Abstract
The title reaction gives products according to the following equations: a) Monoalkylhydroxylamine RNHOH+2DPPH→R-N=O+2DPPH2b) Dialkylhydroxylamine Me2NOH+2DPPH→1/2 Me2N (O) =CH2+1/2 Me2NOH+2DPPH2 (t-Bu) 2NOH+2DPPH→t-Bu-N=O+Me2C=CH2 (or t-BuOH) +2DPPH2The reaction is first-order with respect to both hydroxylamines and 1, 1-dipheny1-2-picrylhydrazyl and the first step in the reaction involves fromation of the corresponding nitroxides.
The effects of substituents and solvents on the reaction rate suggest a mechanism in which the nitroxide is formed by one-electron transfer from the nitrogen of the hydroxylamine followed by a proton transfer from the hydroxyl group.
