       1.3     0.6   2.0   7.5   1.5
  C       C
                      –CH=CH2                    7.8       1.1     0.6   1.9   7.4   1.5
                         –
                      –C – CH
                         –                       7.8       1.3     0.6   1.7   7.6   1.3
                      –phenyl                    7.8       1.2     0.6   2.0   7.5   1.4
               X      –F                         8.4       1.1     0.4   2.7   7.5   1.8
                      –Cl                        8.1       1.1     0.5   2.3   7.5   1.7
                      –Br                        8.0       1.1     0.5   2.2   7.4   1.8
                      –I                         7.9       1.1     0.5   1.9   7.5   1.8
               O      –OH                        8.2       1.1     0.5   2.7   7.4   1.7
                      –OCH3                      8.3       1.0     0.4   2.7   7.4   1.8
      N               –O–phenyl                  8.3       1.1     0.5   2.6   7.4   1.7
                      –OCOCH3                    8.2       1.1     0.5   2.5   7.5   1.7
  Hal          N      –NH2                       8.0       1.1     0.5   2.5   7.4   1.6
                      –NHCOCH3                   8.2       1.2     0.5   2.4   7.4   1.5
                      –NO2                       8.4       1.2     0.5   2.4   7.5   1.5
      O               –C – N
                         –
                         –                       7.8       1.3     0.7   1.8   7.7   1.3
               S      –SH                        7.9       1.2     0.6   2.1   7.5   1.5
                      –S(O)2OCH3                 8.0       1.2     0.6   2.0   7.6   1.4
      N               –CHO                       7.7       1.3     0.6   1.8   7.5   1.3
               O
                      –COCH3                     8.0       1.3     0.6   1.8   7.5   1.3
               ||
      S        C
                      –COOH                      7.9       1.3     0.6   1.9   7.4   1.4
                      -COOCH3                    7.9       1.4     0.6   1.8   7.5   1.3
                      –CONH2                     7.9       1.2     0.6   2.0   7.5   1.3
  C       X           –COCl                      8.0       1.2     0.6   2.0   7.5   1.4
               M      –Li                        6.7       1.5     0.8   0.7   7.4   1.3
                      –MgBr                      6.9       1.5     0.7   0.7   7.4   1.4
  P Si                –P(phenyl)2                7.6       1.2     0.6   1.7   7.4   1.4
                      –PO(OCH3)2                 7.7       1.4     0.6   1.6   7.6   1.4
Natural               –Zn–phenyl                 6.6       2.1     0.7   0.8   7.4   1.5
Products              –Hg–phenyl                 7.5       1.4     0.6   1.1   7.5   1.5


Solvents
                                                   5.5 Aromatic Hydrocarbons                         181

1H Chemical Shifts and Coupling Constants of Condensed Aromatic-
Alicyclic Hydrocarbons (δ in ppm, J in Hz)

                                                                                                             C
                                        7.40
       7.08       2.91                   d     c   3.39    3J      5.5               7.01     2.85
6.99                                                          ab              6.93                   1.60
                         2.04 7.26                  b
                                                           4J
                                                              ac   2.0                                      C       C
                                                    6.55   5J      0.7
                               7.19                           ad
                                               a   6.88    3J      1.9
                                        7.47                  bc
                                                                                                            C       C

                       7.84                    3.91       7.31                             2.87
                                                                                                  7.23
                              7.38                               7.19
                              7.28                                                                   7.22
         3.87 7.55                                                                         7.75 7.29


                                4J                                                           4J                 N
              a    3.34            ab   1.5                              a    7.15              ab   0
                                5J      0                                                    5J      0
                   b  7.11
                                6J
                                   ac
                                   ad   0.5                                    b    7.90     6J
                                                                                                ac
                                                                                                ad   0       Hal
                                3J      6.7                                                  3J      7
                   c 7.31
                                4J
                                   bc                                          c    7.58     4J
                                                                                                bc
                                        1.2                                                          0.6
          d       7.46          3J
                                   bd
                                   cd   8.1
                                                                         d   7.79            3J
                                                                                                bd
                                                                                                cd   8          O

                                                                   -4.03
                                                                                                                N
                                                                              0.72
                  7.04        0.73                                                    1.45
                                        1.54                         H                                          S
                                                                                      2.23; 2.91
                                                                             6.86
                       0.51     1.08 2.62                                                                   C       X


                                                                                                             P Si

                                                                                                            Natural
                                                                                                            Products

                                                                                                            Solvents
              182       5 1H NMR

              Effect of Substituents in Position 1 on the 1H Chemical Shifts of Monosubstituted
              Naphthalenes (in ppm)

      C
                               R                   for R: H       δH , δH , δH , δH = 7.84
                         8                                          1    4    5    8
                                                                  δH , δH , δH , δH = 7.48
  C       C         7                2                              2     3       6     7
                    6                3
                         5      4
  C       C
                    Substituent R          H-2     H-3     H-4     H-5     H-6         H-7     H-8
                C   –CH3                  -0.20   -0.14   -0.17   -0.03   -0.03        0.00    0.12
                    –CH2CH3               -0.15   -0.08   -0.15    0.00   -0.02        0.01    0.21
                    –CH2C – CH
                            –
                            –              0.09   -0.23   -0.23   -0.17   -0.13       -0.03    0.52
                    –CH2Cl                -0.10   -0.18   -0.11   -0.07   -0.05        0.02    0.22
                    –CF3                   0.51   -0.01    0.01    0.06    0.07        0.13    0.35
                    –CH2OH                -0.07   -0.10   -0.09   -0.01   -0.02        0.01    0.18
                    –CH2NH2               -0.14   -0.13   -0.14   -0.05   -0.07       -0.03    0.10
      N                –
                    –C – CH
                       –                   0.22   -0.14   -0.08   -0.08   -0.04        0.05    0.51
                    –phenyl               -0.11   -0.04   -0.06    0.05   -0.13       -0.07   -0.02
  Hal               –F                    -0.35   -0.10   -0.23    0.00    0.05        0.03    0.27
                X   –Cl                    0.06   -0.14   -0.12   -0.02    0.02        0.09    0.42
                    –Br                    0.29   -0.25   -0.04   -0.01    0.04        0.11    0.39
      O             –I                     0.20   -0.46    0.13   -0.22   -0.09       -0.02    0.18
               O    –OH                   -0.75   -0.22   -0.42   -0.05   -0.03       -0.01    0.32
                    –OCH3                 -0.84   -0.25   -0.55   -0.18   -0.12       -0.13    0.33
      N             –O–phenyl             -0.53   -0.10   -0.22    0.03    0.04        0.00    0.37
                    –OCOCH3               -0.31   -0.05   -0.27   -0.14   -0.23       -0.09   -0.01
      S         N   –NH2                  -0.76   -0.22   -0.55   -0.07   -0.05       -0.08   -0.09
                    –N(CH3)2              -0.46   -0.13   -0.36   -0.06   -0.03       -0.06    0.38
                    –NHCOCH3               0.24    0.01   -0.12    0.08    0.04        0.08    0.27
  C       X         –NO2                   0.71    0.02    0.24    0.08    0.04        0.16    0.69
                    –C – N
                       –
                       –                   0.42    0.04    0.23    0.07    0.14        0.21    0.38
                    –NCO                  -0.25   -0.13   -0.18   -0.03    0.05        0.01    0.21
  P Si              –NCS                  -0.13   -0.13   -0.14   -0.04    0.03        0.08    0.21
               O    –CHO                   0.46    0.07    0.20    0.05    0.06        0.17    1.39
Natural             –COCH3                 0.40   -0.02    0.09    0.01    0.02        0.09    0.90
               ||   –COOH                  0.72    0.14    0.34    0.20    0.13        0.20    1.09
Products
               C    –COOCH3                0.65   -0.08    0.08   -0.05   -0.02        0.09    1.09
                    –COCl                  1.03    0.06    0.22    0.02    0.07        0.17    0.88
Solvents
                                             5.5 Aromatic Hydrocarbons                  183

Effect of Substituents in Position 2 on the 1H Chemical Shifts of Monosubstituted
Naphthalenes (in ppm)
                                                                                               C
           8      1
                              R           for R: H        δH , δH , δH , δH = 7.84
      7                                                     1    4    5    8
                                                          δH , δH , δH , δH = 7.48
      6                   3                                 2      3   6      7               C       C
           5      4

                                                                                              C       C
          Substituent R            H-1     H-3     H-4     H-5      H-6      H-7      H-8
          –CH3                    -0.24   -0.18   -0.11   -0.06    -0.09    -0.05    -0.10
    C     –CH2CH3                 -0.22   -0.14   -0.08   -0.05    -0.08    -0.06    -0.08
          –CH(CH3)2               -0.24   -0.15   -0.12   -0.10    -0.12    -0.10    -0.10
          –CF3                     0.28    0.14    0.06   -0.10     0.09     0.06    -0.10
          –CH2OH                  -0.13   -0.08   -0.07   -0.05    -0.04    -0.03    -0.08
          –CH=CH2                 -0.11    0.14   -0.06   -0.06    -0.06    -0.04    -0.06
             –
          –C – CH
             –                     0.19    0.04   -0.05   -0.03     0.02     0.02    -0.03
                                                                                                  N
          –phenyl                  0.20    0.25    0.06    0.01     0.02    -0.02     0.05
    X     –Cl                     -0.04   -0.08   -0.10   -0.05a   -0.03b   -0.01b   -0.12a
          –Br                      0.14    0.05   -0.16   -0.12    -0.02     0.00    -0.06     Hal
          –OH                     -0.72   -0.39   -0.10   -0.09    -0.16    -0.06    -0.18
    O     –OCH3                   -0.76   -0.33   -0.14   -0.10    -0.14    -0.06    -0.14
          –O–phenyl               -0.53   -0.22   -0.01   -0.02    -0.08    -0.04    -0.15
                                                                                                  O
          –OCOCH3                 -0.30   -0.27   -0.04   -0.04    -0.04    -0.02    -0.08
    N     –NH2                    -0.93   -0.62   -0.23   -0.19    -0.27    -0.15    -0.27        N
          –N(CH3)2                -1.07   -0.49   -0.30   -0.29    -0.39    -0.24    -0.33
          –NHCOCH3                 0.33   -0.02   -0.10   -0.11    -0.09    -0.06    -0.09
          –NO2                     0.90    0.70    0.05    0.05     0.19     0.15     0.14        S
          –C – N
             –
             –                     0.40    0.13    0.08    0.06     0.19     0.13     0.06
    S     –SH                     -0.14   -0.19   -0.17   -0.11    -0.09    -0.06    -0.19
    O     –CHO                     0.44    0.45    0.05    0.03     0.14     0.08     0.12    C       X
          –COCH3                   0.58    0.51    0.01    0.01     0.08     0.03     0.01
    ||    –CO–phenyl               0.42    0.46    0.09    0.06     0.13     0.06     0.06
    C     –COOH                    0.83    0.57    0.20    0.19     0.20     0.16     0.31     P Si
          –COOCH3                  0.66    0.50   -0.08   -0.07    -0.01    -0.05     0.00
          –COCl                    0.85    0.58    0.22    0.32     0.17     0.21     0.20    Natural
a                     b
    interchangeable; interchangeable                                                          Products

                                                                                              Solvents
              184           5 1H NMR

              5.6 Heteroaromatic Compounds

              5.6.1 Non-Condensed Heteroaromatic Rings
      C
              1H      Chemical Shifts and Coupling Constants (δ in ppm, |J| in Hz)

  C       C
                  c         b   6.38           3J      1.8            c       b 6.23 3Jab                2.6             c         b      7.09     3J      4.8
                                                  ab                                                                                                  ab
                                               4J      0.9                           4                                                             4J
  C       C   d                 a   7.42          ac              d            a 6.71 Jac                1.3         d                 a   7.31       ac   1.0
                                               4J      1.5                           4J                  2.1                  S                    4J      2.8
                       O                          ad                      N             ad                                                            ad
                                               3J      3.4                H e 8.1,   3J                  2.6                                       3J      3.5
                                                  bc                                    ae                                                            bc
                                                                              broad 3Jbc                 3.5
                                                                                     4J                  2.6
                                                                                        be


                                7.23           3J      5.4                                       3J       0.8                                3J            1–2
                  c         b                     ab            N                 b   7.15          ab             N               b      7.13  ab
                                               4J      1.5                                       4J       0.5                                4J            1.0
              d                 a   7.88       4J
                                                  ac          c                       a   7.68   4J
                                                                                                    ac           c                     a 7.13 ac
                                                                                                                                             4J
                       Se                         ad   2.3 7.90 O                                   bc    0.0 7.74 N                            bc         1.0
      N                                        3J      3.7                                                                   H 13.4
                                                  bc

  Hal

                                    7.98       3J      3.2       8.31                            3J      1.7     7.74                              3J      2.1
      O               N     b
                                               4J
                                                  ab
                                                       1.9
                                                                  c           b       6.38
                                                                                                 4J
                                                                                                    ab
                                                                                                         0.3
                                                                                                                  c               b    6.10
                                                                                                                                                   4J
                                                                                                                                                      ab
                                                                                                                                                           0.0
                  c                 a             ac                 N            a       8.49      ac               N                a   7.74        ac
              8.88 S                    7.41   4J
                                                  bc   0.0                O
                                                                                                 3J
                                                                                                    bc   1.8                 N
                                                                                                                                                   3J
                                                                                                                                                      bc   2.1
                                                                                                                             H 13.7
      N

      S       8.54                    3J
                  c         b       7.26 ab            4.7                            8.19                       7.75                      N       N
                                      4
                  N             a 8.72 Jac             0.4
                                                                          N           N                  N       N                                     8.33
                                      3J               1.7
  C       X            S                 bc                                   O                              N                                 O
                                                                                                             H ≈12


  P Si

Natural               N N                                            8.58                        HN          b  7.58              4J 1.4
                                                                                                                                    ac
                                                                                                      +                           3J + 4J           = 4.4
Products                        8.27                   N         N                        9.18   c             a 7.58               ad    bd
                       N                                     S                                         N                          3J 2.4
                                                                                                     d H 13.5                       cd
                       H 13.5
Solvents                                                                                              Cl–
                                                                       5.6 Heteroaromatics                         185

                         Solvent:             3J 6.0                           Solvent:                        3J 6.0
         c                                      ab                c                                              ab
                          CDCl3       DMSO    4J 1.9
                                                ac                              CDCl3* DMSO**                  4J 1.6
                                                                                                                 ac
d                b                            5J 0.9        d             b                                    5J 0.8
                         a 8.59        8.58     ad                +            a 9.00   8.98                     ad
e                a       b 7.25        7.38   4J 0.4        e              a   b 7.97   8.14                   4J 1.0      C
        N                                       ae               N                                               ae
                         c 7.62        7.75   3J 7.6                           c 8.43   8.67                   3J 7.9
                                                bc               H                                               bc
                                              4J 1.6                                                           4J 1.4
                                                bd                             * p-toluylsulfonate               bd
                                                                                                                          C       C
                                                                               ** HSO3–

                                                                                                                          C       C
        7.32                  3J
                                 ab   6.5
        c
                              4J      1.1
                                 ac                         N
d                b   7.40     5J      0.6               N        b    9.48     3J
                                                                                  ab   2.7           N         N
                                 ad                                            4J
e                a   8.19     4J      1.9      9.88 c            a    8.84        ac   0.0                         9.23
        N                        ae                                            5J
                              3J      7.7                   N                     bc   2.2                 N
                                 bc
        O                     4J      2.1
                                 bd
(in acetone)

                                                                                                                              N
                                                                          7.22
         c                                                                 c
                                                                8.54
                                                                                                                           Hal
                        3J            4.9                                               3J           5.3
d                b 7.56 4 ab                                      d              b 7.83 4 ab
                         J            2.0                                                J           1.0
    N            a 9.22 5 ac                                                     a 8.26 5 ac
        N                Jad          3.5                             N
                                                                           N
                                                                                         Jad         1.0
                        3J
                           bc         8.4                                               3J
                                                                                        4J
                                                                                           bc        8.0                      O
                                                                           O               bd        2.5
                                                                                        3J           6.5
                                                                                           cd
                                                                                                                              N
                                                                          8.24
             c                3J      5.0                                  c                 3J      6.8
    N                b 7.38   4J
                                 ab
                                      2.5                             N          b 7.34      4J
                                                                                                ab
                                                                                                     1.6
                                                                                                                              S
                                 ac                                                             ac
    d                a 8.78   4J      0                           d              a 8.43      4J      2.0
                                 ad                                                             ad
9.27 N                        5J      1.5                       8.98 N                       3J      4.9
                                 bd
                                                                                             5J
                                                                                                bc                        C       X
                                                                                                bd   1.0
                                                                           O                 4J
                                                                                                cd   0
                                                                                                                           P Si
                                                                                             3J      4.1
             N                                                             N                    ab                        Natural
                                                                                             5J      0.8
                                                                  c              b 8.11         ac                        Products
                                                                                             4J      0.6
                     8.63                                         d              a 8.44         ad
             N                                                             N                 4J      0.4
                                                                                                bc
                                                                           O
                                                                                                                          Solvents
              186        5 1H NMR

              Effect of Substituents on the 1H Chemical Shifts of Monosubstituted Furans
              (in ppm)

      C                                                          δH-2 = 7.42 + Zi2
                                         4       3
                                     5            2
                                                                 δH-3 = 6.38 + Zi3
  C       C
                                             O                   δH-4 = 6.38 + Zi4
                                                                 δH-5 = 7.42 + Zi5
  C       C


                                                       H3      H4      H5         H2       H4      H5
                       Substituent                      in position 2 or 5         in position 3 or 4
                                                       Z23     Z24     Z25        Z32     Z34     Z35
                                                       Z54     Z53     Z52        Z45     Z43     Z42
                  C    –CH3                           -0.45    -0.15    -0.17    -0.25   -0.17   -0.12
                       –CH2CH3                        -0.42    -0.12    -0.14
      N                –CH2OH                         -0.12    -0.07    -0.05    -0.07   0.00    -0.06
                       –CH2SH                         -0.22    -0.09    -0.09
  Hal                  –CH2SCH3                       -0.21    -0.09    -0.08
                       –CH=CHCOCH3 (trans)             0.29     0.11     0.08
                  X    –Br                            -0.23    -0.17    -0.17
      O                –I                              0.04    -0.21    -0.05    -0.17   -0.04   -0.26
                  O    –OCH3                          -1.26    -0.14    -0.57    -0.50   -0.36   -0.41
                  N    –NO2                            1.13     0.47     0.47
      N                –C – N
                          –
                          –                            0.48    -0.02    -0.04     0.41    0.14   -0.06
                  S    –SCH3                           0.05     0.01     0.13    -0.22   -0.13   -0.19
                       –SCN                            0.32    -0.02     0.06     0.15    0.11   -0.01
      S           O    –CHO                            0.92     0.25     0.31     0.92    0.47    0.19
                  ||   –COCH3                          0.81     0.16     0.18     0.42    0.28   -0.16
                       –COCO–2-furyl                   1.26     0.27     0.37
  C       X       C    –COOH                           0.97     0.19     0.24    0.70    0.40    0.03
                       –COOCH3                         0.81     0.14     0.18    0.60    0.37    0.01
                       –COCl                           1.14     0.32     0.46
  P Si
                  M    –P(–x-furyl)2                   0.25a   -0.12a    0.03a   -0.16b -0.10b -0.09b
                       –P(O)(–x-furyl)2                0.76a    0.15a    0.30a    0.14b 0.19b 0.31b
Natural                –P(S)(–x-furyl)2                0.77a    0.12a    0.27a    0.10b 0.18b 0.30b
Products               –P+(CH3)(2-furyl)2 I–           1.53     0.49     0.77
                       –HgCl                                                     -0.09 0.02 0.25
Solvents               –Hg–x-furyl                    0.18a    0.24a    0.47a    -0.10b 0.10b -0.10b
              a   x = 2, b x = 3
                                                         5.6 Heteroaromatics             187

Effect of Substituents on the 1H Chemical Shifts of Monosubstituted Pyrroles
(in ppm)

                                                                                                C
                                              δH-1 ≈ 8, broad, solvent-dependent
                        4         3
                    5              2          δH-2 = 6.71 + Zi2
                                                                                               C       C
                             N
                             H1               δH-3 = 6.23 + Zi3
                                              δH-4 = 6.23 + Zi4
                                                                                               C       C
                                              δH-5 = 6.71 + Zi5




                                                         H3      H4
                                                         Z12     Z13
                            Substituent in position 1
                                                         Z15     Z14
                            –CH3                        -0.13   -0.11                              N
                            –CH2CH3                     -0.16   -0.12
                            –CH2CH2CN                   -0.05   -0.07
                            –CH2–phenyl                 -0.12   -0.04
                                                                                                Hal
                            –phenyl                      0.36    0.11
                            –N(CH3)2                     0.11   -0.19                              O
                            –COCH3                       0.56    0.12
                            –CO–phenyl                   0.57    0.18
                            –Si(CH(CH3)2)3               0.08    0.08                              N

                                                                                                   S
                                       H3      H4       H5         H2      H4       H5
      Substituent                       in position 2 or 5          in position 3 or 4
                                                                                               C       X
                                       Z23     Z24     Z25         Z32     Z34     Z35
                                       Z54     Z53     Z52         Z45     Z43     Z42
 C    –CH3                             5.72    5.89     6.36      -0.33   -0.16   -0.26         P Si
      –NO2                             7.11    6.29     7.05       1.06    0.24    0.43
 N    –C – N
         –
         –                             6.88    6.28     7.13       0.83    0.23    0.51        Natural
 S    –SCH3                            6.23    6.10     6.72       0.18    0.05    0.10        Products
      –SCN                             6.53    6.15     6.90       0.48    0.10    0.28
 O    –CHO                             7.01    6.34     7.18       0.78    0.11    0.47
                                                                                               Solvents
 ||   –COCH3                           6.93    6.26     7.06       0.70    0.03    0.35
      –COOCH3                          6.84    6.18     6.91       0.79    0.13    0.29
 C
              188    5 1H NMR

              Effect of Substituents on the 1H Chemical Shifts of Monosubstituted Thio-
              phenes (in ppm)

      C                                                      δH-2 = 7.31 + Zi2
                                      4       3
                                  5            2             δH-3 = 7.09 + Zi3
  C       C
                                          S                  δH-4 = 7.09 + Zi4
                                                             δH-5 = 7.31 + Zi5
  C       C


                                                   H3       H4      H5      H2       H4      H5
                    Substituent                     in position 2 or 5       in position 3 or 4
                                                   Z23     Z24     Z25      Z32     Z34     Z35
                                                   Z54     Z53     Z52      Z45     Z43     Z42
               C     –CH3                          -0.34   -0.20   -0.24   -0.45   -0.22   -0.15
                     –C – C
                        –
                        –                           0.02   -0.29   -0.23
      N              –phenyl                                                0.11   0.28    0.05
                     –2-thienyl                     0.08   -0.09   -0.11
  Hal                –2-pyridyl                     0.48    0.01    0.06
               X     –F                            -0.78   -0.54   -0.86   -0.80   -0.40   -0.31
                     –Cl                           -0.30   -0.35   -0.39   -0.25   -0.17   -0.09
      O              –Br                           -0.05   -0.23   -0.10   -0.23   -0.21   -0.21
                     –I                             0.11   -0.34   -0.01   -0.05   -0.13   -0.30
               O     –OH*                          -0.85    0.44   -3.21
      N              –OCH3                         -0.93   -0.41   -0.82   -1.10   -0.36   -0.17
               N     –NH2                          -1.08   -0.58   -0.96   -1.36   -0.66   -0.36
                     –NO2                           0.69   -0.16    0.19    0.84    0.47   -0.08
      S                 –
                     –C – N
                        –                           0.34   -0.13    0.17    0.52    0.07    0.04
               S     –SH                           -0.13   -0.33   -0.18   -0.33   -0.33   -0.21
                     –SCH3                         -0.16   -0.31   -0.16   -0.44   -0.23   -0.14
  C       X          –S(O)2CH3                      0.90    0.07    0.68    0.85    0.35    0.35
                     –S(O)2Cl                       0.60   -0.07    0.34
                     –SCN                           0.17   -0.18    0.17    0.14   -0.08   -0.06
  P Si
               O     –CHO                           0.69    0.13    0.47    0.81    0.44    0.06
                     –COCH3                         0.60    0.03    0.32    0.74    0.45    0.01
Natural        ||    –CO–phenyl                     0.55    0.06    0.40
Products       C     –COOH                          0.67   -0.05    0.29    0.93    0.48    0.03
                     –COOCH3                        0.70    0.00    0.22    0.67    0.34   -0.16
                                                                           -7.31
Solvents             –CONHNH2                       0.63    0.04    0.41           -7.09   -7.31
                     –COCl                          0.75   -0.07    0.33    0.94    0.37   -0.08
              * Keto form
                                           5.6 Heteroaromatics       189

