Electrochemical Amination of Isomeric Chloroanilines in Aqueous Solutions of Sulfuric Acid

The processes of indirect cathodic amination of para, ortho, and meta-chloroanilines by means of the Ti(IV)–NH2OH system in aqueous solutions of 9–17 M sulfuric acid are studied. The efficiency and regioselectivity of radical cation substitution increase with the increase in electrolyte acidity and temperature. Functionalization of para-chloroaniline in 17 М H2SO4 produces 4-chloro-1,3-phenylenediamine with the mass fraction of 99.7%. Its yield corresponding to the complete conversion of hydroxylamine is 91%. The only side product of amination is para-phenylidenediamine.