Electrochemical amination of para-chloroaniline

Yu.A. Lisitsyn

Kazan Federal University, Kazan, 420008 Russia

E-mail: Yuri.Lisitsyn@kpfu.ru

Received April 11, 2019

Full text PDF

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).

References

1. Minisci F. Novel applications of free-radical reactions in preparative organic chemistry. Synthesis, 1973, no 1, pp. 1–24. doi: 10.1055/s-1973-22123.

2. Citterio A., Gentile A., Minisci F., Polar effects in free radical reactions. Homolytic aromatic amination by the amino radical cation, ^?+NH₃: Reactivity and selectivity. J. Org. Chem., 1984, vol. 49, no 23, pp. 4479–4482. doi: 10.1021/jo00197a030.

3. Kuznetsova N.I., Kuznetsova L.I., Detusheva L.G., Likholobov V.A., Pez G. P., Cheng H. Amination of Benzene and Toluene with Hydroxylamine in the Presence of Transition Metal Redox Catalysts. J. Molec. Catal. A: Chem., 2000, vol. 161, nos. 1–2, pp. 1–9. doi:10.1016/S1381-1169(00)00206-5.

4. Zhu L.F., Guo B., Tang D.Y., Hu X.K., Li G.Y., Hu C.W. Sodium metavanadate catalyzed one-step amination of benzene to aniline with hydroxylamine. J. Catal., 2007, vol. 245, no 2, pp. 446–455. doi: 10.1016/j.jcat.2006.11.007.

5. Parida K.M., Dash S.S., Singha S. Structural properties and catalytic activity of Mn-MCM-41 mesoporous molecular sieves for single-step amination of benzene to aniline. Appl. Catal., A, 2008, vol. 351, no 1, pp. 59–67. doi: 10.1016/j.apcata.2008.08.027.

6. Singha S., Parida K.M. A reusable Mn(II)-dampy-MCM-41 system for single step amination of benzene to aniline using hydroxylamine. Catal. Sci. Technol., 2011, vol. 1, no. 8, pp. 1496–1505. doi: 10.1039/c1cy00247c.

7. Lisitsyn Yu.A., Kargin Yu.M. Electrochemical amination of unsaturated and aromatic compounds. Russ. J. Electrochem., 2000, vol. 36, no 2, pp. 89–99. doi: 10.1007/BF02756893.

   Lisitsyn Yu.A., Makarova O.N., Kargin Yu.M. Electrochemical amination: VII. Introduction of amino group into aromatic ring. Russ. J. Gen. Chem., 1999, vol. 69, no 2, pp. 275–279.

   Lisitsyn Yu.A., Sukhov A.V. Selective synthesis of benzene-1,3-diamines by amination of anilines containing ortho/para-orienting substituents in the para position. Russ. J. Org. Chem., 2015, vol. 51, no. 3, pp. 439–440. doi: 10.1134/S1070428015030264.

   Lisitsyn Yu.A., Sukhov A.V. Electrochemical amination. Selective introduction of two amino groups into an aromatic ring. Russ. J. Gen. Chem., 2017, vol. 87, no. 1, pp. 16–21. doi 10.1134/S1070363217010042.

8. Lisitsyn Yu.A., Sukhov A.V. Electrochemical amination. Selective functionalization of para- and ortho-anisidines in aqueous sulfuric acid solutions. Russ. J. Electrochem., 2018, vol. 54, no. 12, pp. 1294–1294. doi: 10.1134/S102319351813027X.

9. Ingold C.K. Structure and Mechanism in Organic Chemistry. Ithaca, London, Cornell Univ. Press, 1969. ix, 1266 p.

10. Sykes P. Longman Publ. Group, 1986. 416 p.

11. Korenman I.M. Ekstraktsiya v analize organicheskikh veshchestv [Extraction in the Analysis of Organic Compounds]. Moscow, Khimiya, 1977. 200 p. (In Russian)

12. Korenman I.M. Konstanty raspredeleniya organicheskikh veshchestv mezhdu dvumya zhidkimi fazamiThe Distribution Constants of Organic Compounds between Two Liquid Phases]. Gorky, Izd. Gork. Gos. Univ., 1979, no. 5. 72 p. (In Russian)

13. Librovich N.B. Maiorov V.D. Ionic-molecular composition of aqueous sulfuric acid solutions at 25 ?. Bull. Acad. Sci. USSR. Div. Chem. Sci., 1977, vol. 26, no. 3, pp. 621–623. doi: 10.1007/BF01179485.

14. Damaskin B.B., Nekrasov L.N., Petrii O.A., Podlovchenko B.I., Stenina E.V., Fedorovich, N.V. Elektrodnye protsessy v rastvorakh organicheskikh soedineniiElectrode Processes in Solutions of Organic Compounds]. Moscow, Izd. Mosk. Univ., 1985. 312 p. (In Russian)

15. Lisitsyn Yu.A., Kargin Yu.M. Electrochemical amination. II. Effect of electrolyte acidity. Russ. J. Gen. Chem., 1993, vol. 63, no. 6, part 1, pp. 917–920.

The content is available under the license Creative Commons Attribution 4.0 License.