Skip to main content
SpringerLink
Log in

Dimerization and protonation reactions of nitrosonitrobenzenes radical anions

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

Abstract

The electrochemical behavior of 2-, 3-, and 4-nitrosonitrobenzenes (NNB) in DMF (with Bu4NClO4 suppoting salt) in the presence and in the absence of different proton donors (water, phenol, benzoic, acetic, chloroacetic, and sulfuric acids) is studied by the methods of cyclic voltammetry, chronoamperometry and also by electrolysis at the controlled potential. The electrochemical reduction of these compounds is shown to preferentially afford either monomeric (N-nitrophenylhydroxylamines) or dimeric (azoxy compounds) products, which is determined by the interplay between reactions of protonation and dimerization of NNB radical anions. The dimerization reactions proceed fast and reversibly to afford the corresponding dimeric dianions with the basicity much higher as compared with NNB radical anions as the result of which the monomeric products are formed in the presence of “strong” proton donors and the dimeric products form in the presence of “weak” proton donors. Like the effective rate of formation of dimeric products, the basicity of radical anions increases in the row 4- < 3- < 2-NNB.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Gowenlock, B.G. and Richter-Addo, G.B., Chem. Rev., 2004, vol. 104, p. 3315.

    Article  CAS  Google Scholar 

  2. Adam, W. and Krebs, O., Chem. Rev., 2003, vol. 103, p. 4131.

    Article  CAS  Google Scholar 

  3. Zuman, P. and Shah, B., Chem. Rev., 1994, vol. 94, p. 1621.

    Article  CAS  Google Scholar 

  4. Bollo, S., Finger, S., Sturm, J.C., Nunez-Vergara, L.J., and Squella, J.A., Electrochim. Acta, 2007, vol. 52, p. 4892.

    Article  CAS  Google Scholar 

  5. Nunez-Vergara, L.J., Santander, P., Navarrete-Encina, P.A., Valenzuela, J., Sturm, J.C., and Squella, J.A., J. Electrochem. Soc., 2006, vol. 153, p. 144.

    Article  Google Scholar 

  6. Nunez-Vergara, L.J., Santander, P., Navarrete-Encina, P.A., and Squella, J.A., J. Electroanal. Chem., 2005, vol. 580, p. 135.

    Article  CAS  Google Scholar 

  7. Lipsztajn, M., Krygowski, T.M., Laren, E., and Galus, Z., J. Electroanal. Chem., 1974, vol. 57, p. 339.

    Article  CAS  Google Scholar 

  8. Steudel, E., Posdorfer, J., and Schindler, RN., Electrochim. Acta, 1995, vol. 40, p. 1587.

    Article  CAS  Google Scholar 

  9. Nunez-Vergara, L.J., Squella, J.A., Olea-Azar, C., Bollo, S., Navarrete-Encina, P.A., and Sturm, J.C., Electrochim. Acta, 2000, vol. 45, p. 3555.

    Article  CAS  Google Scholar 

  10. Asirvatham, M.R. and Hawley, M.D., J. Electroanal. Chem., 1974, vol. 57, p. 179.

    CAS  Google Scholar 

  11. Grimshaw, J., Electrochemical Reactions and Mechanisms in Organic Chemistry, Amsterdam: Elsevier, 2000.

    Google Scholar 

  12. Lipsztajn, M., Krygowski, T.M., Laren, E., and Galus, Z., J. Electroanal. Chem., 1974, vol. 54, p. 313.

    Article  CAS  Google Scholar 

  13. Fry, A.J., Supplement F2: The Chemistry of Amino, Nitroso, Nitro and Related Groups, Patai, S., Ed., New York: Wiley, 1996.

    Google Scholar 

  14. Zuman, P. and Fijalek, Z., J. Electroanal. Chem., 1990, vol. 296, p. 589.

    Article  CAS  Google Scholar 

  15. Syroeshkin, M.A., Mikhalchenko, L.V., Mendkovich, A.S., Gul’tyai, V.P., and Rusakov, A.I., Chem. Listy, 2009, vol. 103, p. 243.

