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Carboxylic Acid and Derivatives
1) Structure, Bonding and Physical Properties




                                                                                              MW     boiling point (oC)
                                                                            CH 3CH2 CH2CH 3   58           0

                                                                            CH 3CH2 -CHO       58         48

                                                                            CH 3CH2 CH2OH     60          97

                                                                             CH 3COOH          60         118




2) Interesting Carboxylic Acids
                                                                                Food preservatives




            O                                  O

                OH                                 OMe                            Soap
            O                                                                                                             O
                                               OH
                                                                                                                              O   Na
        O       CH3                   Methyl salicylate
                                                                                              Sodium palmitate
       aspirin




3) Nomenclature of Carboxylic Acid
IUPAC: parent chain + oic acid
Salt of carboxylic acid (RCOO-M+): Metal + parent chain + oate



4) Preparation of Carboxylic Acid
4.1 Oxidation of Primary Alcohol and Aldehyde
         OH                       O                             O
1o                    KMnO4                  KMnO4
        C                         C                             C
     R     H                   R    H                       R       OH
       H
                              aldehyde                    carboxylic acid
                                                                                                                   2
4.2 Oxidation or Ozonolysis of Alkene
                                            O                     O
                       [O]                              +
             R'
R                                     R          OH         R'        OH


oxidizing condition: 1) KMnO 4, OH- or 1) O3
                     2) H 3O +         2) H 2O2


4.3 Hydrolysis of Cyanohydrin and Nitrile
    O                    HO CN                   acid       HO COOH
                 HCN
R       R'                   R       R'                     R         R'
                        cyanohydrin

                   CN                             acid
    R        X                   R    CN                                   COOH
                                                                 R
                                 nitrile


4.4 Carbonation or Carboxylation of Grignard Reagent
                 CO2             O                H3O+            O
RMgX
                             R       OMgX                     R        OH



5) Reaction of Carboxylic Acid
                                                                               O

                                                                           R    OR'
                                                                            ester


                                                                                   R'OH, H +

                                                                      Carboxylic acid

                                                 O                             O                     O    O
                                                            SOCl 2                         heat
                                             R        Cl                   R       OH              R     O   R
                                                                                                  acid anhydride
                                          acid chloride
                                                                               x    NH3


                                                                               O

                                                                           R    NH 2
                                                                            amide
                                                                                                                               3
6) Carboxylic Acid Derivatives
                                                                 O
                                                                 C
                                                              R    OH
                                                           Carboxylic acid


                                       O           O                 O                  O     O
                                       C           C                 C                  C
                                   R    OR'    R   N            R    X             R     O   R'
                                    Ester       Amide          Acid halide        Acid anhydride
                                                               (X = halide)


                                       O           O                              O
                                       C           C                              C
                                   C       O   C       N                    R    Z
                                                                     Z = electonegative atom
                                Lactone        Lactame
                              (cyclic ester) (cyclic amide)




6.1 Nomenclature

       Compound      Name ending                                     Example                     Name
       Acid chloride -yl chloride or carbonyl chloride               O                      benzoyl chloride
                                                                         Cl


       Anhydride       anhydride                                     O        O             benzoic anhydride
                                                                         O


       Ester           -ate                                          O                      Ethyl benzoate
                                                                         OCH2 CH3


       Amide           -amide                                        O                      N-methylbenzoate
                                                                         NHCH 3




6.2 Nucleophilic Acyl Substitution

    Nu:- or :NuH 2                                                                            REACTIVITY


                      Nu
    C O                     C O                        C O               O                O    O             O          O
Z                       Z                       Nu
                                                                         C                C                  C          C
                                                                     R    Cl           R     O   R'        R    OR'   R   N
                                                                  Acid chloride       Acid anhydride        Ester      Amide
               Tetrahedron intermediate


                                                                                      LEAVING GROUP ABILITY
                                                                                                                          4
6.3 Reaction of Acid Chloride
                         Acid chloride

    O             H2 O          O                                    O                              OH
                                                 R'MgX                             R'MgX
R       OH                  R       Cl                           R       R'                    R        R'
                                                                                                       R'
              R'OH                                [H]
        O
                                    NH 3
                                                             O               [H]               OH
    R       OR'
                                                         R       H                        R        H
                                O

                            R       NH 2



6.4 Reaction of Acid Anhydride
                           Acid anhydride

    O             H2 O          O        O

R       OH                 R        O        R
              R'OH
        O                                          [H]
                                    NH 3
    R       OR'                                                  O                                 OH
                                                                                   [H]
                                O                            R       H                         R       H
                            R       NH 2



6.5 Reaction of Ester

                                Ester

    O             H2O               O                                         O                            HO R"
                                                        R"MgX                             R"MgX
R       OH                      R        OR'                             R         R''                     R        R''


                                    NH 3           [H]
                                                                 O                 [H]             OH
                                O
                                                             R       H                         R       H
                            R       NH2



6.6 Reaction of Amide
                                                                 Amide

further fuctionalization        O                H 2O            O                       [H]           H     H
                            R        OH                      R       NH 2                              R     NH 2
                                                                                                       amine
                                                            5
6.7 Natural Nucleophilic Acyl Substitution




        6.7.1 Formation of Neurotransmitter Acetylcholine




        6.7.2 Cholesterol Storage

				
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