Kinetics and mechanism of uncatalyzed and ruthenium(lll) catalyzed oxidation of allyl alcohol by N-bromosuccinimide in aqueous alkaline medium

Abstract

The title reaction is carried out in aqueous alkaline medium and is first order in (NBS] both in the presence and absence of ruthenium(III) catalyst. However, the order in [allyl alcohol] is unity in the absence and fractional in the presence of Ru(III) catalyst. Increase in [OH^-] accelerates the reaction rate while the added succinimide retards the reaction rate in both the cases. Increase in the ionic strength and <i>t</i>-butanol content in the reaction medium have negligible effect in both the cases. A mechanism involving the hypobromate ion as the reactive species of the oxidant has been proposed. The reaction constants of individual steps of reaction mechanism have been evaluated.