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					                                                               pKa's of Inorganic and Oxo-Acids                                                                   Chem 206

          Substrate   pKa H2O (DMSO)          Substrate         pKa   H2O (DMSO)    Substrate           pKa H2O (DMSO)       Substrate                pKa H2O (DMSO)
                INORGANIC ACIDS                       CARBOXYLIC ACIDS                             ALCOHOLS                   PROTONATED SPECIES
          H2O                 15.7   (32)         O
                                                                                                                   (31.2)          O
                                                                                    HOH                    15.7
                                                                                                                                   N+                     -12.4
          H3O+                -1.7            X       OH                             MeOH                  15.5    (27.9)    Ph             OH
                                              X= CH3                  4.76 (12.3)   i-PrOH                         (29.3)
                                                                                                                                  +
                                                                                                                                   OH
          H2S                 7.00                                                                         16.5
                                                 CH2NO2               1.68                                                                                -7.8
                                                                                    t-BuOH                 17.0    (29.4)    Ph             OH
          HBr                 -9.00 (0.9)        CH2F                 2.66                                                        +
                                                                                    c-hex3COH                                      OH
          HCl                 -8.0   (1.8)       CH2Cl                2.86                                 24.0
                                                                                                                                                          -6.2
                                                 CH2Br                2.86          CF3CH2OH               12.5    (23.5)    Ph             CH3
          HF                  3.17   (15)
                                                 CH2I                 3.12          (CF3)2CHOH              9.3    (18.2)          H
          HOCl                7.5                CHCl2                1.29                                                         O+                     -6.5
                                                                                    C6H5OH                 9.95    (18.0)    Ph             Me
          HClO4               -10                CCl3                 0.65
                                                 CF3                  -0.25          m-O2NC6H4OH            8.4                       H

          HCN                 9.4    (12.9)                                                                                           O+                  -3.8
                                                 H                    3.77            p-O2NC6H4OH           7.1     (10.8)   Me             Me
          HN3                 4.72   (7.9)       HO                   3.6, 10.3      p-OMeC6H4OH           10.2    (19.1)              O+ H               -2.05
                                                  C6H5                4.2 (11.1)
          HSCN                4.00                                                   2-napthol                     (17.1)              H
                                                  o-O2NC6H4           2.17                                                             O+                 -2.2
          H2SO3               1.9, 7.21           m-O2NC6H4           2.45          OXIMES & HYDROXAMIC ACIDS                Me
                                                                                                                                   +
                                                                                                                                            H
                                                                                                                                      OH
                                                  p-O2NC6H4           3.44                    OH
          H2SO4               -3.0, 1.99                                                  N                                            S                  -1.8
                                                  o-ClC6H4            2.94                                  11.3 (20.1)      Me             Me
          H3PO4               2.12, 7.21,                                            Ph       Ph
                              12.32               m-ClC6H4            3.83                O
                                                                                                                                           N+ OH          0.79    (+1.63)
          HNO3                -1.3                                                                 OH       8.88 (13.7)
                                                  p-ClC6H4            3.99           Ph     N               (NH)
                                                                                          O H                                              Me
          HNO2                3.29                o-(CH3)3N+C6H4 1.37
                                                                                                   OH                         Me           N     OH               (+5.55)
                                                  p-(CH3)3N+C6H4 3.43                Ph       N                    (18.5)
          H2CrO4              -0.98, 6.50                                                                                                  Me
                                                  p-OMeC6H4           4.47                    Me
          CH3SO3H             -2.6   (1.6)                                                                                   SULFINIC & SULFONIC ACIDS
                                                           O
                                                                                                   PEROXIDES
          CF3SO3H             -14    (0.3)
                                              R                OH                                                                  O        O
          NH4Cl               9.24                                                                                                     S                   -2.6
                                              R= H                    4.25           MeOOH                  11.5              Me               OH
          B(OH)3              9.23               trans-CO2H           3.02, 4.38                                                       O
                                                                                     CH3CO3H                8.2
                                                                                                                                       S                  2.1
          HOOH                11.6                cis-CO2H            1.92, 6.23                                              Ph               OH

                        *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
                      For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm

pKa Table.1 11/4/05 1:43 PM
D.H. Ripin, D.A. Evans                                                                         pKa's of Nitrogen Acids                                                                                                     Chem 206

      Substrate                  pKa H2O           (DMSO) Substrate                     pKa    H2O (DMSO)           Substrate                  pKa H2O (DMSO)                Substrate            pKa H2O (DMSO)

