REACTIONS OF CARBOXYLIC ACID DERIVATIVES
Introduction
This page focuses on the preparation of and reactions of carboxylic acid derivatives.
Reactions
Carboxylic acids
Preparation
Oxidative cleavage of alkynes
Oxidation of primary alcohols
Oxidation of alkylbenzenes. Note the necessity of a proton at the benzylic position.
Saponification of esters with sodium hydroxide followed by H3O+
Acid-catalyzed hydrolysis of esters
Acid-catalyzed hydrolysis of nitriles. Note that this mechanism includes hydrolysis of amides.
Treating carbon dioxide with a Grignard reagent and then H3O+ to form a carboxylic acid
Reactions
Reduction of a carboxylic acid with LAH.
Fischer esterification. Note the reversibility of all the steps: you can treat an ester with H3O+ to get the carboxylic acid.
Conversion to acid chloride with thionyl chloride and pyridine.
Acid chlorides
Reactions
Hydrolysis of acid chlorides
Alcoholysis of acid chlorides
Aminolysis of acid chlorides. Note that you can use NH3, NRH2, or NR2H to form primary, secondary, and tertiary amides, respectively.
Reduction of acid chloride to primary alcohol using LAH and H3O+ workup
Reduction of acid chloride using lithium tri(t-butoxy)aluminum hydride and water workup
Reduction of acid chloride using Grignard reagent
Reduction of acid chloride using Gilman reagent
Synthesis of acid anhydride
Acid anhydrides
Reactions that use acid anhydrides are very similar to those of acid chlorides, with a different leaving group. Thus a full discussion will be omitted here, as acid chloride reactions have been discussed extensively. Of particular note, however, is the use of acid anhydrides to protect alcohols. Deprotection can be achieved with sodium hydroxide. Amines can also be protected and deprotected.
Alcoholysis of acid anhydride
Esters
Reduction of an ester with LAH and then water workup. Two equivalents are needed.
Reduction of an ester with DIBAH and then water workup.
Nitriles
SN2 synthesis of nitriles from alkyl halides
Reaction of nitrile with Grignard reagent and then H3O+
Reaction of nitrile with LAH and water workup
Amides
Hydrolysis of amides
Reaction of an amide with LAH and water workup
