Addition–Elimination Reactions of Carboxylic Acids and Derivatives

Abstract

This chapter focuses on the addition–elimination reactions of carbon, oxygen, and nitrogen nucleophiles to carboxylic acids and their derivatives, as well as to carbonic acid derivatives. The esterification of carboxylic acids is discussed, and the Hammett equation and its parameters are introduced to discuss the relationship between reaction rates and equilibrium constants for some reactions of benzoic acid and derivatives. The acidic and basic hydrolysis of carboxylic acid derivatives is discussed, and the Principle of Microscopic Reversibility is introduced. The preparation and hydrolysis of amides are also considered. The generation of alcohols from carboxylic acids and derivatives by the addition of organometallic reagents to carboxylic acid derivatives is also addressed. Ketones are shown to be prepared by the addition of cuprate reagents to acyl chlorides and of organolithium or organomagnesium reagents to Weinreb amides.