          PROTONATED NITROGEN                                                       AMINES                                                    IMIDES                         HYDROXAMIC ACID & AMIDINES
                                                              HN3              4.7 (7.9)                                          O                        O                        O
      N+H4                                 9.2      (10.5)                                                                                                                                                8.88 (13.7)
                                                              NH3              38    (41)                                                                                                    OH           (NH)
      EtN+H    3                           10.6                                                                                    NH         8.30          NH      (14.7)    Ph      N
                                                              i-Pr2NH      (36 THF))                                                                                                  H
      i-Pr2N+H2                            11.05
                                                               TMS2NH      26(THF) (30)                                                                                             NSO2Ph
                                                                                                                                  O                        O                                      R= Me                   (17.3)
       Et3N+H                              10.75 (9.00)       PhNH2 (30.6)                                          Ac2NH                                           (17.9)                           Ph                   (15.0)
                                                                                                                                                                               R        NH2
       PhN+H3                              4.6      (3.6)     Ph2NH (25.0)      Me
                                                                                  Me                                              SULFONAMIDE
      PhN+(Me)                             5.20     (2.50)    NCNH2 (16.9)                                                                                                                  HETEROCYCLES
                   2H
                                                                                 NH (37)                            RSO2NH2  R = Me      (17.5)
      Ph2N+H2                              0.78                    NH (44)                                                       Ph      (16.1)                                          H      (20.95)               H
                                                                                                    Me                           CF3 6.3 (9.7)                                           N
                                                                                                                                                                                                                      N
                                                                                                                                                                                                                            (16.4)
       2-napthal-N+H3                      4.16                                                    Me
                                                                                                                    MeSO2NHPh            (12.9)
      H2NN+H3                              8.12                H2N                  N     (26.5)                                                                                        H                             N
                                                                                                                         GUANIDINIUM,                                                   N
                                                                                                                                                                                             (11.9)
      HON+H3                               5.96                                                                     HYRDAZONES,- IDES, & -INES                                              N                 NH      (23.0)
                                   H                                AMIDES & CARBAMATES                                        N+H2                                                     N
      Quinuclidine           N+            11.0     (9.80)                                                                                (13.6)          NNH2      (21.6)
                                                                   O            R= H          (23.5)                Me2N          NMe2               Ph        Me                         X= O (24)                        N
                                                                                     CH3 15.1 (25.5)                                                                                                          HN
      Morpholine        O              N+H2 8.36
                                                                                                                              O
                                                                                                                                   (18.9)                                     N         X X= S (13.3)                      (18.6)
                                                              R           NH2
                                                                                     Ph       (23.3)                                                                          H
                                                                                                                      Ph          NHNH2                                        X
       N-Me morpholine                     7.38                                      CF3      (17.2)
                        NO2                                                                                         PhSO2NHNH2                                      (17.2)              X= O (14.8)
                                                                              (urea) NH2      (26.9)                                                                                                                   NH
                                                                                                                    PhNHNHPh                                                            X= S (11.8)           N
                             +                                                       OEt      (24.8)                                                                (26.1)                                         N       (13.9)
       O2N                    NH3          -9.3                                                                                                                                N
                                                                   O                           O
                                                                                                                    PROTONATED HETEROCYCLES                                    H                          X
                                                                               Ph                      12 (20.5)                                                                                                       X= O (24.4)
                        NO2                                   Et          N                                                                                                        N                              H
                                                                                 (21.6)    O       NH                                     N                                                                            X= S (27.0)
                                                                          H                                                                           (12) (estimate)          N                          N
                            N+ H                                                                                   DBU                                                              (19.8)
                                           2.97, 8.82                                                                                          +                               H
       DABCO           N+                  (2.97, 8.93)        O                                       Bn                                      N
                                                                                                   O                                           H                                S                             S
                   H
                                                                              n= 1 (24.1)                (20.8)    DMAP                                                                 H    (29.4)                    H       (16.5)
        H3N+                                                        NH                                                                                         +
                       +NH                 6.90, 9.95                         n= 2 (26.4)      O       NH                             +                        NH               N                             N+
                          3
                                                                   ( )n                                            Me2N                   NH   9.2                   6.95                          Me         Me
                             +NH        +NH                                                                                                          HN
                                   3       3                                                                                                                                                                               i-Pr
                                                 -9.0, 12.0    O                                                           R                                                                              Me
                                                                                               O               5.21 (3.4)         R= H (PPTS)
                                                                                                                                     NMe                                                                               N
    Proton Sponge                                (--, 7.50)            (15)                                                                                                                                                           (24)
                                                                                                        O      4.95 (0.90)+          t-Bu H                                                                                       H
                                                      O   NH                                 NH
                                                                         N   (12.1)                                                  N + (18.4)                                                                        N+
                                                                         H                                     6.75 (4.46)           Me
                                                                                                                                     Me
                                                                                                                                                                                                          Me
       PhCN+H                           -10                                                   R                0.72                  Cl, H                                                                                 i-Pr

                                 *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.

