Статья
2020

Electrochemical Amination of Isomeric Chloroanilines in Aqueous Solutions of Sulfuric Acid


Yu. A. Lisitsyn Yu. A. Lisitsyn , A. V. Sukhov A. V. Sukhov
Российский электрохимический журнал
https://doi.org/10.1134/S1023193520050080
Abstract / Full Text

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.

Author information
  • Kazan Federal University, Butlerov Chemical Institute, 420008, Kazan, Russia

    Yu. A. Lisitsyn & A. V. Sukhov

References
  1. Lisitsyn, Yu.A. and Kargin, Yu.M., Electrochemical amination of unsaturated and aromatic compounds, Russ. J. Electrochem., 2000, vol. 36, p. 89.
  2. Lisitsyn, Yu.A., Kargin, Yu.M., and Busygina, N.V., Electrochemical radical cation amination of aromatic compounds, Ross. Khim. Zh., 2005, vol. 49, no. 5, p. 121.
  3. Lisitsyn, Yu.A. and 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, p. 439.
  4. Lisitsyn, Yu.A. and Sukhov, A.V., Electrochemical amination. Synthesis of aniline in aqueous–acetonitrile solutions of sulfuric acid, Russ. J. Electrochem., 2015, vol. 51, p. 1092.
  5. Lisitsyn, Yu.A. and Sukhov, A.V., Electrochemical amination. Selective introduction of two amino groups into an aromatic ring, Russ. J. Gen. Chem., 2017, vol. 87, p. 16.
  6. Lisitsyn, Yu.A. and Sukhov, A.V., Electrochemical amination of benzene in aqueous-acetic solutions of sulfuric acid, Russ. J. Gen. Chem., 2017, vol. 87, p. 929.
  7. Lisitsyn, Yu.A. and Sukhov, A.V., Electrochemical amination of chlorobenzene in aqueous-organic solutions of sulfuric acid, Russ. J. Electrochem., 2018, vol. 54, no. 11, p. 886.
  8. Lisitsyn, Yu.A. and 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, p. 1294.
  9. Sykes, P., A Guidebook to Mechanisms in Organic Chemistry, Longman, 1986.
  10. Ingold, C.K, Structure and mechanism in organic chemistry, Ithaca: Cornell University, 1969.
  11. Vulakh, E.L., Chernykh, T.E., Chernobrovkina, M.N., Mel’nikov, A.I., Borovlev, A.A., Nikulenko, S.N., Ivanov, O.N., Fedotov, P.I., and Merkin, A.A., RF Patent 2547264, 2015.
  12. Korenman, I.M., Ekstraktsiya v analize organicheskikh veshschestv (Extraction in the Analysis of Organic Compounds), Moscow: Khimiya, 1977.
  13. Korenman, I.M., Konstanty raspredeleniya organicheskikh veshchestv mezhdu dvumya zhidkimi fazami (The Distribution Constants of Organic Compounds between Two Liquid Phases), no. 5, Gorki: Gorki State Univ., 1979. p. 29.
  14. Lisitsyn, Yu.A., Makarova, O.N., and Kargin, Yu.M., Electrochemical amination: VII. Introduction of amino group into aromatic ring, Russ. J. Gen. Chem., 1999, vol. 69, p. 275.
  15. Damaskin, B.B., Nekrasov, L.N., Petriy, O.A., Podlovchenko, B.I., Stenina, E.V., and Fedorovich, N.V., Elektrodnye protsessy v rastvorakh organicheskikh soedinenii (Electrode Processes in Solutions of Organic Compounds), Moscow: Moscow Univ., 1985.
  16. Fatouros, N., Krulic, D., and Larabi, N., Electrochemical kinetics of the Ti(IV)/Ti(III) couple in sulfuric acid, J. Electroanal. Chem., 2004, vol. 568, p. 55.
  17. Lisitsyn, Yu.A., Busygina, N.V., Zyavkina, Yu.I., and Shtyrlin, V.G., Electrochemical amination. Ti(IV)/Ti(III) mediator system in aqueous solutions of sulfuric acid, Russ. J. Electrochem, 2010, vol. 46, p. 512.
  18. Remy, H., Lehrbuch der Anorganischen Chemie, Band II, Leipzig: Akademische Geest & Portig K.-C., 1961.