Decomposition of Benzoate Ester Radical Anions

Abstract

The electrochemical reduction of benzoate esters in aprotic media leads to relatively stable radical anions. The radical anions decompose to electroinactive products in an initial EC mechanism. At long‐time scales and/or higher concentrations, the benzoate esters begin to exhibit more complicated mechanistic behavior. The initial rates of decomposition of several benzoate ester radical anions have been determined by digital simulations of cyclic voltammograms, double potential step experiments, and rotating ring‐disk techniques. On short‐time scales, the reduction of t‐butyl p‐toluate is a good example of pure EC mechanistic behavior. The final decomposition products are many and complex for most of the esters studied, but t‐butyl benzoate cleanly gives benzoate anion and t‐butyl p‐t‐butyl benzoate.