Effect of Substituents on the 1H Chemical Shifts of Monosubstituted Pyridines
(in ppm)
                                         δH-2 = 8.59 + Zi2
                       4                 δH-3 = 7.25 + Zi3                     C
                  5        3             δH-4 = 7.62 + Zi4
                  6        2             δH-5 = 7.25 + Zi5                    C C
                      N
                                         δH-6 = 8.59 + Zi 6

                                 H3        H4       H5        H6           C       C
      Substituent                Z23       Z24      Z25       Z26
      in position 2 or 6         Z65       Z63      Z63       Z62
 C    –CH3                      -0.11     -0.08     -0.15    -0.11
      –CH2CH3                   -0.09      0.01     -0.15     0.03
      –CH2–phenyl                0.03     -0.06      0.04    -0.04
      –CH2OH                     0.14      0.03     -0.08    -0.14
      –CH=CH2                   -0.07     -0.14     -0.23    -0.12
      –phenyl                    0.42      0.02     -0.09     0.07
      –2-pyridyl                 1.27      0.04     -0.11     0.00             N
 X    –F                        -0.30      0.16     -0.05    -0.36
      –Cl                        0.09      0.02      0.00    -0.10          Hal
      –Br                        0.26     -0.06      0.03    -0.23
      –I                         0.49     -0.29      0.04    -0.23
 O    –OH*                      -0.63     -0.13     -0.93    -1.17             O
      –OCH3                     -0.51     -0.10     -0.41    -0.43
 N    –NH2                      -0.76     -0.24     -0.63    -0.54
                                                                               N
      –NHCH2CH3                 -0.87     -0.22     -0.69    -0.52
      –N(CH3)2                  -0.77     -0.23     -0.73    -0.44
      –NHNH2                    -0.55     -0.17     -0.58    -0.48
      –NHCOCH3                   1.00      0.09     -0.19    -0.32
                                                                               S
      –NHN=CH–2-pyridyl          0.21     -0.01     -0.42    -0.36
      –NO2                       0.93      0.44      0.45     0.00
                                                                           C       X
      –C – N
         –
         –                       0.52      0.26      0.35     0.15
 S    –SH                        0.34     -0.20     -0.42    -0.91
 O    –CHO                       0.73      0.26      0.31     0.21          P Si
      –COCH3                     0.80      0.22      0.24     0.10
 ||   –CO–phenyl                 0.81      0.27      0.25     0.13
                                                                           Natural
 C    –COOH                      0.87      0.41      0.44     0.17
                                                                           Products
      –COOCH3                    0.91      0.24      0.27     0.17
      –CONH2                     0.98      0.24      0.22    -0.01
      –CH=N–NH–2-pyridyl         0.76      0.05     -0.06    -0.03         Solvents
      –Si(CH3)3                  0.15     -0.22     -0.24     0.09
* Keto form (2-pyridone)
              190    5 1H NMR



                                  H2         H4       H5     H6      H2      H3
      C             Substituent           in position 3 or 5        in position 4
                                  Z32        Z34     Z35     Z36      Z42     Z43
                                  Z56        Z54     Z53     Z52      Z46     Z45
  C       C
               C    –CH3          -0.15     -0.16   -0.07   -0.17   -0.13   -0.13
                    –CH2CH3       -0.13     -0.14   -0.06   -0.17   -0.12   -0.14
  C       C         –CH2–phenyl   -0.08     -0.18   -0.04   -0.14    0.00   -0.15
                    –phenyl        0.25      0.20    0.08   -0.03
                    –CH=CH2                                         -0.12   -0.08
               X    –F            -0.05     -0.21    0.04   -0.13   -0.07   -0.03
                    –Cl            0.09      0.00    0.05   -0.05    0.00    0.05
                    –Br            0.09      0.18   -0.04   -0.07    0.09    0.35
               O    –OH           -0.31     -0.29    0.06   -0.50
                    –OCH3         -0.27     -0.37   -0.04   -0.40   -0.16   -0.42
                    –OCOCH3       -0.15     -0.15    0.08   -0.13
      N        N    –NH2          -0.51     -0.65   -0.20   -0.60   -0.15   -0.74
                    –N(CH3)2                                        -0.38   -0.77
                    –NHCOCH3      0.37      0.50    0.06    -0.16   -0.19    0.16
  Hal               –C – N
                       –          0.32      0.38    0.25     0.26    0.24    0.32
                       –
               S    –S–phenyl                                        0.05   -0.16
      O             –S(O)2OH      0.70      1.14    0.81    0.70
               O    –CHO          0.52      0.58    0.30    0.28     0.31    0.49
                    –COCH3        0.58      0.61    0.20    0.20     0.21    0.50
               ||
      N             –CO–phenyl                                       0.23    0.35
               C    –COOH         0.54      0.57    0.20    0.24     0.20    0.45
                    –COOCH3       0.64      0.67    0.16    0.19     0.19    0.61
      S             –COO–phenyl                                      0.24    0.75
                    –CONH2        0.49      0.50     0.15    0.15
                    –CSNH2        0.68      0.67     0.24    0.26    0.35    0.68
  C       X         –CH=NOH       0.39      0.43     0.19    0.15    0.06    0.32
                    –Si(CH3)      0.08      0.00    -0.21   -0.11   -0.08    0.01

  P Si

Natural
Products

Solvents
                                                             5.6 Heteroaromatics                191

5.6.2 Condensed Heteroaromatic Rings

1H   Chemical Shifts and Coupling Constants (δ in ppm, |J| in Hz)
                                                                                                         C


           7.55
            c
                                    3J 2.5
                                       ab                        7.64
                                                                  c
                                                                                           3J 3.1
                                                                                             ab         C       C
                    b   6.69        5J 0.9                                b   6.52         3J 2.5
7.20   d                               bf             7.12 d                                 ag
                                    3J 7.9                                                 5J 0.7
                         a   7.54      cd                                      a 7.05        bf
7.25   e
                    O
                                    4J 1.2
                                       ce
                                                      7.18 e              N
                                                                                           4J 2.0
                                                                                             bg
                                                                                                        C       C
            f                       5J 0.8                       f        H g 7.81         3J 7.8
                                       cf                                                    cd
           7.47                     3J 7.3                     7.27                        4J 1.2
                                       de                                                    ce
                                    4J 0.9                                                 5J 0.9
                                       df                 (chemical shifts in CDCl3,         cf
                                    3J 8.4                                                 5J 0.8
                                       ef                 coupling constants in              cg
                                    (all other cou-                                        3J 7.1
                                                          acetone)                           de
                                    pling constants                                        4J 1.3
                                                                                             df
                                    negligible)                                            3J 8.1
                                                                                             ef
                                                                                      (all other cou-
                                                                                      pling constants
                                                                                      negligible)           N

           7.82                     3J 5.5                       7.79                     5J 0.2         Hal
            c                          ab                         b                         ab
                    b   7.33        5J 0.8                                                6J -0.1
7.36 d                                 bf             7.41   c           N                  ac
                                    3J 8.0                                                6J 0.4
7.33   e
                         a   7.42      cd
                                    4J 1.1            7.34   d
                                                                               a   8.10     ad
                                                                                          5J 0.0            O
                    S                  ce                                O                  ae
            f                       5J 0.9                        e                       3J 8.2
                                       cf                                                   bc
           7.88                                                  7.58                     4J 1.0
                                                                                                            N
                                    3J 7.2
                                       de                                                   bd
                                    4J 1.0                                                5J 0.7
                                       df                 (chemical shifts in CDCl3,        be
                                    3J 8.0                                                3J 7.4
                                       ef                 coupling constants in             cd
                                                                                          4J 1.2
                                    (all other cou-
                                    pling constants
                                                          acetone)                          ce
                                                                                          3J 8.3
                                                                                                            S
                                                                                            de
                                    negligible)

                                                                                                        C       X
           7.70                                                  7.94                     5J
                                                                                             ab 0.1
                                    3J 8.2
             b                         bc
7.26   c
                    N               4J 1.4
                                       bd             7.51   c
                                                                  b
                                                                          N
                                                                                          6J -0.2
                                                                                             ac          P Si
                                                                                          6J
                                                                                             ad 0.4
                                    5J 0.7
                         a   8.08      be                                      a   8.97
7.26   d                            3J 7.1            7.46   d                            5J
                                                                                             ae 0.1
                e
                    N                  cd                                 S
                                                                                          3J
                                                                                                        Natural
                                                                                             bc 8.2
                    H               (all other cou-               e
           7.70 12.5*               pling constants              8.14                     4J
                                                                                                        Products
                                    negligible)                                              bd 1.1
                                                                                          5J
                                                          (chemical shifts in CDCl3,         be 0.6
           * in DMSO                                      coupling constants in
                                                                                          3J
                                                                                             cd 7.2     Solvents
                                                                                          4J
                                                          acetone)                           ce 1.1
                                                                                          3J
                                                                                             de 8.2
              192         5 1H NMR

                          7.78       8.10
                                                           5J 0.8
                                                              ae                                    7.83                    3J
                                                                                                                               ab   9.1
                           b                               3J 7.8                                       a                   4J
                                     a
                                                              bc                                                 N             ac   1.1
              7.13   c                                     4J 1.2                    7.42   b                               5J
                                          N                   bd                                                     O         ad   0.9
      C       7.36   d                                     5J 1.0                           c                               3J      6.4
                                     N                        be                                                 N             bc
                           e         H f 13.1              3J 7.0                                       d
                                                              cd
                          7.58                             4J 1.2
                                                              ce
  C       C              (in DMSO)                         3J 7.9
                                                              de
                                                           (all other cou-
                                                           pling constants
  C       C                                                negligible)

                         7.95                                                                       7.97                    3J      8.9
                           a                                                                            a                      ab
                                                     3J          8.3                                                        4J
                                     N                  ab                                                                     ac   1.2
              7.39   b                               4J          1.0                 7.53   b                    N
                                                                                                                            5J
                                          N             ac                                                           S         ad   0.9
                                                     5J          0.9                                                        3J
                     c
                                     N                  ad                                  c
                                                                                                                 N             bc   6.7
                                     H ≈16           3J          7.0
                           d                            bc                                              d

                (chemical shifts in CDCl3,
                coupling constants in
                acetone)
      N
                                                                                                    9.21
  Hal                     8.61
                           a
                                                         3J
                                                            ab   8.4                                    b
                                                         4J      1.0
              7.61 b                 N                      ac                                                   N
                                                         5J                                     N
                                          N                 ad   0.8                                                 a   8.70
      O       7.66 c                 S
                                                         3J
                                                            bc   7.0             8.99       c
                                                                                                        N        N
                           d                             4J      1.0                                             H d 13.5
                                                            bd
                          8.08                           3J
                                                            cd   7.9                            (in DMSO)
      N

      S                   7.25                                                           7.68                              3J
                                                                                                                              ab 1.2
                                                            3J 2.7
                           d                                   ab
                                      c   6.28                                              c                              4J
                                                                                                                              af 0.7
                                                            4J 1.2
              6.50   e                                         ac             6.97   d                      N
                                                                                                                           3J
                                                                                                                              cd 9.0
                                                            5J 0.5
  C       X                                   b   6.64         ad                                              b 7.67
              6.31   f           N                          3J 3.9
                                                               bc
                                                                              6.55   e              N                      4J
                                                                                                                              ce 1.3
                           g          a   7.14                                                              a 7.60         5J
                                                                                                                              cf 1.3
                                                            6J 0.5                          f
                                                               bf
                          7.76                                                           8.05
  P Si                                                      5J 1.0
                                                               cg
                                                                                                                           3J
                                                                                                                           4J
                                                                                                                              de 6.6
                                                                                                                              df 1.3
                                                            3J 9.0
                                                               de
                                                                                                                           3J
                                                                                                                              ef 6.8
                                                            4J 1.0
                                                               df
Natural                                                     5J 1.2                                                    (all other cou-
                                                               dg
Products                                                    3J 6.4                                                    pling constants
                                                               ef                                                     negligible)
                                                            4J 1.0
                                                               eg
                                                            3J 6.8
Solvents                                                       fg
                                                            (all other cou-
                                                            pling constants
                                                            negligible)
                                                                 5.6 Heteroaromatics                        193

           7.34       7.27              5J 1.0                       7.44 6.58                     3J 2.2
                                           ac                         c                               ab
            c          b                5J 0.5                                   b                 6J 0.5
                                           bf                                                         ad
6.58 d                                  3J 9.2            6.97   d                                 5J 0.9
                                           cd                                          a 7.80         bf
7.41   e          N
                           N
                                        4J 1.1            6.62   e          N                      3J 8.9         C
                                           ce                                    N                    cd
                       a                5J 1.1                        f                            4J 1.2
            f                              cf                                                         ce
           7.88       7.97              3J 6.4                       8.39                          5J 1.0
                                           de                                                         cf
                                        4J 0.9                                                     3J 6.8         C       C
                                           df                                                         de
                                        3J 7.1                                                     4J 1.0
                                           ef                                                         df
                                        (all other cou-                                            3J 6.9
                                        pling constants
                                                                                                      ef
                                                                                              (all other cou-
                                                                                                                  C       C
                                        negligible)                                           pling constants
                                                                                              negligible)


           6.52                                                      7.19
            a                         3J                              a                             3J
                      O                  ab   7.9                               S                      ab   7.8
6.71   b                       5.77   4J      1.5         7.12   b                       6.42       4J      1.3
                                         ac                                                            ac
       c                              5J      0.4                c                                  5J      1.1
                                         ad                                                            ad
                      O               3J      7.9                               S                   3J      7.1
            d                            bc                           d                                bc

                                                                                                                      N


           7.46 7.70                     3J 9.6                      8.21                           3J
                                                                                                                  Hal
                                           ab
                                                                                O
                                                                                                       ab   6.0
            c          b                 3J 7.7                       c                             3J      8.0
7.23 d                         a 6.36 4 cd                7.42   d                       b   6.34      cd
                                          Jce 1.6                                                   4J
                                                                                                       ce   1.8       O
7.47 e                                   3J 7.4
                                           de             7.68   e                       a   7.88   5J
                                                                                                       cf   0.5
                      O          O       4J 1.1                                 O                   3J
            f                              df                         f                                de   7.0
           7.22                          3J 8.4
                                           ef                        7.47                           4J
                                                                                                    3J
                                                                                                       df   1.1       N
                                    (all other cou-                                                    ef   8.4
                                    pling constants
                                    negligible)
                                                                                                                      S
           7.82       8.12                3J 4.2                     7.72       7.55                5J      1.0
            d          c                     ab                       d          c
                                                                                                    5J
                                                                                                       ac        C X
                                          4J 1.8
                                                                                                       ad   0.9
7.55   e                       b 7.39        ac           7.60   e                       b   8.50   3J
                                          3J 8.2
                                             bc                                                        bc   5.8
7.72                           a 8.92                     7.51                                      5J
                                                                                                                 P Si
       f                                  5J 0.8                 f                   N                      0.9
                      N                      cg                                                        cg
            g                             3J 8.2                      g          a                  3J      8.3
                                             de                                                        de
           8.15                           4J 1.4                     7.86       9.22                4J      1.2
                                             df                                                        df
                                          5J 0.7
                                             dg
                                                                                                    5J
                                                                                                       dg   0.8 Natural
                                          3J 6.9
                                             ef
                                                                                                    3J
                                                                                                       ef   6.9 Products
                                          4J 1.2                                                    4J      1.2
                                             eg                                                        eg
                                          3J 8.5                                                    3J      8.3 Solvents
                                             fg                                                        fg
                                     (all other cou-                                            (all other cou-
                                     pling constants                                            pling constants
                                     negligible)                                                negligible)
              194        5 1H NMR

                         7.90   7.77             3J        6.1                      7.72   7.68
                                                    ab
                          d      c               4J        1.0                       d      c
                                                    ac                                                           4J      1.7
              7.68   e                 b 7.32    3J                 7.62*   e                         b   8.14      ab
                                                    bc     8.5                                                   3J      7.0
      C       7.79   f                 a 8.55    5J
                                                    cg     0.9      7.60*   f                     N
                                                                                                                    bc

                          g
                                 N               3J        8.2                       g                    O
                                                    de                                      a
                         8.77                    4J        1.2                      7.79   8.78
                                 O                  df
  C       C                                      5J
                                                    dg     0.3
                                                 3J        7.2         * assignment uncertain
                                 (all other cou-    ef
                                 pling constants 4Jeg      1.4
  C       C                      negligible)     3J        8.6
                                                    fg

                         8.01   8.18               3J
                                                      ab   5.9                      7.93 9.41                    4J
                                                                                                                    ab   0.0
                          c      b                 5J                                c      b                    5J
                                                      bf   0.8                                                      bf   0.5
              7.86 d                   a   9.29    3J      7.8      7.93*   d                     N              3J      8.0
                                                      cd                                                            cd
                                                   4J      1.5      7.67*                                        4J      1.3
              7.95   e               N                ce                    e                     a       9.35      ce
                                N                  5J      0.8                              N                    5J      0.9
                          f                           cf                             f                              cf
                         8.44                      3J
                                                      de   6.9                      8.06                         3J
                                                                                                                    de   7.0
                                                   4J      1.3                                                   4J      1.3
                                                   3J
                                                      df               * assignment uncertain                    3J
                                                                                                                    df
      N                                               ef   8.6                                                      ef   8.6

                         8.13                                                       7.93 9.44
  Hal                     c
                                                  3J
                                                  4J
                                                     cd   8.4
                                                                                     c      b
                                                                                                                 5J
                                                                                                                 3J
                                                                                                                    ac   0.4
                                N                    ce   1.4                                                       cd   8.2
              7.79   d                 b          5J                 7.85   d                     N              4J
                                                     cf   0.7                                                       ce   1.2
      O              e
                                N
                                       a   8.85   3J
                                                     de   6.9               e                     N              5J
                                                                                                                 3J
                                                                                                                    cf   0.6
                          f                                                          f      a                       de   6.8

      N                                           3J
                                                     ab   8.0                       7.93                       3J 8.2
                                                                                                                  ab
                          d                       4J                                 d                         4J 1.9
                                N                    ac   1.8                              N
                                       c   8.97                      8.76   e                         c 9.10 5 ac
      S                                           5J
                                                  3J
                                                     ad   0.6                                                    Jad 0.9
                                       b   7.58           4.1                   N                     b 7.52 3J 4.1
                          N                          bc                                                           bc
                                 a                                                   f      a                  3J 6.0
                                                                                                                  de
  C       X                     8.40                                                9.28 8.28                  5J 0.9
                                                                                                                  df
                                                                                                           (all other cou-
                                                                                                           pling constants

  P Si
                                                                                                           negligible)
                         9.66                     3J 8.4                                                         3J      8.2
                          d                          ab                                                             ab
                                N                 4J 1.6                             N     N                     4J      2.0
Natural              N                 c   9.14      ac
                                                  5J 0.9                                          c       9.13   3J
                                                                                                                    ac
                                                                                                                         4.3
Products                                             ad                                                             bc
              8.73   e                 b   7.67   3J 4.2
                                                     bc
                                                                                                  b       7.50
                          f      a                5J 0.9                                    a
                                                     df
Solvents                 7.72 8.26                3J 5.6
                                                     ef
                                                                                           8.21
                                                  (all other cou-
                                                  pling constants
                                                  negligible)
                                            5.6 Heteroaromatics                 195

            7.96              3J      8.5            8.08               5J      0.7
                                 ab                                        ae
             d                4J      0.9             e                 3J      8.1
                                 ac                                        bc
                   c   7.35   5J      0.6                    d 7.24     4J      1.0
                                 ad                                        bd
                   b   7.46   3J      7.3                    c   7.42   5J      0.7     C
                                 bc                                        be
    O                         4J      1.3      N                        3J      7.2
             a                   bd            H      b                    cd
                              3J      7.6                               4J      1.2
            7.57                 cd            a     7.42                  ce
                                              8.03                      3J      7.9    C       C
                                                                           de


                                                                                       C       C
            8.16              3J      8.0            7.79               3J      7.7
                                 ab                                        ab
             d                4J      1.1              d                4J      1.1
                                 ac                                        ac
                   c   7.45   5J      0.7                    c   7.58   5J      0.7
                                 ad                                        ad
                   b   7.45   3J      7.2                    b   7.48   3J      7.5
                                 bc                                        bc
    S                         4J      1.2      S                        4J      1.1
             a                   bd                    a                   bd
                              3J      8.1                               3J      7.6
            7.85                 cd            O     7.97                  cd



                                                                                           N
            7.77              3J      7.7     8.59 7.86                 3J       8.9
                                 ab                                        ab
             d
                   c   7.61
                              4J
                              5J
                                 ac   1.1      e       d
                                                             c   7.43
                                                                        4J
                                                                        5J
                                                                           ac    1.1    Hal
                                 ad   0.6                                  ad    0.8
                   b   7.51   3J      7.5                    b   7.71   5J       0.9
                                 bc                                        ae
    S
             a
                              4J
                              3J
                                 bd   1.0      N       a
                                                                        3J
                                                                        4J
                                                                           bc    6.7       O
O       O
            7.80                 cd   7.8            8.22                  bd    1.5
                                                                        3J       8.4
                                                                           cd
                                                                        4J
                                                                           de   -0.5       N
                              3J      8.4                               5J      0.4
            8.32                                      8.27
                                                                                           S
    O                            ab            O                           ae
             d                4J      1.1              e                3J      8.6
                                 ac                                        bc
                              5J      0.5                               4J      1.0
                   c   7.36      ad                          d 7.27        bd
                              3J      7.1                               5J      0.4
                   b   7.70      bc                          c 7.74        be
    O                         4J
                                 bd   1.8      N                        3J
                                                                           cd   7.0    C       X
             a                3J                       b   7.57         4J
            7.46                 cd   8.0      H
                                                                           ce   1.4
                                               a   11.70                3J      8.2
                                                                           de
                                                                                        P Si

                                                                                       Natural
                                                                                       Products

                                                                                       Solvents
              196            5 1H NMR

              5.7 Halogen Compounds

              5.7.1 Fluoro Compounds
      C
              19F (natural abundance 100%) has a spin quantum number I of 1/2. The signals                                                      of
              1H atoms are split by coupling to 19F up to a distance of about four bonds.
  C       C
              1H      Chemical Shifts and Coupling Constants (δ in ppm, |J| in Hz)
  C       C


                  4.27                                         5.45                                               6.25
              CH3 F              2J        46.4            CH2 F2         2J        50.2                     CHF3 2JHF 79.2
                                      HF                                       HF

              1.24                                        1.56
                  b         2
                                                           b
                                                                                2J                                 1.68
                          F JaF             46.4                      F            aF    57.3                                F
                            3J              25.2                  a             3J       20.9
                       a       bF                                                  bF                        0.97        4.30
      N               4.36 3Jab              6.9                 F 5.94         3J
                                                                                   ab     4.5

  Hal         1.34                            4.37
                             F                Hb          F       2J           87.4     3J      12.8                1.45
                                                                     aF                    ab
                                                                  3J           20.1     3J       4.7                H                     F
      O                                       H           Ha
                                                                  3J
                                                                     bF
                                                                     cF        52.4     2J
                                                                                           ac
                                                                                           bc   -3.2                            3J
                                                                                                                                     HF       15.3
                                                    c
                                              4.03        6.17
      N
                      0.27      2J                      64.9
                                   aF
                       c        3J                       9.9                               4.49
      S           H
                                3J
                                   bF
                                                        21.0
                                                                                1.28        H                         1.63        F
                           F       cF                                               H                                    H
              e Hb              3J                       5.9       1.65                                     1.58
              H                    ab                                                              F                                      H 4.94
                                3J                                    H                         H 2.15       H                        H
  C       X                Ha      ac                    2.4                                                                2.03
                                2J                                              H                                 H
                 Hd                                     -6.7      1.12 H 1.86 H 1.42                        1.28 H 1.75 H 1.43
                0.69      4.32 3 bc
                                 Jbd                    10.8
  P Si                          3J
              (in benzene/CFCl3) be
                                3J
                                                         7.7
                                   ce                   12.0
                                                                                                                   4J      -0.8      3J       7.9
Natural                                     3J            3J
                                                                                                CF3                   aF                ab
Products               F                       aF   8.9      ab   8.4                                              5J       0.8      4J       1.2
                                            4J            4J                                                          bF                ac
                                               bF   5.7      ac   1.1                   e              a   7.53    6J      -0.7      5J       0.6
                                            5J            5J                                                          cF                ad
              e              a   7.03               0.2           0.4                                                                4J       2.0
                                               cF            ad                         d              b   7.27                         ae
Solvents      d              b   7.31
                                                          4J
                                                             ae   2.7                                                                3J       7.6
                                                          3J                                    c                                       bc
                                                             bc   7.5                                                                4J       1.3
                       c                                  4J                                7.34                                        bd
                                                                  1.8
                      7.13                                   bd
                                                                             5.7 Halogen Compounds                               197

