Kinetics of Oxidaton of Aliphatic Ketones with Bromamine-T in Acid Medium

Article abstract of DOI:10.1246/bcsj.61.543

The kinetics of oxidation of 2-propanone, 2-butanone, 2-pentanone, 3-pentanone, and 4-methyl-2-pentanone by sodium salt of N-bromo-p-toluenesulfonamide or bromamine-T (BAT) in presence of HClO4 was studied at 30 degC.The rate law is: .Variation of ionic strength of medium or addition of reaction product p-toluenesulfonamide have no effect on the rate.The dielectric effect is positive.The acid-catalyzed enolization of ketone is assumed to be the rate-limiting step and enolization rate coefficients have been calculated.Proton inventory studies made in H2O-D2O mixtures have been employed to calculate the isotropic fractionation factors.Isokinetic temperature is 320 K indicating enthalpy as a controlling factor.