Russian Journal of Electrochemistry

, Volume 54, Issue 11, pp 886–892 | Cite as

Electrochemical Amination of Chlorobenzene in Aqueous-Organic Solutions of Sulfuric Acid

  • Yu. A. LisitsynEmail author
  • A. V. Sukhov


The process of electrochemical amination of chlorobenzene using hydroxylamine and the Ti(IV)/Ti(III) mediator system is studied in aqueous solutions of 6–16 M sulfuric acid containing acetic acid or acetonitrile. The substitution products in these media are isomeric chloroanilines and chlorophenylenediamines, with the exception of 5-chloro-1,3-isomer, phenylenediamines, and aniline. The overall current efficiency of amino compounds corresponding under the experimental conditions to the efficiency by hydroxylamine can reach 71%. Para- and ortho-chloroanilines are obtained in 6 M sulfuric acid and 11.1 M acetic acid with the weight fraction and current efficiency of 97 and 51%, respectively.


cathode Ti(IV)/Ti(III) mediator system hydroxylamine amino cation–radical chlorobenzene cation–radical aromatic substitution chloroanilines chlorophenylenediamines 


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  1. 1.
    Minisci, F., Novel Applications of Free-Radical Reactions in Preparative Organic Chemistry, Synthesis, 1973, no. 1, p. 1.Google Scholar
  2. 2.
    Citterio, A., Gentile, A., Minisci, F., Navarrini, V., Sarravalle, M., and Ventura, S., 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, p. 4479.CrossRefGoogle Scholar
  3. 3.
    Lisitsyn, Yu.A., and Sukhov, A.V., Electrochemical Amination. Functionalization of Anisole in Solutions of 4.0–6.0M H2SO4 and Acetic Acid, Russ. J. Electrochem., 2011, vol. 47, p. 1180.CrossRefGoogle Scholar
  4. 4.
    Lisitsyn, Yu.A., and Sukhov, A.V., Electrochemical Amination of Anisole in 4–6M Solutions of H2SO4 and Acetonitrile, Russ. J. Electrochem., 2013, vol. 49, p. 91.CrossRefGoogle Scholar
  5. 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.CrossRefGoogle Scholar
  6. 6.
    Ingold, C.K, Structure and mechanism in organic chemistry, Ithaca and London: Cornell University press, 1969.Google Scholar
  7. 7.
    Sykes, P., A Guidebook to Mechanisms in Organic Chemistry, Longman Publishing Group, 1986.Google Scholar
  8. 8.
    Korenman, I.M., Ekstraktsiya v analize organicheskikh veshchestv (Extraction in the analysis of organic compounds), Moscow: Khimiya, 1977 (in Russian).Google Scholar
  9. 9.
    Korenman, I.M., Konstanty raspredeleniya organicheskikh veshchestv mezhdu dvumya zhidkimi fazami (The distribution constants of organic compounds between two liquid phases), Issue 5, Gor’ki: Gor’ki State Univ., 1979, pp. 29–30 (in Russian).Google Scholar
  10. 10.
    Chemical encyclopedia, vol. 5, Knunyants I.L., Ed., Moscow: Soviet encyclopedia, 1998, p. 285 (in Russian).Google Scholar
  11. 11.
    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.CrossRefGoogle Scholar
  12. 12.
    Lisitsyn, Yu.A., Kargin, Yu.M., and Busygina, N.V., Electrochemical radical cation amination of aromatic compounds, Ross. Khim. Zhurn., 2005, vol. 49, no. 5, p. 121.Google Scholar
  13. 13.
    Remy, H., Lehrbuch der Anorganischen Chemie, Band II, Leipzig: Akademische Verlagsgesellschaft Geest & Portig K.-C, 1961.Google Scholar
  14. 14.
    Zil’berman, E.N., Reaktsii nitrilov (Reactions of nitriles), Moscow: Khimiya, 1971 (in Russian).Google Scholar
  15. 15.
    Librovich, N.B., and Maiorov, V.D., Ionic–molecular composition of aqueous sulfuric acid solutions at 25-degrees, Bull. Acad. Sci. USSR Div. Chem. Sci., 1977, vol. 26, no. 3, p. 621.CrossRefGoogle Scholar
  16. 16.
    Chemical encyclopedia, vol. 1, Knunyants I.L., Ed., Moscow: Soviet encyclopedia, 1998, p. 164 (in Russian).Google Scholar

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© Pleiades Publishing, Ltd. 2018

Authors and Affiliations

  1. 1.Butlerov Chemical InstituteKazan (Volga) Federal UniversityKazanRussia

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