The oxidation of diphenylhydroxylamine by benzoyl peroxide

Abstract

In the presence of a large excess of diphenylhydroxylamine the title reaction gives benzoic acid and diphenyl nitroxide according to the equation 2Ph₂NOH +(PhCO₂)₂→ 2Ph₂NO·+ 2PhCO₂H. The reaction is of the first order in both peroxide and hydroxylamine. Although this is one of the most clear-cut examples of molecule-induced homolysis known, no convincing evidence has been adduced in favour of any one mechanism. Substituent and isotope effects are consistent with an initial electron transfer from hydroxylamine to peroxide.