                  For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
pKa Table.2 11/4/05 1:43 PM
  D.H. Ripin, D.A. Evans                    pKa's of CH bonds in Hydrocarbons and Carbonyl Compounds                                                                               Chem 206

         Substrate             pKa H2O (DMSO)     Substrate                   pKa H2O (DMSO)         Substrate                pKa H2O (DMSO)      Substrate             pKa H2O (DMSO)
                                                                                                                                                                    O
                 HYDROCARBONS                                          ESTERS                                              KETONES
         (Me)3CH                                              O                                           O                                                             Me
                                   53                                               24.5 (30.3)
                                                                                                                      X
         (Me)2CH2                  51             t-BuO           Me                                Me                                            X
                                                              O                                                                         (26.5)
                                                                                                     X= H
         CH2=CH2                                                          Ph             (23.6)         Ph                              (19.8)    X=       H                     (24.7)
                                   50
                                                  t-BuO                                                                                 (18.7)                                   (25.7)
                                                          O                                             SPh                                                OMe
         CH4                       48    (56)                                                                                                              NMe2                  (27.5)
                                                                                         (20.0)         COCH3                     9     (13.3)
                                                                      N+Me3                                                                                                      (23.8)
                                   46             EtO                                                   SO2Ph                           (12.5)             Br
                                                          O           O                                     O                                              CN                    (22.0)
         CH2=CHCH3                 43    (44)                                       11   (14.2)                                   19-20 (27.1)        O
                                                  EtO                      Me                        Et          Et
                                                                                                                O
         PhH                       43                     O           O
                                                                                    13   (15.7)                                         (28.3)        n
         PhCH3                           (43)                                                        i-Pr       O i-Pr
                                   41             MeO                         OMe
                                                          O                                                                             (27.7)
         Ph2CH2                    33.5 (32.2)                                                       t-Bu O           Me
                                                                                                                                                  n=       4                     (25.1)
                                                                      S                  (20.9)                                                                                  (25.8)
                                                  MeO                                                                                   (26.3)             5
         Ph3CH                     31.5 (30.6)
                                                                  S                                  Ph           i-Pr                                     6                     (26.4)
         HCCH                      24                     O                                                   O                                            7                     (27.7)
                                                                      Ph
                                                                                     [30.2 (THF)]                                                          8                     (27.4)
         PhCCH                     23   (28.8)                                                                            X
                                                  LiO                                                Ph

         XC6H4CH3                                                                                    X= H                               (24.7)
                                                                          AMIDES
                                                                                                        CH3                             (24.4)                                   (28.1)
         X= p-CN                         (30.8)               O                                                                                                 O
                                                                                         (26.6)         Ph                              (17.7)
              p-NO2                      (20.4)                           Ph                            COCH3                           (14.2)
                                                  Me2N
                                                              O                                         COPh                            (13.3)                                   (29.0)
              p-COPh                     (26.9)                                          (25.9)                                                                 O
                                                                          SPh                           CN                              (10.2)
         Me               Me                      Me2N
                                                          O                                             F                               (21.6)
                                         (26.1)                                          (24.9)                                         (22.85)                 O
                                                                      N+Me3                             OMe                                                                      (25.5)
           Me        Me                           Et2N
                                                              O                                         OPh                             (21.1)
                                                                                                        SPh                             (16.9)
                                                                           CN
                                   20    (20.1)           N                              (17.2)         SePh                            (18.6)
                                                                                                        NPh2                            (20.3)                  O
                                                              O           O                                                                                                      (32.4)
                                  15     (18.0)                                          (18.2)         N+Me3                           (14.6)
                                                  Me2N                         Me                       NO2                             (7.7)         Me       Me
                                                              S
         H2                        ~36                                                   (25.7)         SO2Ph                           (11.4)
                                                  Me2N            Me

                          *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
                          For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm

pKa Table.3 11/4/05 1:44 PM
D.H. Ripin, D.A. Evans              pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted Carbon                                                  Chem 206

