Electrochemical amination of para-chloroaniline

Yu.A. Lisitsyn

Kazan Federal University, Kazan, 420008 Russia

E-mail: Yuri.Lisitsyn@kpfu.ru

Received April 11, 2019


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DOI: 10.26907/2542-064X.2019.2.222-230

For citation: Lisitsyn Yu.A. Electrochemical amination of para-chloroaniline. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2019, vol. 161, no. 2, pp. 222–230. doi: 10.26907/2542-064X.2019.2.222-230. (In Russian)

Abstract

The process of cation-radical amination of para-chloroaniline using hydroxylamine and the Ti(IV)/Ti(III) mediator system was studied in aqueous solutions of 9–17 M H2SO4. The substitution products in these media are 4-chloro-1,3-, 4-chloro-1,2-phenylenediamines, as well as para-phenylene­diamine. An increase in the acid concentration was accompanied by a raise in the overall efficiency of the electrochemical process with a decrease in the current yields of the last two diamino compounds. In 17 M H2SO4, the yield and mass fraction of 4-chloro-1,3-phenylenediamine reached 75.2 and 99.7%, respectively.

Keywords: cathode, Ti(IV)/Ti(III) mediator system, hydroxylamine, para-chloroaniline, cation–radical aromatic substitution, 4-chloro-1,3-phenylenediamine

Acknowledgments. The work is performed according to the Russian Government Program of Competitive Growth of Kazan Federal University and supported by the Russian Foundation for Basic Research (project no. 16-03-01061).

Figure Captions

Fig. 1. Platinum cathode potential during para-chloroaniline amination in 9 (1), 11 (2), 13 (3), 15 (4), and 17 М H2SO4 (5).

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