Amine oxidation. Part 16. Kinetic studies on the oxidation of some aminoalcohols by vanadium(V) ions in aqueous perchloric acid

Abstract

The rate of oxidation of aminoalcohols by vanadium(V) ion in aqueous perchloric acid is first order with respect to vanadium(V) and the aminoalcohol. The dependence of the rate on the acidity of the reaction mixture is indicative of the active species being V(OH)₃²⁺. The influence of substrate structure on the rate of oxidation has been studied with fifteen aminoalcohols, two deuteriated aminoalcohols, and two aminoethers. In the proposed mechanism for the oxidation, the rate-determining step is the hqmolytic decomposition of an aminoalcohol–vanadium(V) complex and involves hydrogen-atom abstraction from the C–H bond α to the hydroxy group.