Studies on Sulfenamides. XI. : Electron Spin Resonance Spectra of Radical Cations Electrochemically Generated from N, N-Disubstituted 2-Nitrobenzenesulfenamides

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The paramagnetic species formed by in situ electrochemical oxidation of N-(2-nitrophenyl-thio)dibenzylamine (1) and three N-methyl-4'-substituted 2-nitrobenzenesulfenanilides (4'-CH₃ (2), 4'-C(CH₃)₃ (3), 4'-COOC₂H₅ (4)) have been identified as the radical cations derived from the parent sulfenamides by one-electron transfer. On the other hand, the radicals generated from three 4'-unsubstituted N-alkyl-2-nitrobenzenesulfenanilides (N-CH₃ (5), N-C₂H₅ (6), N-CH₂C₆H₅ (7))have been identified as the radical cations of N, N-dialkyl-diphenoquinone-diimines formed by dimerization of the sulfenanilide radical cations and further oxidation of the dimers. From the voltammetric data, it is proposed that the dimerization takes place before the cleavage of the S-N bond in the sulfenanilide radical cations.