Kinetics and Mechanism of Oxidation of L-Threonine in Acid Media by Sodium N-Chloro-p-toluenesulfonamide

Article abstract of DOI:10.1021/j150624a025

Kinetics of oxidation of L-threonine in the presence of HCl, HClO4, and H2SO4 by chloramine-T (CAT) has been investigated at 35 deg C.The reactions follow identical kinetics in all acids, being first order in CAT, fractional order in substrate and Cl^- ion, and of an inverse fractional order in +>.Variation of ionic strength and addition of the reaction product, p-toluenesulfonamide, or the ions SO4^2- and ClO4^- had no effect on the rate.Decrease of dielectric constant of the medium by adding methanol decreased the rate.The solvent isotope effect was studied by using heavy water.The reactions were studied at different temperatures, and activation parameters have been computed.Mechanisms proposed and the derived rate laws are consistent with the observed kinetics.The rate constants predicted by the derived rate laws, as the concentrations of H⁺ ion, substrate, and Cl^- ion change, are in excellent agreement with the observed rate constants, thus further justifying these rate laws and hence the proposed mechanistic schemes.