Kinetics and mechanism of oxidation of secondary alcohols by bis(2,2'-bipyridyl)copper(II) permanganate

The oxidation of secondary alcohols by bis(2,2'-bipyridyl) copper(II) permanganate (BBCP) in aqueous acetic acid leads to the formation of corresponding ketones. The reaction is first order with respect to BBCP and the alcohols. The reaction rates have been determined at different temperatures and the activation parameters have also been calculated. The reaction rate increases with increase in the concentration of H+ ions. The oxidation of benzhydrol-alpha-d exhibits a substantial kinetic isotope effect (k(H)/k(D) = 5.34). With increase in the amount of acetic acid in the solvent mixture of acetic acid and water, the rate increases. Addition of 2,2'-bipyridine and acrylonitrile has no effect on the rate. Suitable mechanism has been proposed.