    Google Scholar 

  16. Mendkovich, A.S., Syroeshkin, M.A., Mikhalchenko, L.V., Mikhailov, M.N., Rusakov, A.I., and Gul’tyai, V.P., Int. J. Electrochem., 2011, vol. 2011, ID 346043, doi 10.4061/2011/346043.

  17. Rusakov, A.I., Mendkovich, A.S., Gul’tyai, V.P., and Orlov, V.Yu., Struktura i reaktsionnaya sposobnost’ organicheskikh anion-radikalov (Structure and Reactivity of Organic Radical Anions), Moscow: Mir, 2005.

    Google Scholar 

  18. Panicheva, S.E. and Filanovskii, B.K., Zavod. Lab., 1989, vol. 55, p. 519.

    Google Scholar 

  19. Macias-Ruvalcaba, N.A. and Evans, D.H., J. Phys. Chem. B, 2005, vol. 109, p. 14642.

    Article  CAS  Google Scholar 

  20. Melnikov, E.B., Suboch, G.A., and Belyaev, E.Y., Russ. J. Org. Chem., 1995, vol. 31, p. 1849.

    CAS  Google Scholar 

  21. Alway, F.Y., Ber. Deutsch. Chem. Ges., 1903, vol. 36, p. 2530.

    Article  CAS  Google Scholar 

  22. McIntyre, J. and Simpson, J.C.E., J. Chem. Soc., 1952, p. 2606.

  23. Kuhn, R. and Weygand, F., Ber. Deutsch. Chem. Ges., 1936, vol. 69, p. 1969.

    Article  Google Scholar 

  24. Brand, K., Ber. Deutsch. Chem. Ges., 1905, vol. 4, p. 4006.

    Article  Google Scholar 

  25. Lipilin, D.L., Churakov, A.M., Ioffe, S.L., Strelenko, Y.A., and Tartakovsky, V.A., Eur. J. Org. Chem., 1999, p. 29.

  26. http://www.elchsoft.com/DigiElch/Default.aspx

  27. Hammerich, O. and Parker, V.D., Acta Chem. Scand. B, 1981, vol. 35, p. 341.

    Article  Google Scholar 

  28. Amatore, C., Pinson, J., and Saveant, J.-M., J. Electroanal. Chem., 1982, vol. 137, p. 143.

    Article  CAS  Google Scholar 

  29. Hammerich, O. and Parker, V.D., Acta Chem. Scand., 1983, vol. 37, p. 379.

    Article  Google Scholar 

  30. Costentin, C. and Saveant, J.-M., J. Electroanal. Chem., 2004, vol. 564, p. 99.

    Article  CAS  Google Scholar 

  31. Abe, T. and Ikegami, Y., Bull. Chem. Soc. Jpn., 1976, vol. 49, p. 3227.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow, 119991, Russia

    L. V. Mikhal’chenko, M. A. Syroeshkin, M. Yu. Leonova, A. S. Mendkovich & V. P. Gul’tyai

  2. Yaroslavl State University, Yaroslavl, Russia

    A. I. Rusakov

Authors
  1. L. V. Mikhal’chenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. A. Syroeshkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Yu. Leonova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. S. Mendkovich
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. I. Rusakov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. V. P. Gul’tyai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to V. P. Gul’tyai.

Additional information

Original Russian Text © L.V. Mikhal’chenko, M.A. Syroeshkin, M.Yu. Leonova, A.S. Mendkovich, A.I. Rusakov, V.P. Gul’tyai, 2011, published in Elektrokhimiya, 2011, Vol. 47, No. 11, pp. 1289–1294.

This paper is published based on the materials of the 17th All-Russian Conference on the Electrochemistry of Organic Compounds, Tambov (EKhOS-2010).

Rights and permissions

Reprints and permissions

About this article

Cite this article

Mikhal’chenko, L.V., Syroeshkin, M.A., Leonova, M.Y. et al. Dimerization and protonation reactions of nitrosonitrobenzenes radical anions. Russ J Electrochem 47, 1205–1210 (2011). https://doi.org/10.1134/S1023193511110127

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1023193511110127

Keywords

Search

Navigation