Reactions of carboxylic acid derivatives with superoxide

Abstract

The mechanisms of the reactions of superoxide with carboxylic esters, acyl peroxides, and the acyl chlorides of α- and β-bromocarboxylic acids have been investigated. Experimental evidence is presented supporting the view that (a) conversion of an ester into its carboxylic acid does not proceed via the corresponding acyl peroxide; (b) conversion of acyl peroxide into carboxylic acid by superoxide involves either electron transfer to or an S_N² reaction on the peroxidic group; (c)α-bromoacyl chlorides with superoxide give the corresponding aldehyde via a cyclic peroxidic intermediate.