Skip to main content
Log in

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

  • Published:
Russian Journal of Electrochemistry Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Minisci, F., Novel Applications of Free-Radical Reactions in Preparative Organic Chemistry, Synthesis, 1973, no. 1, p. 1.

    Google Scholar 

  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.

    Article  CAS  Google Scholar 

  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.

    Article  CAS  Google Scholar 

  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.

    Article  CAS  Google Scholar 

  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.

    Article  CAS  Google Scholar 

  6. Ingold, C.K, Structure and mechanism in organic chemistry, Ithaca and London: Cornell University press, 1969.

    Google Scholar 

  7. Sykes, P., A Guidebook to Mechanisms in Organic Chemistry, Longman Publishing Group, 1986.

    Google Scholar 

  8. Korenman, I.M., Ekstraktsiya v analize organicheskikh veshchestv (Extraction in the analysis of organic compounds), Moscow: Khimiya, 1977 (in Russian).

    Google Scholar 

  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. 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.

    Article  CAS  Google Scholar 

  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.

    CAS  Google Scholar 

  13. Remy, H., Lehrbuch der Anorganischen Chemie, Band II, Leipzig: Akademische Verlagsgesellschaft Geest & Portig K.-C, 1961.

    Google Scholar 

  14. Zil’berman, E.N., Reaktsii nitrilov (Reactions of nitriles), Moscow: Khimiya, 1971 (in Russian).

    Google Scholar 

  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.

    Article  Google Scholar 

  16. Chemical encyclopedia, vol. 1, Knunyants I.L., Ed., Moscow: Soviet encyclopedia, 1998, p. 164 (in Russian).

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yu. A. Lisitsyn.

Additional information

Original Russian Text © Yu.A. Lisitsyn, A.V. Sukhov, 2018, published in Elektrokhimiya, 2018, Vol. 54, No. 10S, pp. S62–S69.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lisitsyn, Y.A., Sukhov, A.V. Electrochemical Amination of Chlorobenzene in Aqueous-Organic Solutions of Sulfuric Acid. Russ J Electrochem 54, 886–892 (2018). https://doi.org/10.1134/S1023193518130268

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1023193518130268

Keywords

Navigation