An ESR study of the free-radical isomerization of the diphenylmercaptol of butanone
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Heated to 130°C in the presence of tert-butyl peroxide, the diphenylmercaptol of butanone reacts to give 2, 3-bis(phenylthio)butane, 1, 2-bis(phenylthio)butane, 2-phenylthio-2-butene, 2-phenylthiobutane, diphenyl disulfide, thiophenol, and butanone. Similar products are obtained by heating the mercaptol in the absence of the peroxide.
The radicals CH3C(SPh)2ĊHCH3(A), CH3Ċ(SPh)CH(SPh)CH3 (B), and SPh were identified in the product obtained from UV irradiation of the diphenylmercaptol of butanone in the presence of tert-butyl peroxide and 2-methyl-2-nitrosopropane, identification being through ESR study of the spin adducts formed with the nitro-sopropane. Appearance of these radicals supported the assumption that isomerization of the diphenylmercaptol of butanone in the presence of 2, 3-bis(phenylthio)butane proceeds through regrouping of the CH3C(SPh)2ĊHCH3 and CH3Ċ(SPh)CH(SPh)CH3 radicals, and 1,2-migration of the SPh groups.
KeywordsPeroxide Adduct Disulfide Butane Diphenyl
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