Kinetics and mechanism of the oxidative regeneration of carbonyl compounds from oximes by [bis(trifluoroacetoxy)iodo]benzene

The oxidation of several aldo- and keto-oximes by [bis(trifluoroacetoxy)iodo] benzene (TFAIB), in aqueous acetic acid exhibits first order dependence on both the oxime and TFIAB. The oxidation of ketoximes is slower than that of aldoximes. The oxidation of aliphatic oximes correlates well in terms of Pavelich-Taft dual substituent-parameter equation. The reaction constants have positive values. The low positive value of the polar reaction constant indicates a nucleophilic attack by TFIAB on the carbonyl carbon. The reaction is subject to steric hindrance by the alkyl group. A mechanism involving the formation of a cyclic activated complex in the rate-determining step has been proposed.