        CH3         Couplings                     Ha          CF3
                                                                                                    F
                    with CH3:                                                             8.11                          3J
                    4J                                                                                                     aF   10.7
                         2.5                                                  7.51                               7.13   4J
                  F 5 o                                                                                    a
                                                                                                                           bF    5.4       C
                     Jm 0.0
                    6J                                                        7.53                         b     7.38
                       p 1.5
                                                 5J        2.2                            7.84     7.61
                                                      aF                                                                                  C       C

5.7.2 Chloro Compounds
                                                                                                                                          C       C
1H      Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)


3.06                               5.33                              7.26                         1.33
CH3 Cl                             CH2 Cl2                           CHCl3                                       Cl 3J 7.2
                                                                                                          3.47

2.07                                    3.67                                 1.81                      0.92        1.68
             Cl                                      Cl                               Cl                                        Cl
             5.89                  Cl
                                                                  1.06          3.47                        1.41        3.42                  N
        Cl              3J   6.1           3J   6.8
                                                                                                                                           Hal
                                                                 5.48                 3J                       2.05
             Cl                                                  Hb            Cl        ab   14.5
                                                                                                                                              O
                                                Cl
                                                                                      3J       7.5                 H                 Cl
             4.14       3J   6.4                                                         ac
                                                                                      2J      -1.4
                                                                                         bc
    1.55                                1.60                     H
                                                                     c
                                                                               Ha
                                                                 5.39          6.26                                                           N

        0.74
         c
                             3J
                                ab       7.0                                  3.88                                                            S
        H                    3J          3.6                     1.33         H                             1.77        Cl
                                ac                                   H                                         H
                         Cl 2Jbc        -6.0          1.68                                        1.75
e Hb                                                                                 Cl                             H 4.59
H                            3J
                                bd      10.3              H                        H 2.22          H              H        C                      X
                             3                                                                                    2.00
                         Ha Jbe          7.1                     H
                                                      1.18 H 1.84 H 1.58
                                                                                                        H
    Hd                       3                                                                    1.26 H 1.55 H 1.76
                        2.96 Jce        10.6
 0.87
                                                                                                                                           P Si

                                   3J                                                                    3J                               Natural
                                           8.1                                                                   8.1
             Cl
                                   4J
                                      ab                                       CCl3
                                                                                                         4J
                                                                                                            ab                            Products
                                      ac   1.1                                                              ac   1.1
                                   5J      0.5                                                           5J      0.5
    e               a   7.33          ad                                 e            a    7.89             ad
 d                  b   7.28
                                   4J
                                      ae   2.3                           d            b    7.27
                                                                                                         4J
                                                                                                            ae   2.4                      Solvents
                                   3J      7.5                                                           3J      7.5
             c                        bc                                       c                            bc
                                   4J      1.7                                                           4J      1.4
         7.22                         bd                                      7.25                          bd
              198             5 1H NMR

                             8.21                                 3J                 4J                                 7.72* 7.65
                                            Cl
                                                                     ab    7.7          df   1.0                                                 Cl
                                 g                                4J
                                                                     ac    1.1       5J
                                                                                        dg   0.2              7.47**
              7.48      f                           a    7.49     3J       7.8       3J      6.8              7.45**                         7.40
      C                                                           5J
                                                                     bc
                                                                                     4J
                                                                                        ef
              7.43      e                           b    7.28        cg    0.7          eg   0.6                        7.79* 7.74
                                 d          c                     3J       8.1       3J      7.8
                             7.74       7.65
                                                                     de                 fg                           *; **: assignments
  C       C                                                                                                              interchangeable

              5.7.3 Bromo Compounds
  C       C
              1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)


              2.68                                       4.94                            6.82                          1.65
              CH3 Br                                    CH2 Br2                          CHBr3                                       Br
                                                                                                                              3.36

              2.47                                       3.63                            1.89                        0.93       1.84
                            Br 3                                                                      Br
                                 J 6.4                                Br                                                                    Br
      N                 5.86                       Br
                                                                                  1.04         3.36                      1.46        3.42
                   Br
  Hal
                                                                                 5.84                 3J                    2.32
                                                                                 Hb                           14.9
      O
                            Br                                   Br                           Br         ab
                                                                                                      3J       7.1              H                Br
                        4.20                                                                             ac
                                                                                                      2J      -1.9
                                                                                                         bc
                  1.73                                    1.76                   H
                                                                                     c
                                                                                              Ha
      N                                                                          5.97          6.44


      S           0.81
                    c
                                          3J
                                             ab           7.1                                4.09
                   H                      3J              3.8                     1.35        H                         1.79        Br
                                             ac                                      H
                                      Br 2Jbc            -6.1          1.72                                                 H
              e Hb                                                                                  Br         1.78                        H 4.81
  C       X   H                           3J
                                             bd          10.2              H                      H 2.33        H                      H
                                          3                                                                                    2.08
                                      Ha Jbe              7.0                    H
                                                                       1.22 H 1.80 H 1.75
                                                                                                                     H
                  Hd                      3                                                                    1.24 H 1.60 H 1.81
                                     2.83 Jce            10.5
  P Si         0.96


Natural                                          3J                                           Br
Products             Br                             ab   8.0                     8.19                                   7.78        7.98
                                                 4J      1.1                                                                                     Br
                                                    ac                7.51                          7.71       7.48
                                                 5J      0.5
              e                  a   7.49           ad
Solvents                                         4J      2.2          7.44                           7.21      7.46                          7.53
              d                  b   7.22           ae
                                                 3J
                                                    bc   7.4                     7.73        7.70                       7.72        7.68
                        c                        4J
                                                    bd   1.8
                   7.28
                                                                         5.7 Halogen Compounds                                    199

5.7.4 Iodo Compounds

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
                                                                                                                                         C

2.16                                     3.90                            4.91                          1.86
CH 3 I                               CH 2 I2                             CHI3                                        I                  C       C
                                                                                                              3.15
2.96                                                                                                                                    C       C
              I                          3.64                            1.86                         0.93       1.80
                      3J   7.0                       I                                  I                                     I
          5.24                       I
                                                                 1.04           3.16                     1.42        3.20
     I


                                                                6.57                   3J                    2.06
              I                                  I               Hb             I         ab   15.9
                                                                                       3J       7.8              H                 I
          4.24                                                                            ac
                                                                                       2J      -1.5
                                                                                          bc
    1.89                                  1.95
                                                                 H
                                                                     c
                                                                            Ha
                                                                6.23            6.53                                                        N

                                                                                                                                         Hal
    0.76                    3J            7.5
      c                        ab                                         4.18
     H                      3J            4.4                    1.36      H                             1.72        I
                        I   2J
                               ac
                                         -5.9            1.80
                                                                    H
                                                                                                1.73
                                                                                                             H                              O
e Hb
                            3J
                               bc                                                     I                                      H 4.96
H                              bd         9.9             H                         H 2.45       H                       H
                            3                                                                                   2.06
                        Ha Jbe            6.6                   H                                     H
    Hd                      3                        1.30 H 1.67 H 1.97                         1.26 H 1.62 H 1.53                          N
 1.04                  2.31 Jce          10.0


                                                                                                                                            S
                                 3J                                         I
          I                         ab   8.0                    8.02
                                 4J      1.1
                                    ac               7.46                             7.68
                                 5J      0.5                                                                                            C       X
e                 a   7.70          ad
                                 4J      2.2         7.39                              7.02
d                 b   7.10          ae
                                 3J      7.4                    7.62      7.97
          c                      4J
                                    bc
                                         1.8                                                                                             P Si
     7.32                           bd

                                                                                                                                        Natural
                                                                                                                                        Products

                                                                                                                                        Solvents
              200      5 1H NMR

              5.8 Alcohols, Ethers, and Related Compounds

              5.8.1 Alcohols
      C
              1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)

  C       C   Aliphatic and alicyclic alcohols:   δOH = 0.5–3.0 (in DMSO: 4–6) ppm
              Phenols:                            δOH = 4.0–8.0 (in DMSO: 8–12) ppm
  C       C   Hydrogen bonds strongly deshield hydroxyl protons. The position of the signal may
              depend heavily on the experimental conditions including the concentration of the
              sample. If a compound contains several kinds of hydroxyl protons (–OH, –COOH,
              H2O), in general only one signal at an average position is seen because of rapid
              exchange. In dimethyl sulfoxide (DMSO) as solvent, this exchange in most cases
              is so slow that isolated signals are obtained. In this case, the chemical shifts of
              hydroxyl protons are characteristic. However, if the sample contains strong acids or
              amine bases, the exchange rate increases and, also in DMSO, a single signal at an
              average position is observed. Frequently, intermediate exchange rates lead to very
              broad signals extending over several ppm and, therefore, sometimes not discernible
      N       in routine spectra.
                 As a consequence of fast intermolecular exchange of the hydroxyl protons, their
  Hal         coupling with the protons on the adjacent carbon atoms is usually not observed.
              However, in very pure (acid-free) solutions or in DMSO, the exchange is suffi-
              ciently slow so that the H–O–C–H couplings become visible. Their dependence on
      O       the conformation is analogous to that shown by the H–C–C–H couplings (Chapter
              5.1.2). In case of fast rotation: 3JHOCH ≈ 5 Hz. In cyclohexanols, the vicinal cou-
              pling constants for axial hydroxyl protons (3.0–4.2 Hz) are lower than those of
      N       equatorial ones (4.2–5.7 Hz).


      S                b   a                      c        a
                                                          OH
                                                                                  c        a
                                                                                          OH
                     CH3 OH
                                                      b                       d       b

  C       X       CDCl3 DMSO D2O              CDCl3   DMSO D2O              CDCl3     DMSO     D2O
              a   1.13   4.05             a   1.51    4.31              a   1.51      4.31
              b   3.49   3.17  3.34       b   3.71    3.44    3.65      b   3.59      3.34     3.61
  P Si                  3J 5.2
                          ab              c   1.24    1.06    1.17      c   1.59      1.42     1.57
                                                       3J 4.8           d   0.94      0.84     0.89
                                                         ab
                                                       3J 6.9
Natural                                                  bc
Products

Solvents
                                 5.8 Alcohols, Ethers, and Related Compounds                                        201

              c              a                                           a                      b             a
                        OH                        e            c                                          OH
                                                                       OH
                    b
                                                         d         b
                                                                                                                            C
    CDCl3         DMSO D2O                      CDCl3        DMSO        D2O                CDCl3 DMSO D2O
a   1.36          4.30                      a   1.50         4.30                       a   1.37  4.19
b   4.04          3.78   4.02               b   3.64         3.38        3.61           b   1.28  1.11 1.24                C       C
c   1.22          1.04   1.17               c   1.56         1.40        1.51
                  3J 6.2                    d   1.39         1.30        1.35
                    ab
                                            e   0.94         0.87        0.91                                              C       C

                        5.2                                            5.6                                         6.4
                  CH2 OH                                           CH OH                                          C OH
                                                               2                                          3
         (in DMSO)                                    (in DMSO)                                 (in DMSO)

     0.34                                                                h 1.88 2.46         3J
                                                                                                bc 7.0
                                 3J                                                                           3J
         c
                                    ab    6.2                  f       dH                                        cf 2.3
         H                                            1.63 H                    OH a         3J                                N
                                                                                                bd 8.1
                                 3J                                                                           4J
                                          2.9                                                                    cg 5.2
                                                                       H
                                    ac
                                                                                             4J
                                                                                                be 0
                                 2J                                                                           3J
                                         -5.4                                                                    de 10.4
e Hb
                    OH
                                    bc
H                                3J
                                    bd   10.3                     H
                                                         1.41 H e g                Hb        4J
                                                                                                bf -1.1
                                                                                                              3J
                                                                                                                 df 9.7     Hal
                                 3J                                     Hc         4.23      2J -11.0         4J
                                          6.8                                                                    dg -0.9
                        Ha                                                                      cd
    Hd                              be
                                                                        2.24                 3J
                                                                                                ce 7.9
                    3.35         3J                                                                           4J
    0.59                            ce   10.9                                                                    dh 0
                                                                                                              3J -11.0
                                                                                                                 ef            O
                                                                        1.05    H 3.52
                                                                     1.26                        Derivatives
                                                                                                                               N
                                                                         H
                                 CDCl3     DMSO                     OH
e                      a a                                       H                               in DMSO:
                                 1.28      4.33                    2.01
H                    OH                                                                          δOH 4.0–4.5
                         b       4.32      4.09 0.85 H H 1.78 H                                  JCH,OH 4.2–5.7
    Hf               Hb c        1.56      1.44     0.97      1.22                                                             S
         Hd       Hc     d       1.76      1.61          1.35 OH 1.25                            Derivatives
                         e       1.76      1.61            H
                                 1.56      1.44                                                  in DMSO:                  C       X
                                                                 H 4.03
                         f                                          H
                                                                                                 δOH 3.8–4.2
                                                                  1.83
                                                0.86 H H                                         JCH,OH 3.0–4.2
                                                         1.54 H
                                                    0.99      1.49                                                          P Si

                                                                             OH 11.1                  OH 10.57
                                                                                                                           Natural
         OH a           CDCl3       DMSO         3J      8.0                                                               Products
                                                    bc                                                              NO2
                    a   4.69        9.29         4J      1.1                       6.96       7.16
                                                    bd
f             b     b   6.83        6.75         5J      0.5                       8.14
                                                 4J
                                                    be                                        7.58                8.10     Solvents
e             c     c   7.24        7.15            bf   2.2
                                                 3J                                                   7.00
         d          d   6.93        6.76            cd   7.4                 NO2
                                                 4J      1.8            in DMSO                      in CDCl3
                                                    ce
              202           5 1H NMR

              1H Chemical Shifts and Coupling Constants of Enols (δ in ppm,
              J in Hz)

      C                ≈16                                        ≈16                                                     15.5
                        H                                         H                                                        H
                   O         O           3J        9.7        O        O             3J        5.1                    O          O
                                            ab                                            ab
                                         3J        ≈8
  C       C   Ha                  Hc        bc
                                                         Ha                 CH3                              H3 C                    CH3
              8.40 H b ≈9.3                              7.90 H b           2.11                             2.04          H         2.04
                   5.04                                       5.60                                                    5.52
  C       C                                                                                               (in CDCl3, partly enol-
                                                                                                          ized; for the keto form,
                                                                                                          see Chapter 5.11.2)
                            16.6                                          16.2
                             H                                              H                                             O
                       O          O                                   O          O                        12.45
                                                                                                            HO
                                                                                                                               O
              H3 C                      CH3                                           CH3
              2.14                      2.14                                H        2.18                                      O
                       2.27                                                                                 2.00
      N                           1.06                                    6.16                                            O
                                                                                                                (in CDCl3, partly
  Hal                                                                                                           enolized)


      O       5.8.2 Ethers

              1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
      N
                       3.24                                                 3.48                                 3.34         3.34 0.93
                                   2J         -10.6                                        3J
                                                                                                vic 7.0
      S         O                       gem                             O
                                                                                 1.20
                                                                                                                          O
                                                                                                                                   1.59


  C       X                 3.65
                                          3J
                                               vic 6.1                3.40 1.38                                  3.21                1.19
                                  1.13                   alk
  P Si                 O                                          O
                                                                           1.54 0.92
                                                                                                                          O


Natural
Products                                                                                                 6.44                 4J
                              b          a         CDCl3 DMSO D2O                                         Hb
                                                                                                                 3.88            ab 0.3
                                                                                               3.16                           3J
                   O
                                               a   3.40  3.24 3.37                                                   Hc          bc 7.0
Solvents                           O                                                            a    O                        3J 14.1
                                                                                                                                 bd
                                               b   3.55  3.43 3.60                                                            2J -2.0
                                                                                                                Hd               cd
                                                                                                            4.03
                               5.8 Alcohols, Ethers, and Related Compounds                                                203

1HChemical Shifts and Coupling Constants of Cyclic Ethers (δ in
ppm, J in Hz)

                                                             a                                                                   C
                                                   d                                                         O
         O
                                       2.78 H          O    CH3 1.47
                 2.54                                                                                c               a   4.73

In derivatives:                        3.07 H c             H
                                                                 b       3.34                               b 2.72              C       C
                                                                                                     2J
2J                                                                                                      a,gem -5.8
   gem 5–6                                         3J      5.2                                       2J
3J        4.5                                         ab                                                b,gem -11.0
3J
   cis                                             3J      4.2                                       3J          8.7            C       C
   trans 3.1
                                                      bc                                                cis
                                                   3J      3.3                                       3J          6.6
Throughout:                                        2J
                                                      bd                                                trans
                                                           4.2                                       |4Jac| <0.3
Jcis > Jtrans                                         cd



   O                    CDCl3 DMSO                                           O                    CDCl3      DMSO
                                                                                        a
             a      a   3.74  3.60                                                            a   3.65       3.53
           b        b   1.85  1.76                                                      b     b   1.57       1.47
                                                                              c               c   1.64       1.58

                                                                                                                                    N
     O             CDCl3 DMSO D2O                                            O                                   O
                                                                                        3.67                             3.88
                    3.71  3.57 3.75
                                                                                        2.87                             2.57
                                                                                                                                 Hal
     O                                                                       N                                   S
                                                                             H 1.92
                                                                                                                                    O
                                     3J           8.3                                                3J          1.6
                   O                    ab,cis                               O                          ab
  6.31 d                  a   4.31   3J          10.7                d                      4.63     4J         -2.5
                                                                                                                                    N
                                                                                        a
                                        ab,trans                                                        ac
                                     3J           2.5                                                4J
     4.95 c              b 2.58         bc                               c          b   5.89            ad,cis 7.1
                                     4J           2.6                                                4J
                                        bd                                                              ad,trans 4.6
                                     3J           2.6                                                3J          6.3
                                        cd                                                              bc                          S
                                     3J      6.2                                                     3J      7.0
                   O                    ab                                    O                         ab
  3.96 e                  a   6.34   4J      2.0                     e                  a   6.17     4J      1.7                C       X
                                        ac                                                              ac
                                     3J      3.8                                            4.63     4J      1.5
  1.85 d                  b   4.64      bc                           d                  b               ae
                                     4J      0.6                                                     3J      3.4
                    c
                  1.98
                                        bd                                    c
                                                                             2.66
                                                                                                        bc                       P Si

                                                                                                                                Natural
                                     3J
                                        ab   5.0                                                     3J                         Products
       O           O
                                     4J
                                                                             O
                                                                                                        ab   6.0
                          a   7.77      ac   2.4                     d                  a   7.89     5J
                                     5J                                                                 ac   0.3
6.38         d            b   6.43           1.2                     c                  b   6.34     4J
                                     3J
                                        ad
                                             6.3                                                        ad   2.7                Solvents
                   c                    bc                                                           4J      1.1
                                     4J      1.5                                                        bc
                  7.56                  bd                                   O
                                     3J      9.4
                                        cd
              204         5 1H NMR

              1HChemical Shifts and Coupling Constants of Aromatic Ethers (δ in
              ppm, J in Hz)

      C                   a
                              3.75       5J ≈0.8                          3.98
                                            ab                                                                        4.51
                      O                  3J
                                            bc 8.3                        O                                   O
                                         4J                                        1.38                               1.31
  C       C                                 bd 1.0
              f               b   6.90   5J
                                            be 0.4
              e               c   7.29   4J
                                            bf 2.7
  C       C           d                  3J
                                            cd 7.4
                   6.94                  4J
                                            ce 1.8


                                                                                                    3J        8.3
                                                                                                       ab
                              7.23*                                             O                   4J        1.1
                                          5.09                                                         ac
                                                                                                    5J        0.5
                  7.21*                                                   e             a   7.01       ad
                                            O                                                       4J        2.6
                                                                                                       ae
                                                                          d             b   7.32    3J        7.4
                                                                                                       bc
                                                                                                    4J        1.7
                  * assignment uncertain                                           c                   bd
      N                                                                        7.09

  Hal         1H Chemical Shifts and Coupling Constants of Acetals, Ketals, and
              Ortho Esters (δ in ppm, J in Hz)
      O
                                                               1.22              4.90                         4.70
                                  3.20
                          O                          O                                                    O       O
      N       4.44                         4.67           3.60                O         O
                                                                                                                       3.80
                          O                          O                           b     a    3.88
                                                                                                              1.68
      S                                                                       2J
                                                                                 a,gem -7.5
                                                                              3J
                                                                                 ab,cis 7.3
                                                                              3J
                                                                                 ab,trans 6.0
  C       X                                      6.81                                                                 3.32
              O           O                              O                             O    3.31     1.62           O
                                         6.81
                                                                5.90                   4.57                         4.29
  P Si                O
                              5.00
                                                         O
                                                                          1.28         O                            O
                                                                                                   0.91
                                                         2J         1.5
                                                              gem
Natural
Products
                                                                                                                       1.22
                                                          O                                 3.29
                          O                                                    O       O                  O       O
Solvents                                                                                                               3.58
                  O       4.96                       O     5.16
                          O 3.33                          O                    O       O                  O       O
                                           1.23 3.61
                                           5.9 Nitrogen Compounds                205

5.9 Nitrogen Compounds

5.9.1 Amines
                                                                                        C
Amine and Ammonium Protons (δ in ppm, |J| in Hz)

Chemical shifts of amine protons lie around 0.5–6 ppm depending on solvent, con- C          C
centration, and hydrogen bonding. Those of ammonium protons are found between
ca. 7 and 12 ppm. Neighboring H bond acceptors lead to deshielding in all cases.
                                                                                       C    C
                                                        in CDCl3           in DMSO
Amines:       δNH2, δNH              aliphatic            <1–2                2–4
                                     aromatic              3–4                4–7
Ammonium: δNH3+, δNH2+, δNH+         aliphatic            7–11               7–11
                                     aromatic             8–12               8–12

Coupling of amine protons with vicinal H atoms is usually not seen in aliphatic
amines because of their rapid intermolecular exchange. However, for =C–NH–CH
moieties (enamines, aromatic amines, amides, etc.), the exchange rate is slower and
                                                                                         N
splitting (or line broadening at intermediate rates) is often observed. The H–C–N–H
coupling depends on the conformation in a similar way as the H–C–C–H coupling
(see Chapter 5.1.2). For N–CH3 and N–CH2 groups: 3JHCNH ≈ 5–6 Hz.                       Hal
   In acidic media (e.g., in trifluoroacetic acid as solvent), the exchange of the am-
monium protons is slowed down to such an extent that the vicinal coupling H–N+–
C–H generally becomes observable. In other media, signals are usually broad owing       O
to intermediate exchange rates.
   The signals of amine and especially of ammonium protons are often broad-
ened additionally because the 14N–1H coupling is only partly eliminated by the          N
quadrupole relaxation of 14N (spin quantum number, I = 1; natural abundance,
99.6%; 1JNH ≈ 60 Hz). This line broadening has no effect on the vicinal H–C–N–H
coupling so that sharp multiplets can be observed for neighboring H atoms even
                                                                                        S
when the NH proton exhibits a broad signal. In ammonium compounds of high
symmetry, the quadrupole relaxation is slow and the coupling with 14N leads to
triplets of equal intensity for all three lines.
                                                                                       C X


                                                                                        P Si
                                                                        2J 0.5
    NH4 +    1J        52.8                      N+          Br–
                                                                          aN
                                                                        3J 1.6         Natural
                  NH
                                                         b   1.79         bN
                                                                        4J 0.0         Products
                                                  a                       cN
                                                 3.36        c   1.06
                                                                                       Solvents
              206              5 1H NMR

