Oxidation of aromatic secondary and tertiary amines by peroxydisulphate. A kinetic study

Abstract

The kinetics of the oxidation of aromatic secondary and tertiary amines by peroxydisulphate ion under aqueous basic conditions have been investigated. The reaction is first order in amine and first order in S2O82- ion. The order of the reactivity is found to be: N-methylaniline > N,N-dimethylaniline > aniline and N-ethylaniline > N,N-diethylaniline > aniline, and among each class: N-methylaniline > N-ethylaniline and N,N-dimethylaniline > N,N-diethylaniline. This reactivity is explained on the basis of a steric strain in the transition state super- imposed over the usual polar effects.