Derivatives of Carboxylic Acids

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Derivatives of Carboxylic Acids Nucleophilic Acyl
Substitution
Acid Halide Anhydride Ester
Amide Nitrile
Esters
Methyl ethanoate phenyl benzoate
cyclohexyl methanoate
Methyl acetate
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Cyclic Esters Lactones
? ? ?
H2O
?-butyrolactone
Amides
N-ethyl ethanamide N, N-dimethyl
methanamide N-ethyl acetamide N,
N-dimethyl formamide
(DMF common solvent)
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Cyclic Amide - Lactam
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?
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• - caprolactam
• - used to make Nylon

Amides possess important resonance contributors
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The C-N bond has partial double bond character.
Consequently, there is resistance to rotation
about the C-N bond
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NMR spectrum of DMF
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13C NMR 1H NMR
The two methyl groups are not equivalent due to
restricted rotation about the CN bond.
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Anhydrides - without water
anhydride
acetic anhydride
Reactions of Carboxylic Acid Derivatives
Nucleophilic Acyl Substitution
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Substrate Leaving Group
Most reactive
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Least reactive
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Reactions of Acid Chlorides
H2O
HCl
ROH
HCl
NH3
HCl
RCO2H
HCl
H-
Use LiAl(OtBu)3H
RMgX