              1HChemical Shifts and Coupling Constants of Amines and
              Ammonium Salts (δ in ppm, J in Hz)

      C       2.47                                   1.10                                          0.92       1.43         1.11
              CH3 NH2                                            NH2                                                    NH2
                                                         2.74                                         1.35 2.69
  C       C
                                                            0.80                                   1.14–1.69 0.99
              ≈2.3                                1.11                                                         H 1.10
              (CH3 )2 NH
                                                             H                                   0.92
                                                                                                                       N
  C       C                                                  N
                                                      2.66                                                     2.62        2.63

              2.22                              1.03 2.52
              (CH3 )3 N                                                                     0.91    1.41
              2J         -11.7                               N                                                   N
                   gem
                                                                                                  1.29 2.38

              3.21 (in D2O)
                                                                                                1.02 1.45
              (CH3 )4 N+ I–
                                                1.27 3.27                                                     3.40
      N
                                                             N   +
                                                                          I   –                     1.68          N+             Br–
              3.46 (in CDCl3)
  Hal         (CH3 )4 N+ AcO–                            (in D2O)

      O                                       0.88                                 1.0
               1.03 1.15                 1.05 H 1.10                          1.04 H                              1.02
                               NH2              N                                           N                                N
      N       3.07                      2.79        2.64                  2.91                                   2.59             2.23


      S                    c                     3J
                                                                                                    1.64             1.87
                           H 0.20                   ab    6.6                                             H
                                                 3J                                   1.55* H                        NH2
                                                    ac    3.6                                        H
                                     NH2 1.59    2J
  C       X        e Hb
                                                    bc   -4.3
                   H                             3J                                                                  H 3.40
                                                    bd    9.7                         1.64* H         H
                                     Ha 2.22     3J
                       H d 0.32                     be    6.2                                          H
                                                                                                    2.23
  P Si                     (neat)
                                                 3J
                                                    ce    9.9
                                                                                            * assignment uncertain

Natural
Products      1.72*                   1.37                               2.55                                              1.30
                       H              NH2                       1.03      H                                      1.27       NH2
                                                                     H                1.30                        H               3.15
Solvents               H              H 3.31                                      H
                                                                                      NH2                                         H
                                                                                                                             H
              1.28* H     H
                                                                                  1.89                                 1.65
                     1.82 1.55                   0.84
                                                             H                                     0.86        H
                                                            H 1.76 H                                          H 1.53 H
               * assignment uncertain                    0.96            1.03                             0.96             1.54
                                                                5.9 Nitrogen Compounds                             207

                                           3.66          2.83                                   2.94
                           3J      8.0                             3J      8.2                             3J      8.4
         NH2 3.61             ab                HN                    ab                 N                    ab
                           4J      1.1                             4J      1.1                             4J      1.0
                              ac                                      ac                                      ac
e               a   6.67   5J      0.5     e             a 6.61    5J      0.4   e              a 6.74     5J      0.4  C
                              ad                                      ad                                      ad
                           4J      2.5                             4J      2.5                             4J      2.8
d               b   7.14   3J
                              ae           d             b 7.18
                                                                   3J
                                                                      ae         d              b 7.24
                                                                                                           3J
                                                                                                              ae
         c                    bc   7.4            c                   bc   7.3           c                    bc   7.3
      6.75
                           4J
                              bd   1.6        6.70
                                                                   4J
                                                                      bd   1.7          6.72
                                                                                                           4J
                                                                                                              bd   1.8 C C
    δNH in DMSO: 4.94                    δNH in DMSO: 5.52
         2
                                                                                                                         C       C
               3.70                                             2.94                                           3.10
                                                4.62 HN                                               N
         N+ (CH3 )3 Cl–
                                                                6.53                                           6.59
                 8.08
                                                                8.09                                           8.09
                 7.64
      7.59                                               NO2                                          NO2
    (in DMSO)                                  δNH in DMSO: 7.32
                                                                                                                             N
1H  Chemical Shifts and Coupling Constants of Cyclic Amines
(δ in ppm, J in Hz)                                                                                                       Hal
                      2J                         H 2.08                    H 2.01                      H 2.18
     H 0.9               gem ≈1
                                                                                                                             O
                                                 N                         N                           N
     N                3J
                         ab,cis 6.3                     3.63                      2.75                          2.79
b          a   1.61   3J
                         ab,trans 3.8                                            1.59                           1.53
(neat)                                          2.33
                                                                                                      1.53
                                                                                                                             N
         2.23                                                                                              2.26
                                          H 2.59
                                                                        N                              N
                                                                                                                             S
     N                                    N
               2.33                              2.86                            2.32                          2.37
               1.59                              3.67                            3.62                          2.88
                                          O                             O                              N
    1.41                                                                                               H 1.72
                                                                                                                         C       X
5.9.2 Nitro and Nitroso Compounds

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)                                                           P Si
4.34                                           1.58                                              2.01                    Natural
CH3 NO2                                                  NO2       Jvic 7.4                                  NO2
                                                                                                                         Products
                                                  4.43                                         1.03     4.28

1.53                                           1.07    2.07                                      1.59                    Solvents
             NO2                                                  NO2                                        NO2
         4.44                                     1.50 4.47
              208         5 1H NMR

                                                                       4.38
                   NO2                                       1.38       H                                                    NO2
                     4.91                                        H                                               H                 4.43
                                                                                NO2                                                H
      C                 2.26, 2.12             1.67 H                       H                                                  H
                           1.88, 1.70                        H               2.23                            H                2.60
                                                    1.28 H 1.85 H                                        H               H
                                                                1.85                                                     1.62
  C       C

                                                        NO2                  3J      8.4           NO                        3J      7.9
                                                                                ab                                              ab
  C       C   5.87       7.12                                                4J      1.2                                     4J      1.3
              Hb         Ha     3J       7.0                                    ac                                              ac
                                   ab
                                3J      14.6
                                                 e               a   8.27    5J
                                                                                ad   0.4    e                a   7.84        5J
                                                                                                                                ad   0.6
                                   ac                                        4J                                              4J
                                2J       1.4     d               b   7.60       ae   2.4    d                b   7.57           ae   2.0
              Hc         NO2       bc                                        3J                                              3J
                                                        c                       bc   7.5           c                            bc   7.4
              6.55                                                           4J                                              4J
                                                      7.73                      bd   1.5          7.63                          bd   1.4



              5.9.3 Nitrites and Nitrates
      N       1H   Chemical Shifts (δ in ppm)
                                                          1.41        4.71                                                1.59
  Hal               4.78
                           O NO                                             O    NO
              1.39                                   0.96     1.72                                                           O NO

      O             4.52                             1.06        4.39                                                    5.19
              1.37
                           O NO2
                                                            1.78
                                                                       O NO2                           1.37                  O NO2
      N

      S       5.9.4 Nitrosamines, Azo and Azoxy Compounds

              1H   Chemical Shifts (δ in ppm)
  C       X
              Owing to hindered rotation around the N–NO bond, corresponding protons in cis
              and trans positions have different chemical shifts in the neighborhood of the N=O
  P Si        group.
              In general: δcis < δtrans for α-CH3, α-CH2, and β-CH3
                           δcis > δtrans for α-CH
Natural
Products
                           O                                 O                                                       O
                                                      N
Solvents             N                                                                                   N
                                          1.52        N          1.15                0.97       1.75                 1.75            0.93
                     N                                                                                   N
                                             4.26             4.89
              3.76       2.96                                                              1.39 4.07 3.53 1.39
                                                           5.9 Nitrogen Compounds                      209


3.7                           3.4
           N                               N                                                   7.92
       N                               N                                                N
                                                                                   N                   7.50    C
                                                                                                       7.45

                                                                        7.51                                  C       C
4.16                          1.48                              7.54            8.30
           N                                     N                                            8.17
      N+                                   N+                                           N                     C       C
                 3.16                                                             N+
                                                                                                       7.48
      O–                                   O–          1.28
                                                                                  O–                   7.39


5.9.5 Imines, Oximes, Hydrazones, and Azines

1H    Chemical Shifts (δ in ppm)
                             3.4                                  7.46 7.89                 7.20 7.38
                                                                                                                  N
                      CH N                                 7.46                 CH N                   7.22
                     8.40                                                       8.43
                                                                                                               Hal
In aldoximes and ketoximes, the chemical shift difference between syn and anti
protons at the α-CH group, Δδ = δsyn - δanti, depends on the dihedral angle,
φH–C–C=N:                                                                                                         O
                                                 φ            Δδ = δsyn - δanti
                 H       φ
                                                  0o                        1
                                                                                                                  N
                   N                             60o                        0
                                                115o                     -0.3                                     S
                                                                                                     10.18
           9.9                         9.9                             9.3
           OH                          OH                              OH                       N
                                                                                                     OH       C       X
      N                            N                              N
                                                                                       2.23           2.25
H                                      H
                                                            1.89 1.90                                          P Si
6.92 1.86                    1.83 7.52                                                 1.66           1.64
                                                                                            (in DMSO)         Natural
                 8.9                                        6.9                                       7.0     Products
                 OH                                        OH                                        OH
           N                                           N                                       N
                                                                                                              Solvents
2.22               2.50                    2.60                                                       2.30
                       1.74–1.55
              210          5 1H NMR

                                   11.02 7.93 8.28                                                7.56
                                                                                                              11.04 7.94 8.29
              2.14 7.57                   H                                             1.03       H
                                                                                                                        H
              CH3 CH               N      N                          NO2                                    N           N                       NO2
      C
                                                    NO2 9.10
                                                                                                       2.33
                                                                                               1.99                             NO2 9.10

  C       C
                          7.79         11.12 7.96 8.32
              5.78        H                                                                7.69               8.06* 7.14 8.18
              H
                                              H                                                   7.81              H
  C       C                          N        N                          NO2
                                                                                                   CH      N        N                         NO2
                                                     NO2 9.12                     7.3–7.5
              H                H                                                                      * in DMSO: 11.33
              5.74            6.62

                      2.03                                  2.00                         7.44 7.83
                                                                                                       8.66
                           N             H                       N              7.44                    CH          N
                  H            N                                     N                                                  N       CH
                  7.89                               1.83
      N

  Hal         5.9.6 Nitriles and Isonitriles

              1H  Chemical Shifts and Coupling Constants of Nitriles (δ in ppm,
      O       J in Hz)

              1.98                 1.31                                  1.70                  1.35                     0.96 1.63
      N                                                                            CN                      CN                                   CN
              CH3 CN                                CN
                                                                                                        2.67                    1.50 2.34
                                          2.35                     1.08 2.34
                                         3J         7.6
                                              vic
      S
                                                                                                              CN                        3J      7.8
                                                                                                                                           ab
                                                          6.11       5.69                                                               4J      1.3
              1.37                                                              3J                                                         ac
  C       X                    CN                           Hb           Ha        ab   11.8           e                    a   7.66    5J      0.7
                                                                                3J                                                         ad
                                                                                   ac   17.9                                            4J      1.8
                                                                                2J       0.9
                                                                                                       d                    b   7.48       ae
                                                            Hc           CN        bc                                                   3J      7.7
  P Si                                                    6.24                                             7.62
                                                                                                                c
                                                                                                                                        4J
                                                                                                                                           bc
                                                                                                                                           bd   1.3

Natural
                                                    3J       8.4
Products              c                                ab                                                                       1.50
                   H 1.04                           3J                     1.22 H 2.39                                                  CN
                                                       ac    5.1                                                                    H           2.96
                                                    2J                      H
              e Hb
                                   CN
                                                       bc   -4.7                                                                                H
Solvents H                                          3J       9.2    H              H
                                                                                     CN                         H                         H
                                                       bd        1.70                2.08                  1.70                            2.00
                                                    3J                                                                          H
                  Hd 0.96
                                     Ha                      7.1          H                                             H 1.70 H 1.54
                                                       be               H 1.76 H 1.52
                                   1.29             3J       9.5                                                    1.20
                                                       ce            1.20
                                                             5.9 Nitrogen Compounds                              211

1H  Chemical Shifts and Coupling Constants of Isonitriles (δ in ppm,
|J| in Hz)

Because of the symmetrical electron distribution around the N atom, the quadrupole C
relaxation of the nitrogen nucleus is so slow that the 14N-1H coupling becomes ob-
servable and leads to triplets with relative intensities of 1:1:1 (spin quantum number
of 14N: I = 1; natural abundance, 99.6%):                                              C C

                              b          a
                                                         |2JaN|     1.8–2.8
                          CH2 CH2             14
                                                   NC                                                                    C       C
                                                         |3JbN|     1.5–3.5

 2.85                                1.28                                       1.45
     a                               b
                                                         |2JaN| 2.0              b           NC  |2JaN| 1.8
                                                    NC
CH3 NC |2JaN|       2.3                                  |3JbN| 2.4                               3
                                                   a                                   a
                                                                                            3.87 |3JbN| 2.6
                                             3.89        |3Jab| 7.3                              | Jab| 7.0


1.45                                         5.35 H b          H a 5.90 |2JaN| 2.3                3J
 a                                                                                                   ab 8.6
                 | JaN| 2.1
              NC 3
                                                                                |3JbN|     6.1    3J 15.6
                                                                                                     ac
                                                                                |3JcN|     3.1    2J -0.5                    N
                                             5.58 H c          NC                                    bc

                                                                                                                          Hal
5.9.7 Cyanates, Isocyanates, Thiocyanates, and Isothiocyanates

1H       Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)                                                          O
1.45                                                         1.20                                     1.63
           OCN
                           3.02
                              CH3 NCO                                    NCO                                    NCO          N
     4.54                                                         3.37                           0.99    3.26

                                                                                                                             S
1.29                                                                            4.77        6.12
             NCO          0.94           1.58                                     Hb             Ha
                                                                                                             3J
                                                                                                                ab 7.6
                                                       NCO                                                   3J 15.2
            3.72                                                                                                ac       C       X
                                  1.42       3.29                                                            2J -0.1
                                                                                                                bc
                                                                                  Hc             NCO
                                                                                5.01
                                                                                                                          P Si
2.60                      1.53                                            SCN
CH3 SCN                                  SCN
                                                                         3.48                                            Natural
                                  2.98
                                                                                                                         Products
                                                                                                         NCS
3.37                      1.40
CH3 NCS                                  NCS                              NCS                                    7.15 Solvents
                                  3.64                                   3.98
                                                                                                                 7.30
                                                                                                        7.24
              212         5 1H NMR

              5.10 Sulfur Compounds

              5.10.1 Thiols
      C
              1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)

  C       C   Typical ranges of SH chemical shifts:


  C       C     alk–SH           1–2                                   SH            2–4


              The exchange with other SH, OH, NH, or COOH protons is generally so slow that
              the chemical shift is characteristic and the vicinal coupling with SH protons be-
              comes visible (5–9 Hz in aliphatic systems with fast rotation).



              2.00 1.26                     1.31     1.39              1.63      1.33            1.34          1.56
      N       CH3 SH        Jvic 7.4                  SH                             SH                 b SH a 3J
                                                                                                                  ab           5.7
                                               2.44                0.99 2.50                                  3.16
              (in benzene)
  Hal

      O       0.92    1.59       1.32*
                                  SH
                                                            1.43   1.82
                                                                   SH
                                                                                         1.79** H                     SH 1.62

                   1.43    2.52                                                          1.51** H                     H 3.19
                                                                                                      H         H
      N       * in DMSO: 2.17                                                                       2.04* 1.59*
                                                                                          *; **: assignments uncertain

      S                          2.79
                          1.31                                                                                         3J      7.9
                                   H                                           SH                 SH 3.40                 ab
                           H                                           H             3.43                              4J
                                                                                                                          ac   1.2
  C       X                                SH 1.51                                   H                                 5J      0.6
                H                      H                                         H           e            a    7.18       ad
              1.61                     2.01                                      1.9                                   4J      2.1
                       H                                           H                         d            b    7.10    3J
                                                                                                                          ae
                                                               H           H                                                   7.5
  P Si
                      H 1.75 H
                                                                           1.5                    c                       bc
                   1.22          1.34                                                                                  4J      1.5
                                                                                                 7.04                     bd

Natural
Products

Solvents
                                                                          5.10 Sulfur-Compounds                                  213

5.10.2     Sulfides

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
                                                                                                                                          C
2.12             2.10          2.51                                          2.48     0.99                     2.55             2.93
                                                                         S
                                                                                                                                 1.26 C          C
     S                     S                                                                                          S
                                    1.26                                           1.60                   1.25

                                                                                               H a 6.43                   3J             C       C
2.09 2.49        1.42                                              1.42             2.25                                       ab10.3
                                                                                                          H b 5.18 3Jac16.4
     S                                                                                     S                              2J
                                                                                                                               bc -0.3
                                                         S
          1.56       0.92
                                                                                                       H c 4.95


         2.47                                                                3J      7.8
                                                                                ab
     S                                                                       4J
                                                 S                              ac   1.2
                                                                             5J      0.6
                                                                                ad
          7.18                                                               4J
                                        e                    a    7.20          ae   2.0
          7.16                                                               3J      7.4                                                     N
                                        d                    b    7.06       4J
                                                                                bc
  7.02                                                                          bd   1.5
                                             7.20
                                                    c
                                                                                                                                          Hal

                                                                                                                                             O
1H  Chemical Shifts and Coupling Constants of Cyclic Sulfides
(δ in ppm, J in Hz)


 S        2J         0                  S
                                                                 2J
                                                                    a,gem -8.7                     S
                                                                                                                               3.81          N
             gem                                                 2J
          3J         7.2        c               a                   b,gem -11.7                          2.82             S         S
             cis                                                 3J
  2.36    3J                                 3.21                   ab,cis 8.9
             trans   5.7                b                        3J
                                                                    ab,trans 6.3
                                                                                                        1.94
                                                                                                                                 3.11
                                                                                                                                             S
                                      2.94                       4J
                                                                    ac,cis 1.2
                                                                 4J
                                                                    ac,trans -0.2
                                                                                                                                         C       X
                                                                    3J       9.2
     S                                  S                              ab                      S                      S
          3.67        6.06      d               a       3.08        3J
                                                                    4J
                                                                       bc    2.5                       2.57                      2.57     P Si
         5.81                                                          bd    2.2                       ≈1.7                      3.88
                        5.48        c        b          2.62        3J                                                O
                                                                       cd    6.1           ≈1.7                                          Natural
                                                                                                                                         Products
     S                                  S                                      S                                   S
          2.85                                  3.79                                  5.97                                      4.28     Solvents
                        2.08                S                                         5.55                     S          S
     S
                                     2.83                                    2.84                             (in DMSO)
              214           5 1H NMR

              5.10.3         Disulfides and Sulfonium Salts

              1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
      C

                                        1.32                                        1.70                          1.31
                                                                                                                             S
  C       C        S
                       S
                             alk                        S
                                                               S
                                                                                                S
                                                                                                    S                             S
              2.30                            2.69                                1.00 2.66

  C       C
                                           3J      7.5
                                              ab
                                           4J      1.4
                                              ac
                                           5J
                                              ad   0.5                                                          1.01     1.57
                                           4J      2.0
                                              ae                            S                                                         3.75
                            S              3J      7.2                 S           2.7          2.94                  1.84
                       S                      bc
                                           4J      1.6                                      (CH3 )3 S+ I–                                 S+ I–
                                              bd                                   1.9
              e                 a   7.47                                                    (in DMSO)
              d                 b   7.29
      N                c
                   7.24
  Hal
              5.10.4         Sulfoxides and Sulfones

      O       1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)

                                                                                                                                          2.64
      N            O                           O               H 6.08                O                     O                  O
                                                                                                                                      S
                   S                               S                                 S                     S
                                                                       H                   2.42                2.88
      S             2.62                2.61
                                                        H          5.92                    1.92                2.43
              (in DMSO)
                                                       6.77                                                    2.05
              neat: 2.50
  C       X
              O        O                               O        O                           O       O                        O        O
                   S                                       S        1.47                        S                                 S
  P Si                     2.84
                                                   2.80 2.94                             2.85           3.13
                                                                                                                      1.44
                                                                                                        1.41
Natural                                                                                                                       O
Products      O        O H 6.43                             O          O                    O       O                  O S                3.06
                   S                                               S                            S
                                    H                                                                   3.74
Solvents                                                                   3.15                                                           7.94
              2.96 H    6.14                                                                           6.08
                                                                                                                                          7.61
                   6.76
                                                                                                                             7.65
                                                                     5.10 Sulfur-Compounds                                215

5.10.5       Sulfonic, Sulfurous, and Sulfuric Acids and Derivatives

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
                                                                                                                                  C
1.42 3.17                11.1                                                                                             2.86
CH3 CH2           SO2    OH             3.02                                3.91            2.78                          CH3
                                           CH3       SO2             O CH3                  CH3      SO2          N              C       C
Apparently lower δOH                                                                                                      CH3
values in DMSO due to
fast exchange with H2O                                                                                                           C       C
                          3.70                                                                           5.07       2.63
     OH 11–12            OCH3                    Cl                                NH2 7.37                   NHCH3
     SO2                 SO2                         SO2                           SO2                        SO2

                                7.94                         8.02                          7.85                           7.86
                                7.60                         7.61                          7.58
                        7.62                    7.71                             7.58                              7.4–7.7
                                                                             (in DMSO)                                               N
                                                     3.97                                                 O           O
         O       3.64                       O
                                                     4.03               2J
                                                                        3J
                                                                           gem-10.3                             S                 Hal
     O
         S
             O                         O
                                            S
                                                 O                         vic  6.7                       O               3.25
                                                                        3J'
                                                           1.26             vic 6.9
                                                                                                     4.49             2.64
                                                                                                                                     O
                                                                                                          O           O
     O       O 3.94                                  O       O 4.34                                             S
     O
         S
             O                                   O
                                                         S
                                                                 O
                                                                                                          O           O              N
                                                                        1.43                                          4.68
                                                                                                                                     S
5.10.6       Thiocarboxylate Derivatives

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)                                                                  C       X
                                                      O                                                       S
              O
                                                                             3J
                                                                                ab   5.9                                          P Si
                                                 S               a    6.47   4J                          O                7.1
2.41 H3 C          SH 5.09                                                      ac   2.0
                                                                             3J      2.8           7.7                    6.9
                                       4.29      c           b       7.84       bc                                               Natural
                                                                                                             6.4                 Products
                                                      S
              O
                                   9.56 HN                           2.98                                                        Solvents
2.30 H3 C          SCH3 2.27           3.38                          1.72
                                            1.79           1.65
              216          5 1H NMR

              5.11 Carbonyl Compounds

              5.11.1 Aldehydes
      C
              1H    Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)

  C       C
                                                        9–10         3J         0–3
                    alk       CHO                                         vic
                                                        9–10         3J         ≈8
  C       C         alken       CHO                                       vic
                                                        ortho-substituted: 10–10.5
                                      CHO
                                                        meta-, para-substituted: 9.5–10.2
                    R



              9.60                            2.20 9.79                         1.13         9.79                1.67            9.74
              CH2         O                   H3 C CHO                                 a CHO                              a      CHO
                                                  a          b                            b                                       b
              (in TMS)                                                             2.46                        0.97     2.42
      N
              |2Jgem| 42.4                        3J
                                                       ab   3.0                  3J 1.4
                                                                                   ab
                                                                                                                      3J 2.0
                                                                                                                        ab

  Hal
              1.13            9.57                           1.08        9.48
                                                                                                                           9.76
      O            a CHO                                                 CHO                           0.93 1.59
                                                                                                                       a CHO
              2.39    b
                                                                                                                          b
                                                                                                          1.35        2.42
      N        3J
                    ab 1.1
                                                                                                                 3J
                                                                                                                      ab 1.9



      S       6.52        6.37                                                                7.43       9.67
               Hc             Hb      3J       4.7          3J 10.0                            Hc        CHO             3J       7.8
                                         ab                   bc                                           a                ab
                                      4J      <1            4J 17.4                                                      3J      16.0
                                         ac                   bd                                                            bc
                                      4J      <1             2J
  C       X    Hd               O        ad                     cd 1.0                                   H 6.69
                                                                                                          b
              6.35        H a 9.59                                              7.4             7.53
                                                                                        7.4
  P Si

Natural       O           H 10.03             O          H 10.24           O           H 9.95            O          H 11.54
Products
                                                                                                                        8.99
                                                                  2.64
                              7.88    7.77                                              7.76                                     7.69
Solvents
                              7.53    7.33                   7.23                       7.32                                     7.56
               7.63                               7.45                                                       8.71       8.07
                                                                                      2.42
                                                                  5.11 Carbonyl Compounds                                 217

5.11.2 Ketones

1H   Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
                                                                                                                                  C

       O                           O                                    O                                         O
                                            1.06                                 1.60                                     1.11
                                                                                                                                 C       C
2.17                       2.14        2.44                       2.13 2.40            0.93               2.14           2.58
                                                                                                                                 C       C
                                            6.21                                                    6.28
     O                             O          Hc           3J 10.7                 H          O          Hc       3J 11.0
                                                              ab                                                    ab
              1.13                                         3J 18.7                                                3J 17.9
                                                              ac                                                    ac
                                                           2J                                                 H b 2Jbc 1.4
                           2.29
                                                   Hb         bc 1.3         H
2.14                                               5.91                                                   5.82
                                        Ha                                              H          Ha
                                       6.30                                                       6.67


                       O                                       O                                              O
           7.96                                     7.95                1.22                      7.95                 1.77          N
7.46                                    7.45                                           7.42
7.56
                           2.60
                                        7.55
                                                                   2.98
                                                                                       7.55
                                                                                                                  2.93 1.00       Hal

                                                                                                                   O                 O
                   O                                                O
       7.95                    1.22                                          7.90
                                                                                                                          6.78
                            3.54
                                                                                        7.46                                         N
                                                                                        7.57
                                                                                                                   O
                                                                                                                                     S
                                                    2J            -17.5
  O                                O                   aa,gem                          O                           O
                                                    3J             10.0
                                                       ab,cis
                                                    3J              6.3                                                          C       X
                           c            a              ab,trans                                2.17                       2.33
                                                    4J              4.2
                                        3.03           ac,cis
                                                                                              1.98                        1.88
       1.65                        b                4J             -3.0
                               1.96                 2J
                                                       ac,trans
                                                                  -11.1                                           1.71            P Si
                                                       bb,gem

                                                                                                                                 Natural
              1.44                                      7.77         O                               8.01
                                                                                                                   O             Products
0.97           H               O
                                              7.37                                         7.46*                          2.63
                               H                                            2.70
            H         2.40                    7.59                                         7.33*                          2.12 Solvents
           H 2.08 H 2.31                                           3.15
       1.46                                             7.48                                        7.21 2.93
                                                                                              * assignment uncertain
              218           5 1H NMR

              1H    Chemical Shifts of Diketones (δ in ppm)

                   O                               O                O               O         O                        7.96        O
      C                         2.34
                                                                                                            7.87
                                                                                                                                        3.24
                                                               3.0                    3.62 2.17
  C       C             O
                                                                                 For the enol form,                                O
                                                                                 see Chapter 5.8.1
  C       C   Long-Range Coupling in Ketones (|J| in Hz)

              For fixed conformations, the coupling over the C=O group is often detectable for
              W-arrangement of the coupling path.

