The Mechanism of the Oxidation of 2-Butenes by Sodium Bismuthate

Abstract

It was reported by the authors previously that carbonyl compounds and diacetoxyl derivatives are formed by the oxidation of olefins with sodium bismuthate in acetic acid and in chloro acetic acid. In this paper, the reaction of 2-butenes with the same reagent has been investigated to reveal the reaction mechanism. Acetaldehyde and 2, 3-diacetoxylbutane have been formed as oxidation products from 2-butenes in benzene-acetic acid mixtures. Molar ratio of 2, 3-diacetoxylbutane to acetaldehyde has increased with an increase of reaction time and of a fraction of acetic acid in the solvent, while the molar ratio has not changed with varying initial concentrations of 2-butenes and sodium bismuthate. Small amount of water accelerates the formation of acetaldehyde, but prevents that of DA. These experimental results agree well with the assumed mechanism of the oxidation. It is moreover concluded that bismuth(V) acetate is formed by the reaction of sodium bismuthate with acetic acid.