, Volume 47, Issue 11, pp 1205-1210
Date: 02 Dec 2011

Dimerization and protonation reactions of nitrosonitrobenzenes radical anions

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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.

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).