Статья
2018

Electrochemical Amination. Selective Functionalization of para- and ortho-Anisidines in Aqueous Sulfuric Acid Solutions


Yu. A. Lisitsyn Yu. A. Lisitsyn , A. V. Sukhov A. V. Sukhov
Российский электрохимический журнал
https://doi.org/10.1134/S102319351813027X
Abstract / Full Text

The processes of the electrochemical amination of para- and ortho-anisidines using hydroxylamine and the Ti(IV)/Ti(III) mediator system are studied in aqueous solutions of 4–14 M sulfuric acid. The functionalization of para-anisidine results in the formation of 4-methoxy-1,3- and 4-methoxy-1,2-phenylenediamines with a current efficiency of up to 64.3 and 0.56%, respectively. When ortho-anisidine is aminated, 4-methoxy-1,3-phenylenediamine is the only substitution product; its current efficiency reaches 61%. Under the conditions that favor synthesis of 4-methoxy-1,3-phenylenediamine from anisidines, full conversion of hydroxylamine is observed and the current efficiency of the diamino compound corresponds to the yield per amino radical source.

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

    Yu. A. Lisitsyn & A. V. Sukhov

References
  1. 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.
  2. Lisitsyn, Yu.A., Kargin, Yu.M., Electrochemical amination. II. Effect of electrolyte acidity, Russ. J. Gen. Chem., 1993, vol. 63, p. 917.
  3. Korenman, I.M., Konstanty raspredeleniya organicheskikh veshchestv mezhdu dvumya zhidkimi fazami (The distribution constants of organic compounds between two liquid phases), Issue 1, Gor’ki: Gor’ki State Univ., 1975, pp. 21–28 (in Russian).
  4. 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: Publishing House of the Moscow Univ., 1985, p. 258 (in Russian).
  5. 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.
  6. 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.
  7. Remy, H., Lehrbuch der Anorganischen Chemie, Band II, Leipzig: Akademische Verlagsgesellschaft Geest & Portig K.-C., 1961.