85695-75-6Relevant academic research and scientific papers
Benzenesulphenanilidyl Radicals. Reactivity of 4'-Methoxy- and 4'-Methoxy-2-nitro-benzenesulphenanilidyl Radicals
Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
, p. 3049 - 3054 (2007/10/02)
Oxidation of 4'-methoxybenzenesulphenanilide (1a) with lead dioxide at 30 deg C afforded the NN-bis(phenylthio)-p-anisidine (7a) and 2,7-dimethoxypheazine (3a) together with minor amounts of diphenyl (4a), whereas at 10 deg C almost exclusive formation of compound (7a) and the o-benzoquinone di-imine (8a) was observed; compound (8a) was found to be thermally unstable and to give, quantitatively, compounds (4a) and (3a).The reaction products are rationalized by assuming that 4'-methoxybenzenesulphenanilidyl radicals (2a), produced by oxidation of compound (1a), undergo Cortho-N coupling to give the dimer (9a), which is responsible for the reaction products observed.A comparable trend was observed by producing the radical (2a) from reaction of compound (1a) with t-butoxy-radicals and by thermal decomposition of compound (7a).These findings rule out the nitrene mechanism previously suggested for the formation of compound (3) from oxidation of the reagent (1a).Evidence has been found that Cortho-N coupling is the main reaction path, exhibited also by 4'-methoxy-2-nitrobenzenesulphenanilidyl radicals (2c) generated from the corresponding anilide (1c) by reaction with t-butoxy-radicals or oxidation with lead dioxide, which thus rejects a previous claim that the radicals (2) (Ar = Ph and Ar = C6H4NO2-o) exhibit different chemical behaviour.
