Article

Russian Journal of Electrochemistry

, Volume 47, Issue 11, pp 1205-1210

First online:

Dimerization and protonation reactions of nitrosonitrobenzenes radical anions

  • L. V. Mikhal’chenkoAffiliated withZelinskii Institute of Organic Chemistry, Russian Academy of Sciences
  • , M. A. SyroeshkinAffiliated withZelinskii Institute of Organic Chemistry, Russian Academy of Sciences
  • , M. Yu. LeonovaAffiliated withZelinskii Institute of Organic Chemistry, Russian Academy of Sciences
  • , A. S. MendkovichAffiliated withZelinskii Institute of Organic Chemistry, Russian Academy of Sciences
  • , A. I. RusakovAffiliated withYaroslavl State University
  • , V. P. Gul’tyaiAffiliated withZelinskii Institute of Organic Chemistry, Russian Academy of Sciences Email author 

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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.

Keywords

nitrosonitrobenzene electroreduction radical anions cyclic voltammetry controlled potential electrolysis protonation dimerization