The kinetics and mechanism of oxidation of some primary and secondary alcohols with pyridinium dichromate (PDC) catalyzed by p-toluenesulphonic acid (TsOH) has been investigated in acetonitrile medium. The reaction exhibits first-order dependence on [PDC]. Michaelis-Menten dependence is observed on [alcohol]. TsOH enhances the rate of the reaction remarkably. Order dependence on [TsOH] is more than a first-order and less than a second-order. Pyridine retards the rate of oxidation significantly indicating the possibility of a parallel competitive reaction with TsOH. Studies indicate the formation of water even under anhydrous conditions. The kinetic results are analyzed in terms of Taft's original constants (a and Es) and the improved constants (cr* and El). Minor importance of steric effects is well justified by the low values of steric reaction constants.
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