     Substrate            pKa H2O (DMSO)       Substrate           pKa H2O (DMSO)    Substrate           pKa H2O (DMSO)     Substrate pKa H2O (DMSO)
                        NITRILES                                 SULFIDES                            SULFOXIDES                                   SULFONES
                                                                                           O                                    O       O
       NC      X                               PhSCH2X
                                                                                           S         X                              S             X
                                               X= Ph                        (30.8)   Me                                    Ph
      X=       H                      (31.3)       CN                       (20.8)   X= H                         (35.1)                                     (29.0)
                                                                                        Ph                        (29.0)   X= H
               CH3                    (32.5)       COCH3                    (18.7)      SPh                       (29.0)      CH3                            (31.0)
                                      (21.9)       COPh                     (16.9)         O                                  t-Bu                           (31.2)
               Ph
                                      (10.2)       NO2                      (11.8)         S         X                        Ph                             (23.4)
               COPh                                                         (30.8)
                                                   SPh                               Ph                                       CH=CH2                         (22.5)
               CONR2                  (17.1)       SO2Ph                    (20.5)   X= H                         (33)        CH=CHPh                        (20.2)
               CO2Et                  (13.1)                                            Ph                        (27.2)                                     (22.1)
                                                   SO2CF3                   (11.0)                                (18.2)      CCH
                                                   POPh2                    (24.9)      SOPh                                                                 (17.8)
               CN              11     (11.1)                                               O                                  CCPh
                                                                                                                              COPh                           (11.4)
               OPh                    (28.1)   MeSCH2SO2Ph                  (23.4)         S                      (24.5)
                                                                                     Ph         CHPh2                         COMe                           (12.5)
               N+Me3                  (20.6)   PhSCHPh2                     (26.7)                                            OPh                            (27.9)
               SPh                    (20.8)
                                               (PhS)3CH                     (22.8)                   SULFONIUM                N+Me3                          (19.4)
                                                                                                                              CN                             (12.0)
               SO2Ph                  (12.0)
                                               (PrS)3CH                     (31.3)   Me3S+=O                      (18.2)      NO2                            (7.1)
                                                                                           Me                                 SMe                            (23.5)
                                                            Me                                                    (16.3)                                     (20.5)
               HETERO-AROMATICS                     S                                                                         SPh
                                                                                           S+
                                                                            (30.5)   Ph         CH2Ph                         SO2Ph                          (12.2)
                                               S        S                                                                     PPh2                           (20.2)
                                      (28.2)    H
                   Ph                                                                SULFIMIDES & SULFOXIMINES                  O       O
          N                                    (PhS)2CHPh                   (23.0)                                                  S                        (22.3)
                                                                                           NTs                             Ph            CHPh2
                                                        S
                                      (30.1)                 X                             S                                    O       O
      N            Ph                                                                Ph         R                                                            (31.1)
                                                                                                                                    S
                                                        S                            R= Me                        (27.6)   Me               Me
      N                                        X=   Ph                      (30.7)      i-Pr                      (30.7)        O           O
                                      (26.7)                                           O       NTs                                                           (18.8)
                   Ph                               CO2Me                   (20.8)                                                      S
                                                                                           S                      (24.5)   CF3               Me
                                                    CN                      (19.1)   Ph         Me                            O             O
                                               RSCH2CN                                 O       NMe                                      S                    (21.8)
                   Ph                                                       (24.3)                                (33)     CF3                  i-Pr
          N+
                                      (25.2)   R= Me                                       S
                                                                                                                              O             O
                                                                                     Ph         Me
                                                    Et                      (24.0)             N+Me2                                    S                    (26.6)
          O-                                                                           O
                                                                            (23.6)                                (14.4)   CF3
                                                   i-Pr                                    S
                   Ph                 (30.2)                                (22.9)   Ph         Me                          O           O
          O
                                                   t-Bu                                O       NTs                                                           (32.8)
                                                                                                                                    S
                                               PhSCH=CHCH2SPh      (26.3)                  S                      (20.7)   Et               Et
                   Ph                 (30.0)                                         Ph         CH2Cl
          S                                    BuSH          10-11 (17.0)                                                  (PhSO2)2CH2Me                     (14.3)
                                               PhSH          ≈7    (10.3)

                          *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.


pKa Table.4 11/4/05 1:44 PM
D. H. Ripin, D. A. Evans                pKa's of CH bonds at Heteroatom Substituted Carbon & References                                                Chem 206

