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

摘要

Kinetics of oxidation of five vicinal, four non-vicinal diols, and one of their monoethers by bis(2,2'-bipyridyl) copper(II) permanganate (BBCP), has been studied. The vicinal diols yielded the products arising out of the glycol bond fission, while the other diols yielded the hydroxycarbonyl compounds. The reaction is first-order with respect to BBCP. Michaeh's-Menten type kinetics were observed with respect to the diol. There is no effect of added 2,2'-bipyridine on the reaction. The oxidation of [1,1,2,2-~2H_4] ethanediol showed the absence of a primary kinetic isotope effect. A mechanism involving a glycol bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidised by a hydride-transfer mechanism as are monohydric alcohols.