Electrochemical amination: Efficiency of a radical substitution

Abstract

Electrochemical amination of benzene in sulfuric acid electrolytes is studied and experimental conditions for highly efficient synthesis of primary aromatic amino compounds are determined. In the electrolysis of Ti(IV)-NH 2OH-C 6H 6 in 11 M H 2SO 4 solutions containing acetic acid or acetonitrile as organic solvents, aniline and isomeric phenylenediamines are obtained with the total yields by hydroxylamine of 95.6 and 99.6%, respectively. A monoamino compound is the main product of radical substitution in acidic organo-aqueous media. It is found that the use of acetonitrile in electrochemical process is limited to certain sulfuric acid concentrations and temperatures.