Correlation analysis of reactivity in the oxidation of some para- substituted benzhydrols by triethylammonium chlorochromate in non-aqueous media

Triethylammonium chlorochromate (TriEACC) oxidation of some para-substituted benzhydrols (BH) in dimethylsulfoxide (DMSO) leads to the formation of corresponding benzophenones. The reaction was run under pseudo-first-order conditions. The reaction is catalyzed by hydrogen ions. The hydrogen ion dependence has the form: kobs=a+b[H+]. Various thermodynamic parameters for the oxidation have been reported and discussed along with the validity of isokinetic relationship. Oxidation of benzhydrol was studied in 18 different organic solvents. The rate data showing satisfactory correlation with Kamlet–Taft solvatochromic parameters (α, β and π∗) suggests that the specific solute–solvent interactions play a major role in governing the reactivity, and the observed solvent effects have been explained on the basis of solute–solvent complexation. A suitable mechanism of oxidation has been proposed.