Mechanistic study of Pd(II) catalysed oxidation of maleic and crotonic acids by N-chlorosuccinimide in perchloric acid medium

Abstract

The kinetics of oxidation of maleic and crotonic acids by N-chlorosuccinimide (NCS) in perchloric acid are presented. Analysis of the results shows that the observed rates of oxidation indicate zero order in [substrate] and [H⁺]. First order dependence of the reactions on NCS at its lower concentrations tends to zero order in its higher concentration range. The

reaction rate increases with increase in [Pd(II)] but the order in [Pd(II)] is less than unity. The initial addition of Cl^- and five fold excess of added succinimide (NHS) do not affect the rate significantly. Increase in ionic strength has negligible effect on the rate while increase in acetic acid content in reaction medium decreases the rate. Mechanistic steps are discussed on

the basis of kinetic observations and products analysis.