                                 O                                                                    Ha O
                    R                          R       |4J   ab|   0–0.5                                    Hb     |4Jab| 1.0
                            a          b
                                                                                                      Br
      N
                   No W-arrangement                                                     W-arrangement

  Hal
              5.11.3 Carboxylic Acids and Carboxylates

      O       1H    Chemical Shifts (δ in ppm)

                        a                  b                                 a            b                        a               c
      N                 H COOH                                              H3 C COOH                                        COOH
                                                                                                                        b
                  CDCl3 DMSO D2O                                            CDCl3 DMSO                                 CDCl3 DMSO
      S       a    8.05  8.13 8.26                                      a    2.10  1.91                            a    1.16  1.00
              b   10.85 12.50                                           b   11.51 11.91                            b    2.39  2.21
                                                                                                                   c   10.35 11.90
  C       X
                    1.68               11.51 1.21                       11.88       0.93 1.62                 11.96         1.23       11.49
                                                                    COOH
  P Si
                                 COOH                                                                       COOH                   COOH
                                                   2.56
              1.00      2.31                                                            1.39         2.35
Natural
Products                                                            12.2                6.53                                 COOH 12.09
              1.06                             2.43           COOH                        H          O
                          COONa
Solvents                                                                                                                           8.12
                   2.18                                       COOH
                                                                                    H                    OH
                                                                                   5.95                    12.8                    7.45
                                                                                               H
                  (in D2O)                         (in DMSO)                                                                7.62
                                                                                              6.15
                                                          5.11 Carbonyl Compounds                                      219

5.11.4 Esters and Lactones

1H  Chemical Shifts and Coupling Constants of Carboxylic Acid Esters
(δ in ppm, J in Hz)                                                     C
                                         7.33
     O                               O    Hb
          3.76                                      4J -0.7 3J
                 4J | 0.8
          CH3 | ab                             Hc      ab       bc 6.4 C C
                                                    5J    1.6 3Jbd13.9
  Ha    O   b                    Ha    O       4.66 5 ac
8.07                            8.07                 Jad 0.8 2Jcd -1.7
                                             H                                     d
                                                                           4.96
                                                                                                                              C       C
       O                                         O                                                   O
                3.67                                     4.12                                                 4.02 0.95
            O                                        O                                                    O
2.01                                    2.04                  1.26                            2.05                1.65


       O                                     O                                                       O
                    4.99                             4.06 1.39
            O                                    O                                                        O
2.02                1.23              2.04               1.60 0.94                                                1.45            N

                                                                                                                               Hal
                7.28                                                                    d                      3J      8.2
                                   3J                                                                             ab
       O        Ha                    ab 6.3                                   e               c   7.22        4J      1.1
                        4.56       3J 14.1
                                                                     O                                            ac

            O
                           Hb         ac
                                   2J -1.6                                                     b   7.37
                                                                                                               5J
                                                                                                                  ad   0.5        O
                                      bc                                   O                                   4J      2.5
2.13                                                          2.29                      a                         ae
                     Hc                                                                7.08                    3J      7.5
                                                                                                                  bc
                    4.88                                                                                       4J
                                                                                                                  bd   1.7        N

1.15
            O
                    3.67                         1.65
                                                              O
                                                                                               1.17
                                                                                                              O
                                                                                                                       3.67
                                                                                                                                  S
                O                                                   O                                              O
     2.32                                 0.98 2.22                                                2.56
                                                                                                                              C       X


                                                          O
                                                                                                                               P Si
                    O                                                                                     O
0.92 1.61                   3.66             1.20                   3.66                                          4.41
                                                                                              F
                        O                                       O                                             O               Natural
                                                                                              F                        1.40 Products
     1.33 2.31
                                                                                                     F

                                                                                                                              Solvents
              220         5 1H NMR

                   6.41                                         6.37
                     H          O                                H          O                                           O       O
                                         3.77                                       4.21                                            3.92
      C        H                     O                     H                    O
                                                                                          1.30                  8.04
              5.83        H                              5.81          H
                                                                                                                7.43
                         6.12                                        6.13
  C       C                                                                                                                 7.55


  C       C                                1.38                                   1.37                                       7.22
                      O          O                              O          O                            O           O
                                                                                  5.22                                                  7.44
                                     4.36
                                                                                                                                        7.28
              8.05                                       7.99                                    8.21
              7.41                                       7.37                                    7.52
                          7.52                                       7.46                                   7.64


                  O                                  O                      2J -17.5         2J -12.7                           O
                                                            Ha                 ab               cd
      N                                                          2.49
                                                                            3J
                                                                               ac 9.5
                                                                                             3J
                                                                                                ce 7.9
                                                 O                          3J               3J
                                                                               ad 6.9           cf 6.3                                  6.18
              O           3.56                                  Hb                                                          O
  Hal          4.29
                                            He              Hc              4J
                                                                            4J
                                                                               ae 0.3
                                                                                             2J
                                                                                                ef -8.8
                                                                                                                        4.91        7.59
                                           4.32 Hf H d 2.26                    af -0.5

      O                                                                                                                         3J
                          O                                      O                                      O                          ab   9.4
                                                                                                                                4J      1.5
                                                                                                                                   ac
      N
                                                                                                                                5J      1.3
                     O              3.31                    O              6.05                    O                a   6.31       ad
                                                                                                                                3J      6.3
              4.09                  ≈1.6             4.44                  7.10            7.48 d                   b   7.33    4J
                                                                                                                                   bc
                                                                                                            c                      bd   2.4
                         ≈1.6                                   2.50
      S                                                                                                 6.25                    3J
                                                                                                                                   cd   5.0


              5.11.5 Amides and Lactams
  C       X
              Amide Protons (δ in ppm, J in Hz)
  P Si                O                                               O                                             O
                                                                                    alk
                R          NH2                                  R           N                                   R        N
Natural                                                                     H                                            H
Products              5–7                                              6–8.5                                     7.5–10
              R: alk or ar                                      R: alk or ar                                R: alk or ar
Solvents
              Higher values in DMSO or with H bond acceptors in the neighborhood.
                                              5.11 Carbonyl Compounds                  221

The signals of the NH protons are often broad because the 14N–1H coupling is only
partly eliminated by the quadrupole relaxation of 14N (spin quantum number, I =
1; 1JNH ≈ 60). In primary amides, the hindered rotation around the CO–N bond is
another reason for line broadening. At slow rotation, the chemical shifts of the two C
primary amide protons differ by about 0.4–1 ppm. Therefore, at intermediate rota-
tion rates, line widths of up to 1 ppm may be observed.
    Due to the slow intermolecular exchange of amide protons, their coupling to C C
neighboring hydrogen atoms is usually detectable. The splitting of the C–H signal
is clearly observed even in those cases where the signal of the NH proton is broad
and featureless. The H–N–C–H coupling depends on the conformation in a similar
                                                                                     C C
way as the H–C–C–H coupling (see Chapter 5.1.2). For N–CH3 and N–CH2 groups:
3J
   HNCH ≈ 7 Hz.


Tertiary Alkylamides

The rotation around the CO–N bond is usually so slow that, for identical substituents,
two separate signals are observed for cis and trans positions. With different N-
substituents, two separate pairs of signals are observed for the two conformers. In
general, the following relationships hold:                                                        N
  for NCH3, NCH2CH3, and NCH(CH3)2               δcis to O ≤ δtrans to O
  for NCH(CH3)2 and NC(CH3)3                     δtrans to O ≤ δcis to O                       Hal
  for NCH2                                       δcis to O ≈ δtrans to O

Formamides (δ in ppm, J in Hz)                                                                    O
In the more stable conformer of monosubstituted formamides, the substituent occu-
pies the cis position relative to the carbonyl oxygen. In the more stable conformer of            N
asymmetrically disubstituted formamides, the larger substituent occupies the trans
position relative to the carbonyl oxygen.
                                                                                                  S
         O                       O                         O                O          2.88
                  Hb                      b                                             b     C       X
    Ha       N              Ha       N                Ha       NH c    Ha        N
                                     Hc
             Hc                                                 b     8.02        c
                        ≈ 90% in CDCl3           ≈ 10% in CDCl3                  2.97          P Si
    CDCl3 DMSO
a    8.23  7.98             CDCl3 DMSO               CDCl3 DMSO        4J
                                                                          ab    ≈0.3
b    5.80  7.14         a    8.19  8.01          a    8.06  7.81       4J       ≈0.7          Natural
                                                                          ac
c    5.48  7.41         b    2.86  2.59          b    2.94  2.72                              Products
                        c    5.55  7.90          c    5.86  7.90
                                                                                              Solvents
              222          5 1H NMR

                      O                                 O                                                                     O
                                6.6                               3.32
                                                                                           O
                                                                                                   2.71                                       4.78
                                H
              H           N                         H        N                        H        N                        H          N
      C       8.00                                  8.13              1.17                                                                    1.10
                                                             H                                     4.12
                 3.30                                                                                                             2.83
                               1.21                         6.6                                    1.19
  C       C                                                                               ≈ 70%                                   ≈ 30%
                                                                       O
                                                                                8.34
                      O
  C       C                    3.32                               H           NH                               O                             7.15
                                                            8.69
              H           N                                                                                                                  7.33
                                     1.14                                            7.09                 H          N
              8.06                                                                                   8.40            H        7.55
                  3.34                                                               7.37
                                    1.20                                                                           7.14
                                                                        7.21
                                                                       ≈ 35%                                        ≈ 65%
                                                                   3J                                         3J
                                                                      HCNH 10.6                                    HCNH ≈0


      N       Amides of Aliphatic Carboxylic Acids (δ in ppm, J in Hz)

              In monosubstituted acetamides, the substituent of the only observable conformer is
  Hal         cis to the carbonyl oxygen. In disubstituted acetamides, the more stable conformer
              has the larger substituent cis to the carbonyl oxygen.

      O               O
                                                             a
                                                                          O                                         O
                                 Hc                                                  Hd                                           c
                           N                                                   N                                         N         3J
                  a                                                b                                          a                               4.8
      N
                                                                                                                                        bc
                           Hb                                                  Hc                                        Hb

                  CDCl3 DMSO                                      CDCl3 DMSO                                   CDCl3 DMSO
                   2.03  1.76                                      1.17  0.97                                   1.98  1.78
      S       a
              b    5.42  7.30
                                                             a
                                                             b     2.26  2.04
                                                                                                          a
                                                                                                          b     5.53  7.70
              c    5.42  6.70                                c     5.38  7.16                             c     2.80  2.50
                                                             d     6.14  6.62
  C       X
                      O         3.26                                  O                                                 O
                                 a                                             3.18 0.96                                            a 4.01
  P Si                     N                                               N                                                  N
              1.98         Hb        1.14                   ≈2.0           H       1.55                       ≈2.0            Hb         1.13
Natural                   6.7                                                                                                8.1
                                    3J        5.9                                                                                  3J          8.4
                                         ab                                                                                              ab
Products
                      O                                                    O                                              O
Solvents                       3.21 1.35
                                                                                                                                         3.01
                           N                                                   N                                              N
              1.98         H         1.49 0.92                    ≈2.0         H       1.28                        2.08
                          7.05                                                 7.3                                                 2.94
                                                               5.11 Carbonyl Compounds                                    223

  O                                               1.03
            2.70                          O                                                O
                                                       4.52                                          3.46
        N
                                              N                                                  N          1.86                  C
            3.92                                                                 2.05
            1.15                            2.83                                                3.42 1.96
 ≈ 40%                                    ≈ 60%                                                                                  C       C

                                                                                 O
            O          4.11                                                              5.42                                    C       C
                         H     1.03           0.87                                       NH 1.11            0.84
                                 H                                                           H
1.99              N                                                      3.67 H H
                  H H
             5.56 1.85            H                                          2.01               H
                             H 1.66 H                                                      H 1.78 H
                          1.51           1.04                                            1.07         1.01

                                                                                     d                          3J
                   O                                                                                               ab   8.2
                             3.40                                    O       e              c   7.11            4J      1.2          N
                                                                                                                   ac
       2.08              N           1.57*                                                  b   7.32            5J
                                                                                                                   ad   0.5
                                                                                                                                  Hal
                                                                         N                                      4J
                  3.54               1.54*                    2.18       H           a                             ae   2.4
                                                                                 7.49                           3J
                                                                                                                   bc   7.4
                     1.64*                                                                                      4J
                                                                                                                   bd   1.5
           * assignment uncertain
                                                                                                                                     O
Lactams (δ in ppm, J in Hz)

                                                                                                                                     N
                                              O                              O                                    O
            O
                                 6.06                           2.85                                 6.33
                                                                                                                          2.36
2.75
       N           2.82               HN             2.30                N           2.37
                                                                                                        HN
                                                                                                                                     S
                                                                                                     3.31                 1.81
        3.20                             3.40 2.14                       3.39 2.03                              1.79
                                     3J              0.8
                                                                                                                                 C       X
                                          HNCH2



              O
                                                                                                                                  P Si
                                                                             O                                   O
2.94                                          O                                                   2.98
                                                               6.35
        N              2.37         HN               3.35            HN              2.46                   N            2.52 Natural
 3.29                  1.82                       NH          3.21                       1.69     3.36                    1.66 Products
            1.81                                     8.00
                                                                     1.65 1.75                           1.65 1.70
                                              O                                                                                  Solvents
                                    3J             2.2
                                         HNCH2
              224            5 1H NMR

              5.11.6 Miscellaneous Carbonyl Derivatives

              Carboxylic Acid Halides (δ in ppm, J in Hz)
      C
                     O                         O                          O                           O                              O
                                                                                         1.24                             1.22
  C       C               Cl                        Br                        I                             Cl                            Br
              2.66                      2.82                       3.00                    2.93                                3.03

  C       C
                                                                                                                                 3J      8.0
                   6.60                             6.63                                              O          Cl                 ab
                     H          O                     Hc        O                                                                4J      1.2
                                                                        3J 10.6                                                     ac
                                                                          ab                                                     5J
                                                                        3J 17.4                                                     ad   0.6
               H                    F           Hb                   Cl 2 ac                      e                 a   8.11     4J      2.0
              6.25                                                       Jbc 0.2                                                 3J
                                                                                                                                    ae
                          H                     6.16       Ha                                   d                   b   7.49        bc   7.5
                                                                                                                                 4J      1.4
                         6.14                              6.35                                             c                       bd
                                                                                                          7.69

      N
              Carboxylic Acid Anhydrides (δ in ppm)

  Hal                                                                                                     O           O
                   O           O                          O         O                                                       8.13
                                               1.69
                                                                                                                                         7.49
      O                  O                                     O
                                                                                                                O
              2.22                         1.00 2.43                                                                                     7.64

      N
                                                                                  2.33     O                                              O
                              O                       O                                                                   8.04
      S       3.01
                                O
                                        7.05
                                                       O
                                                                     1.70
                                                                                              O
                                                                                                                7.93
                                                                                                                                           O

                                                                                           O
  C       X                   O                       O                                                                                   O
                                                                              (in DMSO)
              Carboxylic Acid Imides (δ in ppm, J in Hz)
  P Si

Natural                       O                            O                              O                                    O
Products 2.77                                2.70                             6.73                               6.72
                                                                3.56                                                                 3.58
                                NH   8.9                   N                               NH         8.5                        N
Solvents                                                            1.17                                                                 1.19
                              O                            O                              O                                    O
                                                                   5.11 Carbonyl Compounds                                 225

           O                                 O                      7.85         O                   7.82           O
2.61                       O                         O       7.85                             7.72
                                                                                                                           3.18
               N                             N                                       NH                              N             C
2.06                                                                                  11.4
       3.81            2.48             3.48     2.36
                                                                                 O                                  O
                                                                    (in DMSO)                                                     C       C
           O                                     O
                                                                                                            3.56
2.57                                  2.97                                                                                        C       C
                                                                                                                1.22
               N Cl                              N Br                                         N C N


           O                                     O
  (in DMSO)


Carbonic Acid Derivatives (δ in ppm, J in Hz)
                                                                                                              4.86
                                                                                                 1.50           H                     N
           O                                     O                      4.54                         H3 C
3.79                                  4.19                                       O                                   O
       O           O                         O       O
                                                                                          O                                 O      Hal
                                 1.31                                            O               4.03 H              O
                                                                                                                H
                                                                                                              4.56
                                                                                                                                      O
           O                                                 O                                              O
2.78                   4.11                                             2.54                                         3.27
       N           O                                     N         N                                  N         N
                                                                                                                                      N
       H                       1.24                      H         H 5.69                             H         H          1.26
   4.8                                                       3J
                                                                  HNCH     4.7
                                                     (in DMSO)                                                                        S

                                                                         2.78                                              2.92 C         X
                   O                                                                                        3.26
   2.97                                                             N                                                N
                                                     3.28
           N               NH2 5.45                                        O                         1.98                   O
0.98       H
                                                                    N                                                N             P Si
      5.92
   (in DMSO)
                                                                                                                                  Natural
3.97                                                         S                                            S                       Products
           S                                                            3.02                                        3.39
                       S                                 N         N                                 N          N
           S
                                                         H         H 6.50                            H          H        1.16     Solvents
                                                             3J            4.8
                                                                  HNCH                               (in D2O)
              226             5 1H NMR

              5.12 Miscellaneous Compounds

              5.12.1 Compounds with Group IV Elements
      C
              Silicon Compounds (δ in ppm, J in Hz)

  C       C   Coupling with silicon: The isotope 29Si (natural abundance, 4.7 %) has a spin quan-
              tum number I of 1/2. Doublets with the corresponding intensity ("Si satellites") are
              usually observed. Typical coupling constants: 1JHSi -150 to -380 Hz
  C       C                                                    2J          5 to 10 Hz
                                                                  HCSi

                    H                              H                             CH3                             CH3
                                           0.19                         0.14                         0.08
              H Si H 3.20                   H3 C Si H 3.58              H3 C Si H 3.83               H3 C Si H 4.00
                    H                              H                             H                               CH3
              1J          -202.5           1J
                   HSi                        HSi -202.5                1J
                                                                           HSi -202.5
                                                                                                     1J
                                                                                                        HSi -190
                                           3J
                                              HSiCH 4.7                 2J
                                                                           HCSi   7.7                2J
                                                                                                        HCSi   7.5
                                                                        3J                           3J
                                                                           HSiCH 4.3                    HSiCH 3.8

      N
                                                         7.3 7.53
                          CH3                                       CH3 0.33                        H            H
  Hal         H3 C Si CH3 0.00                     7.3              Si H 4.45                H Si N Si H 4.35
                          CH3                                       CH3                             H         H
              2J
      O                       5.5                                                                          CH3
                   HCSi                                     1J
                                                               HSi -189                                    2.63
                                                            2J        7.6
                                                               HCSi                            1J          -209.4
                                                            3J                                      HSi
                                                               HSiCH 3.6
      N
                         Cl                       Cl                 Cl                                         7.37
                                   0.42                  0.79                  1.14
                                                                                                                       7.31
      S
              H3 C Si CH3                   Cl Si CH3            Cl Si CH3
                         CH3                      CH3                Cl                                                7.56

                                                                                                                Si H 5.47
  C       X                                                      1.25
              5.88        6.11                                                  3.85
                                           3J 14.6
              Hb              Ha              ab                            O
  P Si                        CH3
                                           3J 20.2
                                           2J
                                              ac
                                                                    O      Si H 4.29
              Hc           Si CH              bc 3.8                                                 1J
                                 3                                          O                             HSi    -199.1
Natural 5.63               CH3 0.06
Products

Solvents                  CH3         OH      pH-dependent shift of the methyl H atoms relative to DSS.
              H3 C Si CF2 P O Between pH 4.3 and 8.2 [1]:                                                0.224 - δ 
                                                                                       pH = 6.246 - log 
                         CH3          OH                                                                 δ - 0.193 
                                                                                                                    
                                           5.12 Miscellaneous Compounds                            227

The silanol hydrogen is exchangeable with D2O. Slow intermolecular exchange is
observed in DMSO as solvent so that the vicinal coupling in H–Si–O–H is detect-
able (3JHSiOH ≈ 2–7 Hz).
                                                                                                          C

          CH3
                                                                                                         C       C
      H Si OH 4.42                             5.45 H Si OH 5.78
                   3J                                       3J
          CH3        HSiOH 1.8                                 HSiOH 2.0
                    (in DMSO)                                (in DMSO)                                   C       C



Germanium, Tin, and Lead Compounds (δ in ppm, J in Hz)


          CH3                                 CH3                                    CH3
H3 C Ge CH3 0.13                         H3 C Sn    CH3 0.07                    H3 C Pb CH3 0.71
          CH3                                 CH3                                    CH3                     N
                                        2J 117     51.9 (7.6 %)
                                          HC Sn
                                        2J 119
                                          HC Sn    54.3 (8.6 %)                                           Hal

5.12.2 Phosphorus Compounds                                                                                  O
31P (natural abundance, 100%) has a spin quantum number I of 1/2. Couplings to
protons through up to 5 bonds are usually observed.                                                          N
Phosphines and Phosphonium Compounds (δ in ppm, J in Hz)
                                                                                                             S
                          0.98 2.63                 1.06
PH3 1.79
                                                                                                   0.97 C        X
                         H3 C     PH2               H3 C                              H3 C
1J
     HP   184.9          1J
                            HP 186.4                       P   H 3.13                        P     CH3
                         2J
                            HCP 4.1                 H3 C                              H3 C
                         3J
                            HCPH 8.2                1J
                                                       HP 191.6
                                                                                       2J
                                                                                            HCP    2.1    P Si
                                                    2J
                                                       HCP 3.6
                                                    3J
                                                       HCPH 7.7                                          Natural
                                                                                                         Products
                                                               2.52 1.28
                                                                   a   b
                         2J
                                                                                    2J      12.8         Solvents
              a   1.20      aP   13.7                                               3J
                                                                                       aP
          P              3J                                    P+          I–               18.0
                            bP    0.5                                               3J
                                                                                       bP
                         3J       7.6                                                  ab    7.6
              b   0.96      ab
              228        5 1H NMR

