Kinetics and mechanism of oxidation of some para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B(CAB)

The kinetics of oxidation of ethyl S-phenylmercapto acetate and several para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B have been studied in 50% (V/V) aqueous ethanol medium containing phosphate buffer. This oxidation is of first order with respect to substrate and zero order with respect to oxidant. A catalytic effect of mercury is observed and the order with respect to mercury is fractional (0.74). The increase in pH decreases the rate of oxidation and the order with respect to H⁺ is 0.05. In general electron-releasing substituents accelerate the rate while electron-attracting groups retard the rate. A good correlation is found to exist between log k ₁ and Hammett constants. Susceptibility of the reaction to the steric effect of ortho-substituents has been analyzed in the light of application of Taft's steric energy parameters. © John Wiley & Sons, Inc.