   Substrate             pKa H2O (DMSO)        Substrate          pKa H2O (DMSO)   Substrate           pKa H2O (DMSO)
                                                                                                                                       REFERENCES
                    ETHERS                                PHOSPHONIUM                                  NITRO
                                                                                                                              DMSO:
                                               P+H4                       -14      RNO2
     CH3OPh                          (49)                                                                                     JACS 97, 7007 (1975)
                                               MeP+H3                     2.7      R= CH3                      ≈10   (17.2)   JACS 97, 7160 (1975)
     MeOCH2SO2Ph                     (30.7)
                                               Et3P+H                     9.1         CH2Me                          (16.7)   JACS 97, 442 (1975)
     PhOCH2SO2Ph                     (27.9)                                                                                   JACS 105, 6188 (1983)
                                               Ph3P+CH3                   (22.4)      CHMe2                          (16.9)   JOC 41, 1883 (1976)
     PhOCH2CN                        (28.1)    Ph3P+i-Pr                  (21.2)      CH2Ph                          (12.2)   JOC 41, 1885 (1976)
              O                                                                                                               JOC 41, 2786 (1976)
                                               Ph3P+CH2COPh               (6.2)       CH2Bn                          (16.2)
     MeO                             (22.85)                                                                                  JOC 41, 2508 (1976)
                   Ph                          Ph3P+CH2CN                 (7.0)          CH2SPh                      (11.8)   JOC 42, 1817 (1977)
                                                                                         CH2SO2Ph                    (7.1)    JOC 42, 321 (1977)
                                                                                         CH2COPh                     (7.7)    JOC 42, 326 (1977)
                   SELENIDES                           PHOSPONATES &                                                          JOC 43, 3113 (1978)
                                                      PHOSPHINE OXIDES             O2N                                        JOC 43, 3095 (1978)
               O                                      O                                                                       JOC 43, 1764 (1978)
                                                                                             n                                JOC 45, 3325 (1980)
     PhSe                            (18.6)    (EtO)2P        X
                   Ph                                                                                                         JOC 45, 3305 (1980)
                                               X=     Ph                  (27.6)                                     (26.9)   JOC 45, 3884 (1980)
     PhSeCHPh2                       (27.5)                                        n=    3                                    JOC 46, 4327 (1981)
                                                      CN                  (16.4)
     (PhSe)2CH2                      (31.3)                                              4                           (17.8)   JOC 46, 632 (1981)
                                                      CO2Et               (18.6)                                              JOC 47, 3224 (1982)
                                                                                         5                           (16.0)
     PhSeCH2Ph                       (31.0)           Cl                  (26.2)                                              JOC 47, 2504 (1982)
                                                                                         6                           (17.9)   Acc. Chem. Res. 21, 456 (1988)
     PhSeCH=CHCH2SePh                (27.2)           SiMe3               (28.8)                                     (15.8)   Unpublished results of F. Bordwell
                                                  O                                      7
                                               Ph2P       X                                                                   Water:
                   AMMONIUM                                                                            IMINES
                                               X=     SPh                 (24.9)                                              Advanced Org. Chem., 3rd Ed.
                                                                                         N        Ph                             J. March (1985)
     Me3N+CH2X                                        CN                  (16.9)
                                                                                                                     (24.3)   Unpublished results of W. P. Jencks
     X= CN                           (20.6)                                        Ph        Ph

        SO2Ph                        (19.4)                PHOSPHINES               Oxime ethers are ~ 10 pka units less      THF:
                                     (14.6)                                         acidic than their ketone counterparts     JACS 110, 5705 (1988)
            COPh
                                                                                    Streitwieser, JOC 1991, 56, 1989
            CO2Et                    (20.0)    Ph2PCH2PPh2                (29.9)                                              See cited website below for additional
                                                                                                                              data
            CONEt2                   (24.9)    Ph2PCH2SO2Ph               (20.2)

                        *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.

               For a comprehensive compilation of Brodwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
pKa Table.5 11/4/05 1:45 PM
                                       DMSO Acidities of Common Heterocycles
                                                 Bordwell, ACR, 1988, 21, 456
                               Bordwell http://www.chem.wisc.edu/areas/reich/pkatable/index.htm


                                                  N                         N                  N                    N
                                N                                                              N                        N
            N              N                  N                             N              N                        N
            H              H                  H                             H              H                        H

        23.0              19.8               18.6                      16.4                13.9              11.9            18.0



                                   O                           O                         O
                                                                                                   O
                 O                       O                         O
        N                      N                           N                               N                N       O             N     O
        H                      H                           H                               H                H                     H


       24.0                    20.8                        15.0                     12.1                   26.4                  24.0

                                                                                                                                             Me
                                   O                   S                                                                Me                         Me
                                                                                               S                                        Me
                                                                        S                                               N                     N
                                                                                                       H
                                                                                H                                            H                     H
                                                                                               N+
            N        S                                                  N           Me                                  N+                    N+
            H                      N                   N                                       Me                                       Me
                                   H                   H                                                                Me                         Me
                                                                                                                                             Me
          13.3                    14.8                11.8             29.4                16.5                   18.4                       24




Pka Table.6.cdx 11/4/05 1:45 PM

				
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