                                             2J 	11.7
              5.64       6.16                   aP                             7.33 7.46       1.68 1.00
                                             3J 	30.2
               Hb          Ha                   bP
                                             3J 	13.6
                                                cP                              	
                                                                            7.30	           P
      C                         CH=CH2       3J 11.8
                                                ab
               Hc          P                 3J 	18.4
                                CH=CH2          ac
              5.59                           2J
                                                bc 2.0
  C       C


  C       C                    ≈7.3 ≈7.3
                                a   b              3J
                                                      aP   7.5                                                 3J 13.1
                                                                                                                  aP
                       P                 c         4J 	    1.4                      +
                                                                                    P      Cl–                 4J 	 3.7
                                                      bP                                                          bP
                                        ≈7.3       5J 	    0.7                             a     7.64          5J
                                                      cP                                                          cP 2.1
                                                                                                 b   7.83
                                                                                           c     7.95



      N
              Phosphine Oxides and Sulfides (δ in ppm, J in Hz)
  Hal
                                                                 7.51
                                                                          7.47
      O       1.10
               b                                                          7.73                       6.72
                       a   1.65                                                                          Ha
                                                           a
                     P     O                             CH3      P     O                  6.21                   P   O
      N                                                  2.02
                                                                                                 H
                                                                                                     b
                                                                                                         Hc
               3J      11.9                                                                          6.25
      S           aP
               4J 	
                  bP   16.3
                                                           3J                                  2J 	25.9       3J 	12.9
               5J 	
                  ab    7.8                                     aP	13.2                          aP              ab
                                                                                               3J 	41.8       3J 	18.9
                                                                                                 bP              ac
  C       X                                                                                    3J 	22.3
                                                                                                 cP
                                                                                                              2J
                                                                                                                 bc 1.8



  P Si                                                                                               7.3–7.6
                                    c       1.62                                                                  7.3–7.6
Natural                  7.49
Products 1.32              b                                                                                      7.71
                                        H a 7.85    1J 	 481.7
                                                       aP
                                                    4J     0
                                        P     O        bP                                                P    O
                                                    5J     0
Solvents                                H              cP
                                                    5.12 Miscellaneous Compounds                                               229

        1.85                                                                                            1.78        2J        25.9
                                                        1.17                               6.60                          aP
                                                        b                                       Ha      CH3 d 3J 45.3
7.06 CH3                   1.74 CH3                               a   1.81                                      bP
  H P S                    H3 C P S                                                 6.14                P S 3JcP 25.4
                                                                                      H                             2J                 C
                                                                                                                       dP 13.5
                                                                P         S                b
        CH3                         CH3                                                                 CH3
                                                                                                                    3J 11.8
                                                                                                Hc                     ab
 1J                          2J                                                            6.26                     3J 17.9
    HP 14.3                       HCP   13.0                                                                           ac
                                                        2J      11.3                                                2J                C       C
                                                                                                                       bc 1.8
 2J
    HCP 4.4                                             3J
                                                           aP
                                                           bP   18.1
                                                        3J       7.5
                                                           ab
                                                                                                              7.50                    C       C
                                                                                                                c
                                                                      c       1.67                                       b     7.44
        6.82                                    7.50                                                                     a     7.72
            Ha                          1.31        b                     H a 7.86
6.17               P     S                                                P     S                               P     S
   H
        b                                                                 H
            Hc
        6.34
2J
   aP   24.9     3J
                    ab   11.7                   1J
                                                   aP       466.2                                       3J 13.3
                                                                                                           aP
                                                                                                                                          N
3J      47.0     3J      17.9                   4J            4.8                                       4J
   bP               ac                             bP                                                      bP 3.1
3J
   cP   25.5     2J
                    bc    1.6                   5J
                                                   cP         1.1                                       5J
                                                                                                           cP 2.1                      Hal

Phosphinic and Phosphonic Acid Derivatives (δ in ppm, J in Hz)
                                                                                                                                          O
                                                                                                             1.37
            12.0                                    7.76 12.79
                                                                OH                                           4.15
                                                                                                                                          N
1.52        OH                                                                                                      b O
  H3 C P           O                                            P         O
                                                                                                            6.81 H a P O
            CH3                                                 H 6.11
                                                                                                                                          S
                                           7.3–7.6           1J
                                                                                                                          O
                                                                  HP 570.4
  2J        14.4
       HP

                                                                                                                1J       691.7
                                                                                                                   aP
                                                                                                                3J         7.1        C       X
                                                                                                                   bP


             3.66                                    3.65                                            7.40 7.72                3.76     P Si
            OCH3 b                             1.72 OCH3 c                                              b      a
                                                                                                                         OCH3 d
1.43                                                a
                                                            P     O                            7.48 c
 H3 C P O                                                                                                                P O          Natural
  a
            OCH3                                b           OCH3                                                         OCH3         Products
                                               1.06                                                         3J
  2J        17.3                                2J -18.0                                                       aP   13.3
     aP                                            aP                                                       4J       4.1
  3J        11.0                                3J                                                                                    Solvents
                                                   bP 19.5
     bP                                                                                                        bP
                                                                                                            5J       1.2
                                                3J
                                                   cP 10.0
                                                                                                               cP
                                                                                                            3J      11.1
                                                3J
                                                   ab 7.5
                                                                                                               dP
              230         5 1H NMR

              Phosphonous and Phosphorous Acid Derivatives (δ in ppm, J in Hz)

                     O                O            c 1.20          2J          9.7                                                            2J         8.7
                                                                      aP                                                                         aP
      C                       P              b    4.20             3J          9.5                                                  1.01      3J         8.0
                                                                      bP                               N          N                 c            bP
                              CH3                                  4J          6.0                                                            4J        ≈1.0
                                                                      cP                                    P                                    cP
                                  a    1.10                                                                                b       2.96       3J         7.5
                                                                                                            CH3 a 1.18                           bc
  C       C
                                                                                          1.25
                      O               O       a                     O           O             b 3JaP            8.0
              H3 C            P             CH3                            P                    4J                                  N         N
                                                                                      a                         0.6                                     a
  C       C                                 3.49                                                3J
                                                                                                   bP                                     P
                                                                                                                                                   2.48
                              O                                            O         3.85          ab           7.1
                 H3 C                                                                                                                     N        3J 9.1
                                  3J        10.8
                                       aP                                                                                                            aP


              Phosphoric Acid Derivatives (δ in ppm, J in Hz)

                                                        1.35 4.11                                               1.28 4.06
                                  3.78                         b    a                                                 b        a
                              OCH3                                                                                                  O
                                                                        O             3J         8.0                                          3J        10.0
                                                                                         aP                                                        aP
      N       CH3 O P O                                            O P          O     4J         0.9                       O P            S 4JbP         0.7
                                                                                         bP
                              OCH3                                                    3J         7.1                                          3J         7
                                                                                         ab                                                        ab
  Hal
                                                                        O                                                           O
                    3J        11.0
                         HP

              Phosphorus Ylids (δ in ppm, J in Hz)
      O

      N
                                                  Pc                                                                                 Pc
      S                           P
                                      b
                                                                                                                 P
                                                                                                                      b
                                                  H a 1.72                                                                           CH3 a 1.82
                                                       2J      12.7                                                                       3J       15.9
  C       X                                            2J
                                                          ab
                                                                                                                                          3J
                                                                                                                                             ab
                                                          ac   -1.2                                                                          ac     3.6

  P Si
              5.12.3 Miscellaneous Compounds
Natural
Products Organometallic Compounds (δ in ppm, J in Hz)
                                                                                            6.65       7.29
                                            -1.32 (in benzene)                                Hb           Ha             3J        19.3
                     Li       CH3                                                                                            ab
Solvents                                                                                                                  3J        23.9
                                            -1.74 (in ether)                                                                 ac
                                                                                                                          2J         7.1
                                                                                              Hc           Li                bc
                                                                                            5.91
                                                     5.12 Miscellaneous Compounds                           231

6.15     6.66                                                         5.92           6.45
 Hb      Ha              3J      17.7            7.15 7.74                Hb          Ha           3J      11.9
                            ab                                                                        ab
                         3J      23.3                                                              3J      18.7
                            ac             7.08               MgBr                                    ac
 Hc      MgBr
                         2J
                            bc    7.6                                     Hc          HgBr
                                                                                                   2J
                                                                                                      bc    3.1    C
5.51                                                                  5.52
  (in THF)
                                                                                        7.40 7.44                 C       C
                     1.06 1.35
                Hg                                                             Hg                      7.24
                             1.82 0.91                                                                            C       C


Boron Compounds (δ in ppm, J in Hz)

1.50            2.26                                                            0.34        1.10
                                                      -0.49 4.01
BH3    . CH SCH
          3          3
                                                 H   Hm H t                      H3 C          H         CH3
                                                   B   B                                   B       B
1J 11 104                                        H   H   H                       H3 C          H         CH3
  H B
                                                 2J         7.5                 3J          3.0
(11B: 80.4%,    I = 3/2)                            mt                               HH                               N
                                                 1J 11     46.2
                                                    m B
                                                 1J 11    133.0
                                                    t B                                                            Hal
                                                                           7.75 7.55               8.2
0.86    1.23     1.30
                                 B
                                     OH   7.33                                                     OH                 O
                                                                     Br                        B
                                     OH
   1.23 1.23 0.57                                                                                  OH
     (in DMSO)                                                            (in DMSO)                                   N

                                                                                                                      S
                                                                                            Na+
                             1.55 0.91
                                                                                    –
                     O                                                          B
                             3.73
          O     B                                                                                                 C       X
                         O                                                              7.20
                                                                                        6.94
                                                                               6.80                                P Si
                                                                     (in DMSO)
                                                                                                                  Natural
                                                                                                                  Products
5.12.4 References
                                                                                                                  Solvents
[1] M.D. Reily, L.C. Robosky, M.L. Manning, A. Butler, J.D. Baker, R.T. Winters,
DFTMP, an NMR reagent for assessing the near-neutral pH of biological samples,
J. Am. Chem. Soc. 2006, 128, 12360.
              232               5 1H NMR

              5.13 Natural Products

              5.13.1 Amino Acids
      C
              Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)

  C       C
              7.47 4.28
                     b                                        3.58
                                                                                                             1.86                                1.49
                  a                       OH                                 O–               7.41                  OH                                   O–
              +
                  H3 N                             +
                                                       H3 N                                   +                                  +
                                                                                                                                     H3 N
  C       C                                                                                       H3 N
                                                                                                         4.49                                3.79
                                    O                                O                                          O                                   O
                      3J    5.7
                           ab                           (in D2O)                                       (in TFA)                          (in D2O)
                      (in TFA)


                                                                                                     1.11
                                                                                                    ≈2 g                 1.21                     g     1.10
                           1.25       d             1.00       1.04                          ≈2          e
                                                                                                 c,d         1.10                    d                  1.55
                                                                                                                                                 e,f
              7.33              c   2.60                        2.26                7.38                        f        2.28            c              1.70
      N           a                                                                      a
                                          OH                         O–                                      OH                                        OH
              +
                  H3 N      b                  +
                                                   H3 N                              +
                                                                                         H3 N b                          +
                                                                                                                             H3 N b
                                                          3.61
  Hal                    4.32 O                                  O                                4.28 O
                                                                                                                         7.35
                                                                                                                             a           4.41 O
                      3J         5.7                   (in D2O)                               3J          5.5        3J                       3J
                         ab                                                                      ab                     ab           5.5         cf 8.4
      O               3J
                      3J
                         bc      4.2                                                          3J
                                                                                                 bc      ≈6.7        3J
                                                                                                                        bc           3.6      2J -13.6
                                                                                                                                                 ef
                                 6.9                                                          3J         ≈6.7        3J                       3J
                         cd                                                                      bd                     cd           7.0         eg 7.0
                                                                                              3J          6.1        3J                       3J
                       (in TFA)                                                                  eg                     ce           6.1         fg 7.0
      N                                                                                       3J
                                                                                                 ef       5.7
                                                                                                   (in TFA)                          (in TFA)
      S
                                                                                             1.67                                              1.33
                   HO                 4.51                                   HO                d                                     HO
                                c,d
  C       X                           4.56                                               c   4.82                                              4.26
                                          OH                                                       OH                                                   O–
              +
                  H3 N b                                                 +
                                                                             H3 N b                                          +
                                                                                                                                 H3 N
                  a      4.65                                                a     4.44                                                   3.60
  P Si        7.70                  O                                    7.63                O                                                   O
                      3J                                                         3J          5.5                                         (in D2O)
                         ab ≈6                                                      ab
Natural               3J
                         bc 4.0*
                                                                                 3J
                                                                                    bc       4.5
Products              3J
                         bd 4.0*
                                                                                 3J
                                                                                    cd       6.5
                      2J -13.5
                         cd                                                       (in TFA)
Solvents
                         (in TFA)
                      * average value
                                                                                      5.13 Natural Products                                      233

    1.84                                                                                                 2.27                                    2.14
        e                                                                                                    f
                          3.36                                                                   S                                           S
        HS                                    HS            3.12
                    c,d   3.41                                                2.50                                              2.09–
                                                            3.18                                     e   2.96                                    2.64    C
                                                                              2.65 c,d                                          2.23
                                              –
                                           Cl
                           OH                                       OH
+
    H3 N b                                +
                                            H3 N 4.35                                                    OH                                       O–
    a        4.68                                                             +
                                                                                  H3 N b                                   +
                                                                                                                               H 3N
7.58                 O                                        O                   a       4.67                                        3.86              C       C
                                                                              7.73               O                                           O

3J          5.3       2J -15.5                    (in D2O)                3J           5.5    2J -15.7                            (in D2O)
3J
   ab
                      3J
                         cd
                                                                          3J
                                                                             ab
                                                                                              3J
                                                                                                 cd                                                     C       C
   bc       5.0*         ce 9.1*                                             bc        7.7       ce 6.5*
3J          5.0*      3J                                                  3J                  3J
   bd                    de 9.1*                                             bd        4.4       de 6.5*
       (in TFA)                                                                   (in TFA)
    * average value                                                            * average value


                          ≈7.45                                               7.43                                                    7.03
                                                                                                                                                  OH
                   7.3            ≈7.45                            7.33                   7.38                        7.27
3.37                                                         3.13                                        3.34                                               N
             c,d                                                                                                     c,d
3.64                                                         3.29                                        3.60
    +
        H3 N b
                           OH                           +
                                                            H3 N
                                                                               O–
                                                                                                             +
                                                                                                                 H3 N b
                                                                                                                                       OH
                                                                                                                                                         Hal
                                                                   3.99
        a      4.68 O                                                     O
                                                                                                                 a    4.64 O
    7.33                                                                                                     7.4
             3J
                bc 8.5                                             (in D2O)                                           3J
                                                                                                                         bc 8.5
                                                                                                                                                            O
             3J                                                                                                       3J
                bd 4.5                                                                                                   bd 4.5
             2J -14.5                                                                                                 2J -15.0
                cd                                                                                                       cd
                                                                                                                                                            N
              (in TFA)                                                                                                 (in TFA)
                                                                                              6.97
                                                                                                 h                                                          S
                                                                                              NH3 +                                     NH3 +
                                                    O              OH                 3.38   g                                  2.98
                     O                                                                                   f   2.00                                1.73
                                                                                                                                                        C       X
                                     2.55         c,d
                                                               e   3.01           2.26                   e   ≈1.8                                1.43
3.55         c            OH
                                     2.63
                                                                                          c,d                                   1.68
                                                                                  2.35
+
    H3 N b
                          OH
                                      +
                                          H3 N b
                                                                   OH
                                                                                  +
                                                                                      H3 N b
                                                                                                             OH
                                                                                                                               H2 N
                                                                                                                                                  OH     P Si
    a        4.76                         a        4.60                               a                                               3.44
7.73                 O
                                     7.71                    O                               4.52 O                                          O
                                                                                  7.60                                                                  Natural
            3J
               ab  5.1            3J       5.5          2J -15.5               3J         5.8    2J -15.0                             (in D2O)          Products
            3J                       ab                    cd                     ab                cd
                   4.7            3J       5.6*         3J                     3J         5.6*   3J
                                                           ce 6.2*                                  ce 6.0*
               bc
                                     bc                                           bc
             (in TFA)             3J       5.6*         3J                     3J         5.6*   3J
                                     bd                    de 6.2*                bd                de 6.0*                                             Solvents
                                       (in TFA)                                          (in TFA)
                                    * average value                                   * average value
              234           5 1H NMR

              6.19 + H2 N                  NH2 6.19                                             +
                                                                                                    H2 N          NH2

                                                            3J          5.5
                 6.50       d HN                g   3.43       ab                                          HN
      C                                                     3J          5.3*                                          3.21
                                                               bc
                    2.25 c                     e    ≈2.00   3J          5.3*                                          1.63
                                               f    ≈2.08      bd
                    2.34 d                                  2J      ≈ -15.0                         1.63
                                                               cd
  C       C                                         OH      3J          6.5*                                          OH
                                                               eg
                    +
                        H3 N b                              3J                                      H2 N
                                                               fg       6.5*                               3.27
                        a       4.46 O                      3J
                    7.60                                       gh       5.3                                       O
  C       C
                       (in TFA)                                                                        (in D2O)
                    * average value




               2.06 d                  b       2.42          1.63 d            b   1.96       1.05 d            b    1.04
               2.04 e                  c       2.14          1.60 e            c   1.68       1.07 e            c    1.45
              3.46 f                                OH      3.04 f                      O–   2.08 f                        O–
      N       3.39 g N                 a                    2.95 g N           a             2.36 g N           a
                                H2 +            O                       H2 +        O                      H          O
  Hal                               4.33                                   3.74                                2.81
              3J                    3J                      3J             3J                3J                 3J
                 ab 8.5                cd 5.5                  ab 8.4         cd 5.6            ab 8.6             cd 6.7
              3J                    3J                      3J             3J                3J                 3J
                 ac 6.5                ce 7.5                  ac 6.2         ce 7.8            ac 6.6             ce 8.5
      O       2J -13.5
                 bc
                                    2J -13.0
                                       de
                                                            2J -13.5
                                                               bc
                                                                           2J -13.0
                                                                              de
                                                                                             2J -12.0
                                                                                                bc
                                                                                                                2J -11.0
                                                                                                                   de
              3J                    3J                      3J             3J                3J                 3J
                 bd 7.5                df 5.5                  bd 7.6         df 5.7            bd 8.1             df 5.5
              3J                    3J                      3J             3J                3J                 3J
                 be 5.5                dg 7.5                  be 5.4         dg 7.9            be 5.9             dg 8.1
      N       4J
                 bf -0.4
                                    3J
                                       ef 7.5               4J
                                                               bf -0.4
                                                                           3J
                                                                              ef 7.9         4J
                                                                                                bf -0.6
                                                                                                                3J
                                                                                                                   ef 7.7
              4J                    3J                      4J             3J                4J                 3J
                 bg 0.0                eg 5.5                  bg 0.0         eg 5.7            bg 0.0             eg 5.7
                                    2J -11.0                               2J -11.0                             2J -10.5
                                       fg                                     fg                                   fg
      S
                 (in D2O, pH 2.0)                               (in D2O, pH 7.0)              (in D2O, pH 13.0)

  C       X


  P Si                      ≈5                 2.95                                              HO 4.35 2.17
                                           b                3J
                  HO            d
                                           c   2.56            ab   8.2                                              2.44
                                                            3J
Natural        3.9* e                                          ac 10.4                         3.37
                                                     OH     2J                                                              O–
Products       3.9* f         N a                              bc -15.0                        3.49         N
                                                            3J <2
                 8.00
                                 +
                            g H2   O                           bd                                           H2 +
                                                                                                                      O
                                                            3J
                 8.60       h          ≈5                      cd 4.2
Solvents                                                                                                            4.67
                    (in TFA)                                                                           (in D2O)
                 * average value
                                                                              5.13 Natural Products                   235

                                a       7.05                                                        ≈8
                            NH3 +               4.71                                                NH3 +     3.53
       3.79 c                   b                                                       3.04
                                            OH                                                               O–
       3.57 d                                                                           3.33                                 C
                                                     3J
                                                                                    7.58
                                    O                   bc 4.0               7.05                        O
                                                     3J
                                7.25                    bd 8.0                                       7.26
                                                     2J -15.5                6.96                                           C       C
                    N                                   cd                                        N
                    H                                                                             H 11.1
                                                                                    7.36
           (in TFA)                                                                     (in DMSO)                           C       C
                                7.82
               7.66             NH3 +             4.91                                     7.42      NH3 +    4.06
       N        c                                    3Jab 6.4                       N
                        b               a       OH 4                                                         O–
  d                                                   Jcd 1.4                8.69
8.73       N        3.87                                                                N
                                                                                        H     3.36
           H                                O                                                 3.38       O

                (in TFA)                                                                    (in D2O)

                                                                                                                                N
5.13.2 Carbohydrates
                                                                                                                             Hal
Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)

                                                                                                                                O
           3.61                                                                     ≈3.7
            H 3.93 3.23
                    H
                                                                                     H ≈3.7 3.52
                                                                                         H
                                                                                                                                N
                                    HO                                                            HO
       HO                                                                      HO
         HO                                          OH                          HO                          H 5.20
                            H                                                                H                                  S
                    H 3.32                                                               H ≈3.7
                           OH                                                                   OH
                             H                                                                    OH
                3.43      4.58                                                          ≈3.7
                 (in D2O)                                                                (in D2O)                           C       X


                                            g                                                                                P Si
                                            H
                                                                                    D2O       DMSO
                                                          c H                  a               4.55
                            h                   HO        H                    b    4.07       3.72                         Natural
                                                                   OH
                        HO
                                                                               c    3.54       3.14                         Products
                          HO                                            Hb
                                    f                H                         d               4.51
                                                He
                                                              OH               e    3.64       3.37                         Solvents
                                                               d OH a
                                                                               f               4.46
                                                                               g    3.27       2.93
                                                                               h               4.31
              236                 5 1H NMR

                                                                                     D2O*       DMSO          D2O        DMSO
                              g
                                      OH l                                       a              6.58    3J
                                                                                                           bc 7.8
                                                                                                                      3J
                                                                                                                         ab    6.5
                          H
                                                    c
                                                                                 b   4.51       4.27    3J
                                                                                                           ce 9.5
                                                                                                                      3J
                                                                                                                         cd 4.5–6
      C                                j,k                                       c   3.13       2.89    3J            3J
              h                                     H O                                                    eg 9.5        ef 4.5–6
              HO                                                                 d              4.84    3J      9.5 3Jgh 4.5–6
                                                                                                           gi
                HO                                                        OH a   e   3.37       3.10    3J      2.8 3Jjl       5.5
                                                                                                4.84       ij
  C       C           f                        Hi                                f                      3J      5.7 3Jkl       6.0
                                      He
                                                        OH                       g   3.30       3.10       ik
                                                                                                        2J -12.8
                                                            d Hb
                                                                                 h              4.84       jk

  C       C                                                                      i   3.35       3.04
                      (in DMSO ca. 80%)                                          j   3.60       3.42
                                                                                 k   3.75       3.66 (* relative to internal
                                                                                 l              4.48 acetone at δ = 2.12)

                                                                                     D2O*       DMSO          D2O       DMSO
                              g
                                      OH l                                       a              6.20    3J
                                                                                                           bc   3.6 3Jab 4.5
                                                                                     5.09       4.91                  3
                                                                                                           ce 9.5 3Jcd 6.8
                          H                                                      b                      3J
                                       j,k          c
              h                                     H O                          c   3.41       3.10    3J
                                                                                                           eg 9.5 3Jef 4.8
              HO                                                                 d              4.84    3J
                                                                                                           gi   9.5 Jgh 5.5
                HO                                                        Hb     e   3.61       3.42    3J
                                                                                                           ij   2.8 3Jjl 5.7
      N               f                    Hi                                    f              4.64    3J
                                                                                                           ik   5.7 3Jkl 6.2
                                      He
                                                        OH                       g   3.29       3.04    2J -12.8
                                                                                                           jk
                                                            d OH a
  Hal                                                                            h
                                                                                 i   3.72
                                                                                                4.77
                                                                                                3.57
                      (in DMSO ca. 20%)
                                                                                 j   3.72       3.57
                                                                                     3.63       3.42 (* relative to internal
      O                                                                          k
                                                                                 l              4.37 acetone at δ = 2.12)

