Kinetics and mechanism of oxidation of substituted benzaldehydes by 4-(dimethylamino)pyridinium chlorochromate

Kinetics of oxidation of substituted benzaldehydes by 4-(dimethylamino)pyridinium chlorochromate (DMAPCC) in protic solvent system has been studied at 303 K. The product of oxidation has been identified as benzoic acid. A unit order dependence of the reaction with respect [DMAPCC] and [benzaldehyde] has been observed. The reaction has been found to be catalysed by H+ stop ions. Decrease in the dielectric constant of the medium decreases the rate. To study the effect of structure reactivity relationships some para-substituted benzaldehydes were subjected to oxidation kinetics by DMAPCC at four different temperatures and thermodynamic parameters were calculated. The isokinetic plot and Exner plot shows that all the para-substituted benzaldehydes are oxidised by the same mechanism. The Hammett plot is linear with positive rho value. From the observed kinetic results a suitable mechanism was proposed.