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

Yu. A. Lisitsyn Yu. A. Lisitsyn , A. V. Sukhov A. V. Sukhov
Российский электрохимический журнал
Abstract / Full Text

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.

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

    Yu. A. Lisitsyn & A. V. Sukhov

  1. Minisci, F., Novel Applications of Free-Radical Reactions in Preparative Organic Chemistry, Synthesis, 1973, no. 1, p. 1.
  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.
  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.
  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.
  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. Ingold, C.K, Structure and mechanism in organic chemistry, Ithaca and London: Cornell University press, 1969.
  7. Sykes, P., A Guidebook to Mechanisms in Organic Chemistry, Longman Publishing Group, 1986.
  8. Korenman, I.M., Ekstraktsiya v analize organicheskikh veshchestv (Extraction in the analysis of organic compounds), Moscow: Khimiya, 1977 (in Russian).
  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).
  10. Chemical encyclopedia, vol. 5, Knunyants I.L., Ed., Moscow: Soviet encyclopedia, 1998, p. 285 (in Russian).
  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.
  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.
  13. Remy, H., Lehrbuch der Anorganischen Chemie, Band II, Leipzig: Akademische Verlagsgesellschaft Geest & Portig K.-C, 1961.
  14. Zil’berman, E.N., Reaktsii nitrilov (Reactions of nitriles), Moscow: Khimiya, 1971 (in Russian).
  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.
  16. Chemical encyclopedia, vol. 1, Knunyants I.L., Ed., Moscow: Soviet encyclopedia, 1998, p. 164 (in Russian).