Electrolysis of α-bromocarboxylic acids

Abstract

The electrolysis of α-bromovaleric, α-bromocaproic, α-bromodiethylacetic, and α-bromoisobutyric acids in both methanol and water has been studied. This represents the first detailed study of the behavior of α-halocarboxylic acids during Kolbe electrolysis.Under the experimental conditions, Kolbe dimer of the α-bromoacid is not produced, even in small amounts, in either solvent. In methanol, hydrogen ester and bromoester were the major electrolysis products. In water, straight-chain acids gave alkyl halide, 1,1-dibromoalkane, and Kolbe dimer of hydrogen acid, whereas branched-chain acids gave ketone and other products from bromination of the ketone. In both solvents, considerable free bromine was produced.