                                                                                     D2Oa       DMSOb           DMSO
      N                           k
                                  H                     OH
                                                            l
                                                                          a      a              4.48           3J
                                                                                                                  ab 7.4
                                                                                                                         c
                                       f                                         b   3.68       3.39           3J     5.4c
                      j                                              OH                                           ac
                                      H                                          c   3.53       3.25           2J -11.3d
              h H                              O                                                                  bc
      S       H                                             OH
                                                                    b,c          d   3.76       3.55           3J
                                                                                                               3J
                                                                                                                  de 6.8
                                                                                                                         c
                                                                                                                         d
                     HO                                         e                e              4.23              df 10.1
                                                                                     3.86       3.58           3J     5.8c
                  HO g                              H                            f                                fg
                                                        d                                                      3J        d
                                                                                                4.38              fh 4.0
                  i                                                              g
  C       X                                                                      h   3.96       3.62           3J     3.8c
                                                                                                                  hi
                                                                                 i              4.32           3J     1.9d c
                                                                                                                  hj             o
                                                                                 j   4.00       3.77           3J     1.6d at 25 C
  P Si                                                              a 25% β-D
                                                                                 k   3.68       3.41
                                                                                                                  hk
                                                                                                               2J -12.1d d at 70 oC
                                                                                                                  jk
                                                                    b 75% β-D
                                                                                 l              5.14
Natural           3.52, 3.40                                                              f,g   3.48, 3.37                  2J
                                                                                                                               ab   -11.0
Products      HO                           O                                         HO           O      OH
                                                                                                                            3J
                                                                                                                               cd     7.1
                                                            OH                                                              3J        5.9
                                                                                                           OH                  de
                          H                         OH                           3.53   eH                                  3J        2.3
Solvents      3.69                                                                                       a,b   3.40, 3.23   3J
                                                                                                                               ef
                              H                     OH                                       H OH H OH                         eg     3.6
                                      OH H                                                                                  2J      -11.3
                  3.72   3.77                                                         3.79 d    c 3.80                         fg
               (in DMSO, 20% α-D)                                                    (in DMSO, 55% β-D)
                                                                   5.13 Natural Products                             237

5.13.3 Nucleotides and Nucleosides

Chemical Shifts and Coupling Constants (δ in ppm, J in Hz)
                                                                                                                            C

         NH2                                                                   O
                                D2O DMSO
                                                                                                       3J      7.5         C       C
                              a 5.97 5.57                                                                 ab
 a            N                                                 5.47   a            NH 11.02           3J
                              b 7.50 7.31                                                                 bc   5.7
 b
                              Jab 7                             7.41   b
         N         O                                                           N        O                                  C       C
         H                                                                     Hc
                                                                             10.82
                                                                           (in DMSO)

                          O                                                         O
     1.75
                                  NH 11.0                                  N
                                                                                         N
                                                                8.98
          7.28
                          N            O                                   N        N          NH2
                          H                                                H
                      10.6                                                                                                     N
                                                                            (in TFA)
                 (in DMSO)
                                                                                                                            Hal
                      NH2 d                    D2O       DMSO CDCl3 TFA
                                           a   8.62      8.12  8.11 8.88                                                       O
          N
                              N            b                  12.8
     a
                                  c        c   8.57      8.10  8.14 9.31
          N
          Hb
                      N                    d                   7.09                                                            N

                                                                                                                               S
                          NH2 7.24                                                                     O
                                                                                        1.78
          5.75    a                N                                                                           NH 11.3     C       X
          7.87    b                                                                         7.71
                          N            O                                                               N          O
                  3.56                           2J                                             3.55
5.09 HO           3.66                           3J
                                                    ab    7.4
                                                          3.8
                                                                               5.04 HO          3.60                        P Si
                      O                             cd                                             O
         3.83                 c    5.79                                                 3.77               6.18
                                                                                                                           Natural
          3.95                d   3.95                                                   4.26           2.08               Products
                  OH OH                                                                        OH
             5.06* 5.36*                                                                        5.25
                                                                                                                           Solvents
            (in DMSO)                                                                        (in DMSO)
         * interchangeable
              238     5 1H NMR

                                             NH2 7.41                                   NH2 7.31
                                  N                                              N
                                                 N                                              N
      C                    8.17                                         8.13
                                  N                  8.38                        N                  8.34
                                             N                                          N
                      3.70                                                3.62
              5.48 HO 3.58                                    5.25 HO     3.53
  C       C
                              O                                            O
                    3.99              5.91                        3.88               6.34
  C       C         4.17              4.64                        4.41           2.73
                            OH OH                                         OH     2.26
                           5.24 5.51                                     5.31
                       (in DMSO)                                         (in DMSO)



                                             O                                              O

                                  N                                              N
      N                                          NH 10.75                                       NH 10.7
                       7.97                                             7.95
                                  N                                              N
  Hal
                                             N        NH2                                   N        NH2
                      3.63
              5.10 HO 3.55                             6.52               3.55                         6.50
                                                              4.99 HO
                              O                                            O
      O             3.90              5.72                        3.83               6.14
                    4.11              4.43                        4.36           2.53
                                                                                 2.22
      N
                            OH OH                                         OH
                        5.20 5.45                                          5.31
                       (in DMSO)                                         (in DMSO)
      S

  C       X


  P Si

Natural
Products

Solvents
                        5.14 Spectra of Solvents and References   239

5.14 Spectra of Solvents and Reference Compounds

5.14.1   1H   NMR Spectra of Common Deuterated Solvents
                                                                         C
500 MHz; ≈1 000 data points per 1 ppm; δ in ppm relative to TMS
                                                                        C       C


                                                                        C       C




                                                                            N

                                                                         Hal

                                                                            O

                                                                            N

                                                                            S

                                                                        C       X


                                                                         P Si

                                                                        Natural
                                                                        Products

                                                                        Solvents
              240   5 1H NMR




      C


  C       C


  C       C




      N

  Hal

      O

      N

      S

  C       X


  P Si

Natural
Products

Solvents
                           5.14 Spectra of Solvents and References                241




                                                                                           C


                                                                                          C       C


5.14.2   1H   NMR Spectra of Secondary Reference Compounds                                C       C

Chemical shifts in 1H NMR spectra are usually reported relative to the peak posi-
tion of tetramethylsilane (TMS) added to the sample as an internal reference. If
TMS is not sufficiently soluble, a capillary with TMS may be used as external refer-
ence. In this case, owing to the different volume susceptibilities, the local magnetic
fields in the sample and reference differ, and the peak position of the reference
must be corrected. For a D2O solution in a cylindrical sample and neat TMS in a
capillary, the correction amounts to +0.68 and -0.34 ppm for superconducting and
electromagnets, respectively. These values must be subtracted from the chemical
                                                                                              N
shifts relative to the external TMS signal if its position is set to 0.00 ppm. Alterna-
tively, secondary references with (CH3)3SiCH2 groups may be used. The following
spectra of two such secondary reference compounds in D2O were measured at 500              Hal
MHz with TMS as external reference. Chemical shifts are reported in ppm relative
to TMS upon correction for the difference in the volume susceptibilities of D2O and
TMS. As a result, the peak for the external TMS appears at 0.68 ppm.                          O

                                                                                              N

                                                                                              S

                                                                                          C       X


                                                                                           P Si

                                                                                          Natural
                                                                                          Products

                                                                                          Solvents
              242     5 1H NMR

              5.14.3 1H NMR Spectrum of a Mixture of Common Nondeuterated
              Solvents

      C       The following 1H NMR spectrum (500 MHz, δ in ppm relative to TMS) of CDCl3
              containing 18 common solvents (0.05–0.4 vol%) is shown as a guide for the identi-
              fication of possible impurities. Where the signals of several solvents overlap, insets
  C       C   show signals for the individual compounds from separate spectra. Peaks in these
              insets are labeled with the corresponding chemical shifts from their main spectrum
              but their values may differ by up to 0.03 ppm. Signals that are particularly prone to
  C       C   vary in their position are marked with *. THF: tetrahydrofuran; EGDME: ethylene
              glycol dimethyl ether.




      N

  Hal

      O

      N

      S

  C       X


  P Si

Natural
Products

Solvents
6 Heteronuclear NMR Spectroscopy




6.1     19F   NMR Spectroscopy

6.1.1 19F Chemical Shifts of Perfluoroalkanes (δ in ppm relative to
CFCl3)

 -63           -89                -83                  -83                          -82
  CF4          F3 C               F3 C                  F 3C                        F3 C
                      CF3                CF2 -131              CF 2   -130                 CF2 -127
                                  F3 C                  F 2C                        F2 C -123
                                                               CF 3                      CF2
                                                                                    F3 C
                            -81                       -85
                            F3 C                       F3 C
                                 CF2 -126                   CF2 -129
                            F2 C -122                  F2 C -125
                                 CF2                        CF2 -124
                            F2 C                       F2 C
                                 CF3                        CF2
                                                       F3 C

  -75                   -73                            -70                           -80
  F3 C -189                F3 C -187                    F3 C -179                    F3 C
       CF CF3                  CF CF3                       CF CF3            -71       CF2 -117
  F3 C                     F2 C -116                F3 C CF                    F3 C CF -184
                               CF3 -83                      CF3                         CF2
                                                                                   F3 C



         -65                             -55                                  -60
          F3 C                        F3 C          CF3                      CF3    CF3
                     CF3                                              F3 C            CF3
                                    F3 C             CF3
                     CF3                                              F3 C    CF2         CF3
          F3 C                        F3 C          CF3
                                                                              -97
244     6 Heteronuclear NMR

19F Chemical   Shifts of CF3 Groups (δ in ppm)


      Substituent              δ             Substituent        δ
      –H                      -78            –F                -63
                                        X
 C    –CH3                    -62            –Cl               -29
      –CH2CH3                 -70            –Br               -18
      –n-C7H15                -67            –I                 -5
      –CH2OH                  -78       O    –OH               -55
      –CH2NH2                 -72            –O–cyclohexyl     -58
                              -64            –O–CF3            -58
      –CH2COOH
                                             –O–phenyl         -58
      –CH2CH2–1-pyridinium    -75
                                             –O–CO–CO–O–CF3    -31
      –C(CF3)3                -65
                                        N    –NH2              -49
      –CF3                    -89
                                             –C– N
                                                –
                                                –              -53
      –CF2CF3                 -83
                                             –NC               -51
      –perfluorocyclohexyl    -70
                              -82
                                        S    –SH               -32
      –CCl3                                  –S–CF3            -39
      –CH=CH2                 -67            –SS–CF3           -47
      –C – CH
         –
         –                    -56            –SO3H             -79
      –phenyl                 -64            –S(O)2–phenyl     -79
      –C6F5                   -55            –COCF3            -85
                                        O
      –4-nitrophenyl          -64            –CO–phenyl        -58
                                        ||   –COOH             -77
      –4-aminophenyl          -62
      –C6(CF3)5               -53       C    –COO–             -74
                              -75            –COOCH2CH3        -74
      –1-naphthyl
                                             –COF              -76
      –2-naphthyl             -73
      –2-pyridyl              -68       P    –P(O)(OCH2CH3)2   -73
                                             –P(CF3)2          -51
      –3-pyridyl              -62
                                             –P+(phenyl)3      -58
      –4-pyridyl              -65
                                                     6.1 19F NMR          245

19F Chemical   Shifts of CHF2 Groups (δ in ppm)

    Substituent                 δ           Substituent               δ
    –H                        -144          –CCl3                   -122
    –CH3                      -110          –phenyl                 -111
    –CH2CH3                   -120          –O–CH3                   -88
    –CH2CH2CH3                -117          –O–CF3                   -86
    –CH2–phenyl               -115            –
                                            –C– N
                                              –                     -120
    –CF3                      -141          –S–phenyl               -121
    –CF2CF3                   -138          –COOH                   -127
    –cyclohexyl               -126          –P(CF3)2                -126


19F Chemical   Shifts of CH2F Groups (δ in ppm)

    Substituent                 δ           Substituent               δ
    –H                        -268          –CCl3                   -198
    –CH3                      -212          –CH=CH2                 -216
    –CH2CH3                   -212          –C – CH
                                               –
                                               –                    -218
    –CH2CH2CH3                -219          –phenyl                 -206
    –CH2CH2CH2CH3             -219            –
                                            –C– N
                                              –                     -251
    –CH2OH                    -226          –CO–phenyl              -226
    –CH2–phenyl               -216          –COOH                   -229
    –CF3                      -241          –COO–                   -218
    –CF2CF3                   -243

19F Chemical   Shifts of CF2R2, CHFR2, and CFR3 Groups (δ in ppm)

    Substituent                 CF2R2       CHFR2         CFR3
    –CH3                          -85         -165        -131
    –CH2CH3                       -92         -183        -156
    –CF3                         -132          -77        -189
    –phenyl                       -89         -167        -127
    –Cl                            -7          -81          0
246       6 Heteronuclear NMR

19F Chemical    Shifts of Monosubstituted Perfluoroalkanes (δ in ppm) [1]

    CF3 -81.7              CF3 -81.8              CF3 -81.8                  CF3 -81.8
F2 C -125.9           F2 C -127.0            F2 C -126.9                F2 C -126.8
    CF2 -123.0             CF2                    CF2                        CF2
F2 C -121.7           F2 C                   F2 C                       F2 C
    CF2 -121.7             CF2                    CF2                        CF2
F2 C -121.7           F2 C                   F2 C                       F2 C
    CF2 -122.6             CF2 -120.9             CF2 -118.0                 CF2 -113.7
F2 C -116.8           F2 C -68.7             F2 C -64.0                 F2 C -59.0
    COOH                   Cl                     Br                         I


    CF3 -80.5           CF3 -86.0       F3 C -85.2        F3 C -85.2
F2 C -126.3         F2 C -131.0     -75.6   CF2 -121.1 -190.7 CF CF3 -76.9
    CF2 -122.8          CF2 -127.4 F3 C CF -189.8         F2 C -119.5
F2 C -121.8         F2 C -126.6             CF2   -117.3      CF2 -125.3
    CF2 -121.6          CF2 -126.4      F2 C -124.2       F2 C -125.9
F2 C -121.6         F2 C -126.3             CF2 -124.8        CF2 -125.0
    CF2 -121.7          CF2  -125.1     F2 C -117.8       F2 C -117.9
F2 C -121.6         F2 C -117.8             SO2 R             SO2 R
    CF2 -123.6          SO2 R
F2 C -115.2
                               -110.3 CF3 -83.0                    -74.1    CF3 -74.1
              F3 C CF3 -66.5       F2 C CF3 -64.1                   F3 C CF -184.9
            F3 C C             -105.5 C                            -179.8 CF CF3 -75.0
      I
                    CF2 -108.6     F2 C CF3 -64.1                       F2 C -113.3
                F2 C -121.5            CF2 -120.0                           CF2 -122.7
                    CF2 -124.2     F2 C -117.1                          F2 C -116.2
                F2 C -117.6            SO2 R                                SO2 R
                    SO2 R                                                    R: NHCH2 C6 H5
Halogen Bonding (δ in ppm) [2]
                                               b F     dF          F2        F2
                                                   2      2
                                        X        C      C          C         C
                                              C      C        C         C         X
                                            a F2   c F2       F2        F2

X                  in cyclohexane                                  in pyridine
            a        b        c         d              a           b              c     d
–F        -81.1    -121.7   -122.5   -126.1        -80.9      -122.1         -122.8   -126.2
–Br       -65.1    -118.1   -122.6   -123.2        -67.7      -117.9         -122.2   -122.8
–I        -60.0    -114.6   -122.5   -123.3        -71.6      -115.2         -122.0   -122.8
                                                           6.1 19F NMR             247

6.1.2 Estimation of 19F Chemical Shifts of Substituted Fluoroethylenes
(δ in ppm relative to CFCl3) [3]
                                  Rcis      F

                                Rtrans      Rgem
     δC=CF = -133.9 + Zcis + Ztrans + Zgem + Scis/trans + Scis/gem + Strans/gem


    Substituent R                            Zcis         Ztrans        Zgem
    –H                                      -7.4         -31.3         49.9
    –CH3                                    -6.0         -43.0          9.5
    –CF3                                   -25.3         -40.7         54.3
    –CH=CH2                                   –            –           47.7
    –CF=CF2                                -23.8         -38.9         44.7
    –phenyl                                -15.7         -35.1         38.7
    –F                                       0.0           0.0          0.0
    –Cl                                    -16.5         -29.4           –
    –Br                                    -17.7         -40.0           –
    –I                                     -21.3         -46.3         17.4
    –OC2H5                                 -77.5           –           84.2
    –COF                                   -46.5         -56.8         54.1
    –SCH3                                  -25.1         -43.7         16.6

    Substituent        Substituent          Scis/trans   Scis/gem     Strans/gem
    –H                 –H                  -26.6            –           2.8
    –H                 –CF3                -21.3            –            –
    –H                 –CH3                   –           11.4           –
    –H                 –OCH2CH3            -47.0            –            –
    –H                 –phenyl              -4.8            –           5.2
    –CF3               –H                   -7.5         -10.6         12.5
    –CF3               –CF3                 -5.9          -5.3         -4.7
    –CF3               –CH3                 17.0            –            –
    –CF3               –phenyl             -15.6            –         -23.4
    –CH3               –H                     –          -12.2           –
    –CH3               –CF3                   –          -13.8         -8.9
    –CH3               –phenyl                –          -19.5        -19.5
    –OCH2CH3           –H                   -5.1            –            –
    –phenyl            –H                     –             –          20.1
    –phenyl            –CF3                -23.2            –            –
248               6 Heteronuclear NMR

6.1.3 Coupling Constants in Fluorinated Alkanes and Alkenes (JFF in
Hz)
                        F3 C         |3JFF| <1                                           F3 C          |3JFF| 1.1
|4J   FF|   8.9                CF2                                  |4J   FF|   8.5              CF2
                        F2 C         |3J   FF| 1.8                                       F2 C          |3JFF| 2.2, 1.1
                               Cl                                                                COOH

                                                               |5JFF| 6.8                 F3 C
                                                                                                          |4JFF| 13.6
                          F3 C CF3                                                         CF2
                        F3 C C
                                                 |4JFF| 13
                                                                                  F3 C CF                       |5JFF| 6.8
                                 CF2                                                       CF2
|5JFF| 13                   F2 C                                                      F2 C
                                 CF2                 R: NHCH2 C6 H5                        CF2
                            F2 C                                                      F2 C
                                 SO2 R                                                     SO2 R


                                                           F3 C          |3JFF| 0.3
                                                                  CF2
                                                           F2 C          |3JFF| 6.0
                                            |3JFF| 10.3           CF2
                                                            FC           |3JFF| 140
                                             |3JFF| 8.7           CF
                                                           F3 C
                          F3 C                                                               F3 C
      |4JFF| 9.8                 CF2                                                                 CF2
                                                                           |5JFF| 2.4
                          F2 C               |4JFF| 12.2                                     F2 C             |5JFF| 3.0
      |4J   FF|   5.8            CF2                                                                 CF2
                           FC                |4JFF| 26.1                   |5JFF| 7.2           FC
 |4JFF| 21.0                     CF                                                                  CF       |5JFF| 1.5
                          F3 C                                                               F3 C


                                                                                                   |5JFF| 2.5
 |3JFF| 0.8
                          CF3                                            CF3                                  CF3
                                                                                      |4JFF| 9.5
                   F2 C         |3JFF| 1.6                        F2 C                                 F2 C
|3JFF| 13.3               CF2                   |4JFF| 8.2               CF2
                                                                                                                   6
                                                                                                              CF2 | JFF| 4.6
          FC    |3JFF| 2.3            FC      FF| 3.4                             |4J                   FC
|3JFF| 7.6 FC CF2                      FC CF2                                                            FC CF2
                           |4JFF| 8.2
               CF3                         CF3                                                               CF3
                  |3JFF| 12.5                              |4JFF| 7.6
                                                                                            6.1 19F NMR                        249

                                                 3J        +19.1
                                                      FF
                      3J        -132
           F               FF                    F             F                                          F
                                                                                 2J        +36.4
                                                                                      FF
                  F                                                                                       F


                                                                       3J        -119
                                                      F                     FF
                                2J        +87
                                     FF
                                                      F            F
                                                     3J        +33
                                                          FF
                |3JFF| 21                                                                  3J        +73.3
                                                                                                FF

               F3 C             F                                                          F            F
                                                                2J
                                                                     FF +124
   |2JFF| 12     F              N3                                                         F            F     3J        -114
                                          |3JFF| 127                                                               FF



                                                                            |5JFF| 11.3
                                                |5JFF| 1.3
                       F3 C                 F                          F3 C                CF3

                           Cl               CF3                          Cl                 F



6.1.4 19F Chemical Shifts of Allenes and Alkynes (δ in ppm relative to
CFCl3, |JFF| in Hz)


               -176 F                           H              -107 F                            H
                               C C C                                            C C C
                           H                    H                           F                    H


  -273 F                   H          -261 F                         F            -203 F                          CF3
                                                     |3J   FF| 2.1                                   |4JFF| 4.3
250           6 Heteronuclear NMR

6.1.5 19F Chemical Shifts and Coupling Constants of Fluorinated
Alicyclics (δ in ppm relative to CFCl3, |JFF| in Hz)

 -218                    -160                           -171                    -174                            -165                        -160
   F                          F                             F                       F                               F                           F




   -151                           -135                          -133                                -133                                  -120
       CF2                    CF2                                   CF2                              CF2                                  CF2
                                                            F2 C            CF2             F2 C             CF2                  F2 C           CF2
F2 C         CF2         F2 C   CF2
                              CF2                                                                                             F2 C                  CF2
|2JFF| 160                                                   F2 C       CF2                 F2 C             CF2
                          |2J     FF|   220                                                          CF2                          F2 C           CF2
                                                                                                |2JFF| 284                                CF2


                      F -186

                                                                        F -166                                                  F -130


                          -122              -189                                                                F
                                                                                                            F               F -121
                              F                 F                                               F                             F
              -140                 F        F                -70                                    F               F
                     F                                  CF3                                                         F
        -142 F                                      F                                           F                               F -224
                              F         F           -132                                    F                               F
                          F                 F                                                           F       F
                   -124                    -120                                                     F               F


                                                |2JFF| 286                  F               F
                                                                                F       F
                                                                    F                               CF3
                                                                F                               F
                                                                                    F
                                            |2JFF| 284                  F
                                                                            F
                                                                                        F           |2JFF| 291
                                                                            |3JFF| 13
                                  |4JFF| 25
  |3J   FF|   13.5                F                 F                                           |4JFF| 2 F                        F
                                       F        F                                                                     F       F
                         F                                  CF3                                          F                                CF3
                     F                                  F                                            F                                F
                                            F                                               |4JFF| 6             F        F
 |3J
                                  F                     |4JFF| 3
       FF|   13.5             F                 F                                                            F                F
                                                                                                                |3J   FF|   0
                              |4JFF| 20
                                                     6.1 19F NMR       251

6.1.6 19F Chemical Shifts and Coupling Constants of Aromatics and
Heteroaromatics (δ in ppm relative to CFCl3)


Estimation of 19F Chemical Shifts of Substituted Fluorobenzenes [4]
                        3   2

                    4           F    δF = -113.9 + ∑ Zi
                        5   6

      Substituent                         Z2,6       Z3,5         Z4
       C    –CH3                         -3.9        -0.4       -3.6
            –CF3                          0.4         3.1        5.8
            –CH=CH2                      -4.4         0.7       -0.6
               –
            –C – CH
               –                           –           –         3.3
       X    –F                          -23.2         2.0       -6.6
            –Cl                          -0.3         3.5       -0.7
            –Br                           7.6         3.5        0.1
            –I                           19.9         3.6        1.4
       O    –OH                         -23.5         0.0      -13.3
            –OCH3                       -18.9        -0.8       -9.0
            –OCOCH3                        –           –        -3.7
       N    –NH2                        -22.9        -1.3      -17.4
            –NHCOOCH3                      –          0.1       -7.1
            –NHCONH2                       –          0.9       -8.1
            –N3                         -11.4         2.8       -0.3
            –NO2                         -5.6         3.8        9.6
            – C–N
                –
                –                         6.9         4.1       10.1
            –NCO                         -9.2         2.3       -2.2
       S    –SH                          10.0         0.9       -3.5
            –SCH3                         6.5         1.2       -4.5
            –S(O)2F                       7.5         5.8       13.8
            –S(O)2–CF3                    9.5         5.5      -14.3
            –S(O)2OCH2CH3                  –          3.7        9.1
       O    –CHO                         -7.4         2.1       10.3
            –COCH3                        2.5         1.8        7.6
       ||   –COOH                         2.3         1.1        6.5
       C    -COOCH3                       3.3         3.8        7.1
            –CONH2                        0.5        -0.8        3.4
            –COF                        -14.8         3.0        6.2
            –COCl                         3.4         3.5       12.9
            –B(OH)2                       6.8         0.8        2.1
            –Si(CH3)3                    13.8         0.3        1.6
252       6 Heteronuclear NMR

