Electrochemical preparation of orthophenylenediamine on different cathodes in sulfuric acid

The electrochemical reduction of nitro group of orthonitroaniline (ONA) is carried out on Pb, Cu, and Sn electrodes. The effect of current density, temperature, and acid concentration on product yield is studied. The polarization curve for ONA in acidic condition is recorded. Under preparative electrolysis, ONA gives a mixture of hydroxylamine and phenylenediamine, the proportion of phenylenediamine increasing with the electrolysis time. The product formation is confirmed by thin-layer chromatography, melting-point test, UV-visible, IR, and NMR methods. The operating conditions are optimized for a good yield of orthophenylenediamine. The catalytic activity of different metals for the reduction of nitro group is discussed. The percent yield of orthophenylenediamine is found to be high on the lead electrode.