Electrochemical coupling reactions of benzyl halides on a powder cathode and cavity cell

Benzyl halides adsorbed on a cathode made of pure or silver-doped graphite powder were reduced in an undivided cell using an aqueous electrolyte and an inert anode, in the absence or presence of benzaldehyde. The product ratio is influenced by the applied potential, the leaving halide group and presence/absence of silver electrocatalyst. The highest yield of bibenzyl was obtained from the electrolysis of benzyl bromide on silver-doped graphite at a constant potential equal to -1.0V vs Ag/AgCl (sat. KCl). Benzyl chloride is less prone to dimerization, but undergoes efficient carbonyl addition to benzaldehyde, especially in the presence of silver. The results can be interpreted as a competition of radical and anionic processes. (C) 2010 Elsevier Ltd. All rights reserved.