Kinetics and Mechanism of the Oxidation of Alcohols by N-Bromoacetamide in Alkaline Solution

Article abstract of DOI:10.1021/jo00167a034

The kinetics of the oxidation of seven secondary alcohols by N-bromoacetamide has been studied in alkaline solution.The main product of the oxidation is the corresponding ketone.The reaction is first order with respect to the oxidant and alcohol.The oxidation of benzhydrol-α-d indicates the absence of a primary kinetic isotope effect.The rate decreases with the increase in the concentration of hydroxide ion.Addition of acetamide decreases the reaction rate.The rates were determined at four different temperatures, and the activation parameters were evaluated.Theactivation enthalpies and entropies of the oxidation of the seven alcohols are linearly related.Hypobromite ion has been postulated as the reactive oxidizing species.A mechanism involving rate-determining nucleophilic attack of hypobromite ion on the alcohol molecule has been proposed.