Electrochemical Reduction of N-Bromosuccinimide. Reaction Mechanism for Formation of the Succinimidyl Radical

Article abstract of DOI:10.1021/jo00346a026

The electrochemical reduction of N-bromosuccinimide in acetonitrile at a platinum cathode generates the succinimidyl radica;l in an overall process for which the n value is 1.The succinimide anion, generated by two-electron reduction of N-bromosucinimide, is an intermediate in this process, and its electron-transfer reaction with the N-bromo imide generates the radical.The intermediacy of the succinimide anion is demonstrated by trapping experiments in which the anion is captured by alkylating agents to give N-alkylsuccinimides.With increasing capture of the anion the n value for the electrochemical reaction approaches 2 as a limit.The reduction of N-bromosuccinimide by the succinimide anion, added as a quaternary ammonium succinimide, in a purely chemical system has also been studied.Rate constants for the pertinent reactions have been measured, and the reaction mechanisms have been discussed.