Electrochemical amination of N,N-dimethylaniline

Yu.A. Lisitsyn

Kazan Federal University, Kazan, 420008 Russia

E-mail: *Yuri.Lisitsyn@kpfu.ru

Received January 17, 2021


ORIGINAL ARTICLE

Full text PDF

DOI: 10.26907/2542-064X.2021.1.20-28

For citation: Lisitsyn Yu.A. Electrochemical amination of N,N-dimethylaniline. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2021, vol. 163, no. 1, pp. 20–28. doi: 10.26907/2542-064X.2021.1.20-28. (In Russian)

Abstract

The process of indirect cathodic amination of N,N-dimethylaniline using the Ti(IV) – NH2OH system was studied in aqueous solutions of 7–16 M sulfuric acid at 40 ?C. An increase in the acid concentration was accompanied by a raise in the efficiency of amine radical cation substitution. In 16 M H2SO4, N,N-dimethyl-p- and N,N-dimethyl-m-phenylenediamines (2:3) were obtained with the total current and dimethylaniline yields of 94% and 100%, respectively. Comparative analysis of the results of amination of N,N-dimethylaniline and aniline in the sulfuric acid media was carried out.

Keywords: cathode, Ti(IV)/Ti(III) mediator system, hydroxylamine, N,N-dimethylaniline, amine radical cation aromatic substitution

References

  1. Lisitsyn Yu.A., Makarova O.N., Kargin Yu.M. Electrochemical amination: VII. Introduction of amino group into aromatic ring. Russ. J. Gen. Chem., 1999, vol. 69, no. 2, pp. 275–279.
  2. Lisitsyn Yu.A., Kargin Yu.M. Electrochemical amination of unsaturated and aromatic compounds. Russ. J. Electrochem., vol. 36, no. 2, pp. 89–99. doi: 10.1007/BF02756893.
  3. Lisitsyn Yu.A., Busygina N.V., Kargin, Yu.M. Electrochemical cation-radical amination of aromatic compounds. Ross. Khim. Zh., 2005, vol. 49, no. 5, pp. 121–128. (In Russian)
  4. Fatouros N., Krulic D., Larabi N. Electrochemical kinetics of the Ti(IV)/Ti(III) couple in sulfuric acid. J. Electroanal. Chem., 2004, vol. 568, nos. 1–2, pp. 55–64. doi: 10.1016/j.jelechem.2004.01.006.
  5. Lisitsyn Yu.A., Busygina N.V., Zyavkina Yu.I., Shtyrlin V.G. Electrochemical amination. Ti(IV)/Ti(III) mediator system in aqueous solutions of sulfuric acid. Russ. J. Electrochem., 2010, vol. 46, no. 5, pp. 512–523. doi: 10.1134/S1023193510050046.
  6. Lisitsyn Yu.A., Kargin Yu.M. Electrochemical amination. III. Reactivity of aromatic compounds. Russ. J. Gen. Chem., 1993, vol. 63, no. 11, pt. 2, pp. 1764–1766.
  7. Michejda Ch.J., Campbell D.H. Amphoteric amino radicals. Tetrahedron Lett., 1977, vol. 18, no. 6, pp. 577–580. doi: 10.1016/S0040-4039(01)92698-X.
  8. Damaskin B.B., Petrii O.A. Praktikum po elektrokhimii [Laboratory Course in Electrochemistry]. Mosсow, Vyssh. Shk., 1991. 288 p. (In Russian)
  9. Librovich N.B. Maiorov V.D. Ionic-molecular composition of aqueous sulfuric acid solutions at 25?. Bull. Acad. Sci. USSR, Div. Chem. Sci., 1977, vol. 26, no. 3, pp. 621–623. doi: 10.1007/BF01179485.
  10. Damaskin B.B., Petrii O.A., Tsirlina G.A. Elektrokhimiya [Electrochemistry]. St. Petersburg, Lan', 2015. 672 p. (In Russian)
  11. Lisitsyn Yu.A., 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, pp. 1294–1297. doi: 10.1134/S102319351813027X.
  12. Lisitsyn Yu.A. Electrochemical amination of para-chloroaniline. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2019, vol. 161, no. 2, pp. 222–230. doi: 10.26907/2542-064X.2019.2.222-230. (In Russian)
  13. Lisitsyn Yu.A., Sukhov A.V. Electrochemical amination of isomeric chloroanilines in aqueous solutions of sulfuric acid. Russ. J. Electrochem., 2020, vol. 56, no. 5, pp. 426–430. doi: 10.1134/S1023193520050080.
  14. Citterio A., Gentile A., Minisci F., Navarrini V., Serravalle M., 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, pp. 4479–4482. doi: 10.1021/jo00197a030.
  15. Ingold C.K. Structure and Mechanism in Organic Chemistry. Ithaca, London, Cornell Univ. Press, 1969. 1266 p.
  16. Nomenklaturnye pravila IYuPAK po khimii. T. 5. Fizicheskaya organicheskaya khimiya [IUPAC Nomenclature Rules for Chemistry]. Vol. 5: Physical organic chemistry. Moscow, VINITI, 1985. 380 p. (In Russian)
  17. Sykes P. A Guidebook to Mechanism in Organic Chemistry. Longman Publ. Group, 1986. 416 p.


The content is available under the license Creative Commons Attribution 4.0 License.