OXIDATION OF ALIPHATIC KETONES BY BROMAMINE-B: A KINETIC STUDY

Article abstract of DOI:10.1016/S0040-4020(01)82067-6

The kinetics of oxidation of propan-2-one, butan-2-one, pentan-2-one, pentan-3-one and 4-methyl pentan-2-one by sodium N-bromobenzenesulphonamide or bromamine-B (BAB) in perchloric acid medium was studied at 30 deg C.The rate shows a first order dependence each on and +> and is independent of .Variation of ionic strength of medium and addition of the reaction product benzenesulphonamide have no effect on the rate and the dielectric effect is positive.The proposed mechanism involves acid catalysed enolisation of ketone in the rate limiting step followed by a fast interaction with the oxidant.This is supported by the magnitude of inverse solvent isotope effect of 1.62 +/- 0.01 observed in D2O medium.Activation parameters Ea, ΔH^*, ΔS^*, ΔG^* and log A have been calculated by studying the reaction at different temperatures (293-309 K).