Oxidation by cobalt(III) acetate. Part 4. Kinetics and mechanism of the oxidation of glycols in acetic acid

Abstract

The oxidative cleavage of 1,2-glycols by cobalt(III) acetate in acetic acid was studied kinetically in order to clarify the reaction mechanism. The rates were first-order in both cobalt(III) acetate and substrate for the oxidation of all the diols used. cis-Cyclopentane-1,2-diol and decalin-9,10-diol were more rapidly oxidized than the corresponding trans-isomers, respectively, whereas cis-cyclohexane-1,2-diol was more slowly oxidized than the trans-isomer. The oxidation of trans-2-methoxycyclohexanol was much slower than that of the corresponding diol. The mechanism involving the formation of a bidentate complex between cobalt(III) acetate dimer and glycol is discussed.