              F       F                                                   F       F
  -163                                       -64           -147                        -55
      F                   F                  CF3                  F                    CF3


              F       F                                    -160           F       F -141




Estimation of 19F Chemical Shifts of Substituted Pyridines, Pyrimidines, Pyra-
zines, and Triazines (δ in ppm) [5]
                                      δF = Y + ∑ Zi

To estimate the 19F chemical shifts of substituted 6-ring heteroaromatics, the same
increments, Zi, can be used as for substituted fluorobenzenes (see preceding page).
However, different base values, Y (as given below), apply depending on the number
and position of nitrogens and the position of the fluorine substituent in question:
                                                 F
                          F                                                        F

                                                                          N                      N
      F           N               N              N         F          N                      N
Y:        -47.8               -3.0           -18.3             -45.7                    -3.5

                                                                                             F
                                                       F                      N
          N               N                  N                                         N         N

      F           N           N        F           N           F              N              N
Y:        -67.7           -52.1              -18.7                    -41.8             -74.6
                                                                                                              6.1 19F NMR                            253

Coupling Constants in Aromatics and Heteroaromatics (JFF in Hz)



 3J           -20.8             4J        +6.5                    5J        +17.6
      FF                             FF                                FF
          F                          F                                      F                                     F                 3J        -20.3
                                                                                                                                         FF
                     F                                                                              F                         F 4JFF -3.0
                                                                                                                                    5J          +3.9
                                                                                                                                         FF

                                                   F                                                F                         F
                                                                            F                                     F

           4J        +8.6 CH3                                                          4J        +5.1
                FF                            5J                                            FF                 NH 2
                                                   FF +8.6
                                                                                                                               5J          +5.1
                                                                                                                                    FF
4J                   F                    F                                                      F                        F
     FF   -0.1                                     3J
                                                                            4J
                                                                                 FF   -7.3
                                                        FF    -20.9                                                                   3J
                                                                                                                                           FF   -20.5
                     F                    F                                                      F                        F
                                               3J
                                                    FF -19.4
                                                                                                                                   3J        -20.8
                              F                                                                                F                        FF

                                          4J           -2.3                                                                   4J        -2.4
                                               FF                                                                                  FF

                                                    4J           +6.7 NO2
                                                         FF                               5J
                                                                                               FF   +6.7
                                                              F                       F
                                  4J                                                           3J           -21.2
                                       FF     +5.4                                                  FF
                                                              F                       F
                                                                                            3J          -19.9
                                                                            F                    FF

                                                                                       4J        -0.4
                                                                                            FF



                                                                                                         5J        +26.0
                                                                                                              FF
                         4J
                              FF -15.0                 5J                                                             F
                                                            FF   +26.3
 4J                      F           N             F
      FF      +13.7                                         3J                                                N           N
                                                                 FF   -20.3
                         F                         F                                                    F                         F
                                                        3J
                                     F                       FF -18.1                                                 F
                                                                                                                               3J            +17.9
                                                                                                                                      FF
                                                   4J
                                                        FF 0.0
254        6 Heteronuclear NMR

6.1.7 19F Chemical Shifts of Alcohols and Ethers (δ in ppm relative to
CFCl3)
                                   OH                 OH                  HO       OH
            OH
            CF3           F3 C                 F3 C     CF3              F3 C      CF3
            -55          -78                   -88                       -93


F3 C -85                F3 C -84                      F3 C         -57           F3 C -85
    CF2 -133                 CF2 -129          -83        O                           CF2 -133
F2 C -88                F2 C -129                F3 C CF -149                    F2 C -86
    O                        CF2 -87                      CF2 -86          -83        O
F2 C -92                  O                             O                    F3 C CF -148
    CF3 -91                  CF2 -56                      CF2 -92                     CF2 -84
                          O                          F3 C -91                       O
                             CF2 -57                                                  CF2 -92
F3 C -84                  O                                                      F3 C -91
     CF2 -129                CF2                 F3 C -82
F2 C -129                 O                          CF2 -130                    F3 C -84
     CF2 -87                 CF2                 F2 C -84                             CF2 -131
   O                    F2 C                         O                           F2 C -84
     CF2 -54                 CF2                 F2 C -83                  -80        O
   O                    F3 C                         CF2 -129                F3 C CF -144
     CF2                                         F2 C -83                             CF2 -82
                                                 n
F2 C                                                 O                              O
                               O                                                 n
     CF2                F2 C         CF2         F2 C -88                             CF2 -91
                               -91
F3 C                    F2 C         CF2             CF3 -87                     F3 C -89
                               O



             F2 C CF2                                 F3 C                         F3 C
        F2 C          CF2
             O     O     CF2                                 CF2                          CF2
    F2 C
                        O CF                          F2 C                         F2 C
 F2 C O                      2
                                                         O                              O
F2 C                                     CF2
                                                 F3 C CF                        F3 C CF
       O          -89                O
                                                         CF2                            CF2
F2 C                                     CF2
                                                       O                              O
 F2 C O                          O CF2               n
                                                         CF CF3
                                                                                    n
                                                                                        CF CF3
       F2 C     O     O    CF2                      O                              O
           F2 C          CF2
                F2 C CF2                                 F -130                         OH -132
                                                       +26
                                                                                   6.1 19F NMR                  255

6.1.8 19F Chemical Shifts of Fluorinated Amine, Imine, and Hydroxyl-
amine Derivatives (δ in ppm relative to CFCl3)

      F +147                            F +19                              CF3 -57                     CF3 -58
      N                      -84        N                                  N                           N H
F          F                   F3 C          F                    F3 C         H               F3 C
                                                                                                        H

    -92                      F3 C -82                    F3 C -82                                 F3 C -82
      F        H                CF2 -128                      CF2 -121                                CF2 -121
          N
F3 C           H         F2 C -117                  F2 C -106                         -84 F2 C
-75                          N F                        N F                                   N CF
                          F +17                 F2 C CF -91                            F2 C CF
                                                                                                     2
                                                        2                                      2
                                                                                                 F2 C CF
                                            F3 C                                   F3 C                  3


           CF3 -56                           CHF2 -96
                                                                                                      CF3 -84
           N
                                   F2 HC
                                             N
                                                 CHF2
                                                                                     -129 F2 C
 F3 C          CF3
                                                                                             CF2 -120
                                                   -63                           -86   F2 C
    -53 CF3 -93
                    F2                               F2        -57                         N CF2
          N         C        CF3                     C    CF3                     F2 C CF
F3 C           C         N                  F3 C N     N
                                                                                            2
                                                                                              F2 C CF
               F2                                                           F3 C CF                   2
                                                                                     2
                         CF3                     F2 C CF2 -93                                        CF3

                                                                                                   CF3 -84
          CF3 -53                       CF3 -55                       CF3 -54                 F2 C -90
          N                             N                             N                          N
F2 C           CF2 -95          F2 C         CF2 -95          F2 C         CF2            F2 C     CF2 -86
                                                                     -94
F2 C         CF2 -134           F2 C         CF2 -88          F2 C         CF2        F2 C      CF2 -123
          C                             O                             N                  F2 C CF2 -129
          F2 -136
                                                                      CF3
                                                                                          H             -71 CF3
    F3 C            F -16               F3 C         H
-59                                    -62 N                                   -98        N           -99      N
           N
                                                                                   F2 C       O         F2 C         O
                    H                                F -46                             C                    C
                                                                                   -81 F2               -83 F2

          F2 -104
          OH                                             O–                                    F3 C -82
     N    C      CF3                                     N                                         CF2 -125
F3 C   C      N
                 -66                             F3 C         CF3 -68
       F2                                                                                     F2 C -96
              OH
                                                 Ph3 P        PPh3                         N O
          F2 -105                                                                                   -129
          O                                              Pt                         F2 C CF
                                                                                            2
                                                   O          O                                F2 C CF
     N    C      CF3                                                 -62        F3 C
                                                                                              -89
                                                                                                       2

                                            F3 C N -109 N CF3
F3 C   C      N -69                                                                                  CF3
       F2
              O                                  F2 C CF2                                                      -82
256         6 Heteronuclear NMR

6.1.9 19F Chemical Shifts of Sulfur Compounds (δ in ppm relative to
CFCl3)
       H                   F -352              CF 3    -39                      S                             S
                                                                         F2 C         CF2 -133        F2 C          CF2
   S                   S                   S                                                                  -92
       CF3                                     CF 3                       F2 C CF2 -87                F2 C          CF2
                           CF3                                                                                S
      -32              -57

           -167                  +93                           +57
                F                      F                             F                               SF3 +7
                                  F                          F            F
            S                          S                             S                -88 F2 C
                           +34 F                             F            F                          SF3
                F                      F                             F


                                                                                                     +72
                                                  -48                +52
                    F       F -14                                F                        -26         F
                                                        F                                        F
                        S                                        S                                    S
                F3 C         CF3                      F3 C
                                 -58             -70             F                                    F


                                       -65                               +12
                                    CF3                                   F
                                  F   F                              F          CF3
                              +19   S                   +50               S         -64
                                  F   F                              F          CF3
                                    CF3                                   F


                                                                                                 O
                       O                                                                                   F +65
                                                       O                                              S
                                                                 OH
                       S                   -78             S                                              O
            F3 C            CF3                  F3 C
                                                               O
                    -70

                                                            -71
                                                             CF3
                                               -65                   O–
                                                 F3 C        S
                                                                     O–
                                                             CF3
                                                                6.1 19F NMR         257

6.1.10 19F Chemical Shifts of Carbonyl and Thiocarbonyl Compounds
(δ in ppm relative to CFCl3)
                                            O

                                        R        F


    Substituent R                  δ                 Substituent R             δ
    –H                            +41                –phenyl                  +17
    –CH3                          +49                –F                       -23
    –C(CH3)3                      +22                –NH–CH2CH2CH3            -16
    –CH2F                         +26                –O–cyclohexyl             -8
    –CF3                          +15                –O–phenyl                -17
    –CF(CF3)3                     +31                –S–phenyl                +47
    –CH=CH2                       +24



                                                                H
                 O        O                                 O       O

          F3 C                                       F3 C
         -81                  N                      -77                N



                                                                H
                     O        O                             O       O

                                                     F3 C               CF3
                         F -187                      -77



                     S                                      S

                 F       F +41                  -75 F3 C        F +53
258      6 Heteronuclear NMR

6.1.11 19F Chemical Shifts of Fluorinated Boron, Phosphorus, and
Silicon Compounds (δ in ppm relative to CFCl3, JFP in Hz)
                                                      –                                  –
                               -151 F             F          -120 F              F
                                             B                               B
                                         F        F                     F        OH



             F                F                  –                               CF3         F3 C              –
     F                                   F
                 FF
 F                                           F               F3 C                                        CF3
                                   F -132                                                                -63
         F           B                                                                   B
         F                         F
 F                                           F -168          F3 C                                        CF3
                 FF
     F                                   F -164
             F                F                                                  CF3         F3 C



                                                                                               –
             F           F -34                H3 C        F -219                     F
                 P                                    P                          F           F -71
                         1J
                              FP -1441                      1J                       P
                 F                                    CH3        FP -830         F           F 1J -706
                                                                                     F           FP

                                         O                                   O
                                         P                  H3 C             P
                                  H3 C     F -65                        O        F -87
                                         CH3                                 O
                                                                   H3 C




                                     F           F               H3 C        CH3
                                         Si                             Si
                                     F           F -164          H3 C        F -160
                                                                      6.1 19F NMR                   259

6.1.12 19F Chemical Shifts of Natural Product Analogues (δ in ppm
relative to CFCl3, JFF in Hz)
   H3 N+     COO–                      H3 N+      COO–            H3 N+        COO–




                         F                                                                     OH
                       -116                            F -113                        F -137

                                          F -125         H3 N+    COO–
               H3 N+         COO–
                                                                                         F -122


                                                                          N
                                   N
                                                                          H
                                     H


      OH                                 OH                                   OH

               O                                   O                                      O
HO                            HO                                  HO
 HO                            HO                          F       HO
               OH                                  OH -139                         -205    F       -151
                 F -146                                                                        F
                                                                               3J        ≈ 19.5
                                                                                    FF


                    OH                                                F -235
                           -222
                             F O         -150                                   O
            HO                                                AcO
             HO                           F                     AcO
                             3J                                               AcO
                                  FF ≈ 12.4                                          F     -150

                       H                                                  H
                                         F -119
           AcO             O                               AcO              O
              AcO        OAc                                  AcO         OAc
                                                                                         F -138
                             AcO                                              AcO


                                   O                             NH2
               -171 F                             -171    F
                                         NH                           N

                                   N          O                  N        O
                                   H                             H
260     6 Heteronuclear NMR

6.1.13 References

[1] G. Arsenault, B. Chittim, J. Gu, A. McAlees, R. McCrindle, V. Robertson,
    Separation and fluorine nuclear magnetic resonance spectroscopic (19F NMR)
    analysis of individual branched isomers present in technical perfluorooctane-
    sulfonic acid (PFOS), Chemosphere 2008, 73, S53.
[2] P. Metrangolo, W. Panzeri, F. Recupero, G. Resnati, Perfluorocarbon–hydro-
    carbon self-assembly, Part 16. 19F NMR study of the halogen bonding between
    halo-perfluorocarbons and heteroatom containing hydrocarbons, J. Fluorine
    Chem. 2002, 114, 27.
[3] R.E. Jetton, J.R. Nanney, C.A.L. Mahaffy, The prediction of the 19F NMR
    signal positions of fluoroalkenes using statistical methods, J. Fluorine Chem.
    1995, 72, 121.
[4] C.A.L. Mahaffy, J.R. Nanney, The prediction of the 19F NMR spectra of fluoro-
    arenes using statistical substituent chemical shift values, J. Fluorine Chem.
    1994, 67, 67.
[5] J.R. Nanney, C.A.L. Mahaffy, The use of the 19F NMR spectra of fluoropyri-
    dines and related compounds to verify the 'statistical' substituent chemical shift
    values of fluoroarenes, J. Fluorine Chem. 1994, 68, 181.
                                              6.2 31P NMR      261

6.2   31P   NMR Spectroscopy

6.2.1 31P Chemical Shifts of Tricoordinated Phosphorus, PR1R2R3 (δ
in ppm relative to H3PO4)

      Substituent R1      R2             R3               δ
             –H           –H             –H             -235
      H2     –CH3         –H             –H             -164
             –CH2CH3      –H             –H             -127
             –phenyl      –H             –H             -124
      H      –CH3         –CH3           –H              -99
             –CH2CH3      –CH2CH3        –H              -55
             –phenyl      –phenyl        –H              -41
             –OCH3        –OCH3          –H              171
      C      –CH3         –CH3           –CH3            -63
             –CH2CH3      –CH2CH3        –CH2CH3         -20
             –CH2CH2CH3   –CH2CH2CH3     –CH2CH2CH3      -33
             –CH(CH3)2    –CH(CH3)2      –CH(CH3)2        20
             –C(CH3)3     –C(CH3)3       –C(CH3)3         62
             –phenyl      –CH3           –CH3            -48
             –phenyl      –phenyl        –CH3            -28
             –phenyl      –phenyl        –phenyl          -6
      X      –CH3         –CH3           –F              185
             –CH3         –CH3           –Cl              92
             –CH3         –CH3           –Br              88
             –CH3         –F             –F              244
             –CH3         –Cl            –Cl             192
             –CH3         –Br            –Br             184
             –CH3         –I             –I              131
             –F           –F             –F               97
             –Cl          –Cl            –Cl             220
             –Br          –Br            –Br             227
             –I           –I             –I              178
      O      –OCH3        –CH3           –CH3             91
             –OCH3        –OCH3          –CH3            183
             –OCH3        –OCH3          –OCH3           140
             –OCH2CH3     –OCH2CH3       –OCH2CH3        138
      N      –N(CH3)2     –CH3           –CH3             39
             –N(CH3)2     –phenyl        –phenyl          65
             –N(CH3)2     –N(CH3)2       –CH3             86
             –N(CH3)2     –N(CH3)2       –N(CH3)2        123
      S      –SCH3        –SCH3          –SCH3           125
262    6 Heteronuclear NMR

6.2.2 31P Chemical Shifts of Tetracoordinated Phosphonium Com-
pounds (δ in ppm relative to H3PO4)


31P Chemical   Shifts of Symmetrically Substituted Phosphonium Compounds,
PR+4
  Substituent R             δ            Substituent R          δ
  –CH3                      25           –n-butyl               34
  –CH2CH3                   41           –phenyl                23
  –n-propyl                 31           –OCH3                   5



31P Chemical   Shifts of Triphenylphosphonium Compounds, P(phenyl)3R+
  Substituent R             δ            Substituent R          δ
  –CH3                      23           –CH=CH2                19
  –CH2CH3                   26           –CH=C=CH2              19
  –CH2Cl                    24           –C – C–phenyl
                                            –
                                            –                    5
  –CH2OH                    18           –NH2                   36
  –CH2COCH3                 26           –N(CH3)2               48
  –CH2COOCH2CH3             21           –OCH2CH3               62




                                             27
                  N
                P 68                         P
                  N



                                     H
                                     N


                                     P 21


                                     N
                                     H
                                                                       6.2 31P NMR                  263

6.2.3 31P Chemical Shifts of Compounds with a P=C or P=N Bond (δ
in ppm relative to H3PO4)

           290
           P

                                   -2                     20                              15
                               P                      P                               P




389   Si              92       N
 P                    P
      Si                       N                  7                                        15
                                              P                                       P

                                                                                                O

                 18
                 P
                               O
                      O                                                      -20
                                                                           P
                                                                   P
                                                                   25


                           3
                           P   N
                                                                                 32
                                                               P       N P
                                                      n-C12H27             n-C12H27




                           7                                               3
                           P   N                               P       N     P




                                        NO2
264    6 Heteronuclear NMR

6.2.4 31P Chemical Shifts of Tetracoordinated P(=O) and P(=S) Com-
pounds (δ in ppm relative to H3PO4)


31P Chemical   Shifts of Tetracoordinated P(=O) Compounds
                                                                 O
                                                                 P
                                                            R1        R3
                                                                 R2

      Substituent R1          R2              R3                       δ

      C        –CH3           –CH3            –H                       63
               –CH3           –CH3            –CH3                     41
               –CH2CH3        –CH2CH3         –CH2CH3                  48
               –phenyl        –phenyl         –phenyl                  27
               –CH3           –CH3            –F                       66
      X        –CH3           –CH3            –Cl                      65
               –CH3           –CH3            –Br                      51
               –CH2CH3        –CH2CH3         –Cl                      77
               –phenyl        –phenyl         –Cl                      43
               –CH3           –F              –F                       27
               –CH3           –Cl             –Cl                      44
               –CH3           –Br             –Br                       9
               –CH2CH3        –Cl             –Cl                      55
               –F             –F              –F                      -36
               –Cl            –Cl             –Cl                       2
               –Br            –Br             –Br                    -103
      N        –N(CH3)2       –N(CH3)2        –N(CH3)2                 24
               –H             –H              –OCH3                    19
      O        –CH3           –H              –OH                      35
               –CH3           –CH3            –OH                      31
               –CH3           –CH3            –OCH3                    52
               –phenyl        –phenyl         –OH                      29
               –phenyl        –phenyl         –OCH3                    32
               –CH3           –Cl             –OCH2CH3                 40
               –Cl            –Cl             –OCH3                     6
               –F             –F              –OCH2CH3                -21
      2O       –H             –OCH3           –OCH3                    11
               –CH3           –OH             –OH                      31
               –CH3           –OCH3           –OCH3                    32
               –CCl3          –OCH2CH3        –OCH2CH3                  7
               –phenyl        –OH             –OH                      18
               –phenyl        –OCH3           –OCH3                    21
               –Cl            –OCH2CH3        –OCH2CH3                  3
                                                    6.2 31P NMR             265

      Substituent R1          R2              R3                       δ

      3O       –OH            –OH             –OH                       0
               –OCH3          –OCH3           –OCH3                     0
               –OCH2CH3       –OCH2CH3        –OCH2CH3                 -1
               –OCH(CH3)2     –OCH(CH3)2      –OCH(CH3)2              -13
               –O–phenyl      –OH             –OH                      -4
               –O–phenyl      –O–phenyl       –OH                     -11
               –O–phenyl      –O–phenyl       –O–phenyl               -18
      S        –S–n-butyl     –S–n-butyl      –OH                      37
               –S–n-butyl     –S–n-butyl      – S–n-butyl              62



31P Chemical   Shifts of Tetracoordinated P(=S) Compounds
                                                                 S
                                                                 P
                                                            R1        R3
                                                                 R2

      Substituent R1          R2              R3                       δ

      C        –CH3           –CH3            –CH3                     59
               –CH2CH3        –CH2CH3         –CH2CH3                  53
               –phenyl        –phenyl         –phenyl                  43
               –CH3           –CH3            –Cl                      87
      X        –phenyl        –phenyl         –Cl                      80
               –CH3           –CH3            –Br                      63
               –CH2CH3        –F              –F                      111
               –CH3           –Cl             –Cl                      81
               –CH2CH3        –Cl             –Cl                      95
               –F             –F              –F                       32
               –Cl            –Cl             –Cl                      29
               –Br            –Br             –Br                    -112
               –Br            –I              –I                     -315
      N        –N(CH2CH3)2    –N(CH2CH3)2     –N(CH2CH3)2              78
      O        –CH3           –OCH3           –OCH3                   100
               –OCH2CH3       –OCH2CH3        –OCH2CH3                 68
               –CH3           –S–n-propyl     –S–n-propyl              78
      S        –S–n-butyl     –S–n-butyl      –OCH3                   111
               –S–n-propyl    –S–n-propyl     –S–n-propyl              93
266   6 Heteronuclear NMR

6.2.5 31P Chemical Shifts of Penta- and Hexacoordinated Phospho-
rus Compounds (δ in ppm relative to H3PO4)


                    F                        Cl                      Br
               F             F       Cl           Cl        Br            Br
                    P                      P -81                     P
                         -80                                              -74
                F        F               Cl Cl                  Br       Br



                    O                        O                            O
                                         O        O              O      O
                    P                        P                        P -71
                         -88                      -67
                                         O        O                  O O




                                                                 O
                                                            O             O
                        P -89                                    P
                                                                      -85
                                                            O        O




                    –                        Cl         –                      F             –
                                    Cl            Cl                  F              F
         P                                   P                                 P
                                    Cl            Cl                  F            F
             -145                            Cl -299                           F -144



                                     –


                                                                          N3
                                                                                         –
                                                                O               N3
                    P                                                     P
                                                                O            N3
                                                                          N3 -143
                             -152
                                                                                                      6.2 31P NMR                           267

6.2.6 31P Chemical Shifts of Natural Phosphorus Compounds (δ in
ppm relative to H3PO4)
                          HO                                                                          O
                                                    O                                                     -4.3
                                                         -3.9          HO                          P O–
                        HO                          P O–                                         O
                                           O                                                        O–
                                                     O–
                                                                                        OH

                                                                                –
                          HO                                                     O
                         HO P O                         O                   –
                                                                                O P O                     O
                        -1.5                                            -1.1
                               O               CH3                                  O             NH2


       O                                        +
                                                    NH 3          H3 C CH3                                O
                                                                                                                                        O
                O   –                                                + N CH3                                                                3.7
                                                                                                  HO                                 P O–
                                                                                                                                   O
                                                                                                                                      O–
        N CH3                                  O        3.7
HN         O                                        P     O          O 3.2                       H3 C           N
       HN P -2.5
                                       –
                                           O–                           P O
                                                O                 –
                                                                    O–
              –
          O– O                                                         O


             O                                    O                                       O                                         O
           H                                    H                                   +