Electrochemical amination. synthesis of aniline in aqueous–acetonitrile solutions of sulfuric acid

© 2015, Pleiades Publishing, Ltd. The process of indirect cathodic amination of benzene is studied in aqueous media containing 4-10 M H2SO4 and, accordingly, 13.8–7.1 M CH3CN. At 50°C, electrolysis in the system of Ti(IV)–NH2OH–C6H6 results in formation of aniline and also small amounts of isomeric phenylenediamines and diphenyl. The current efficiency of aniline is maximum in the catholyte containing 8 M H2SO4 and 9.4 M CH3CN. Under these conditions, full conversion of hydroxylamine is observed; the 80% current efficiency of aniline corresponds to the efficiency of the amino radical source and its mass fraction among the products of electrolysis exceeds 97%