Oxidation of secondary alcohols is an important part of synthetic organic chemistry. Various studies are carried out at different reaction conditions to determine the best mechanistic pathways. In our study, oxidation of different secondary alcohols was done by using Benzimidazolium Fluorochromate in Dimethyl Sulphoxide, which is a non-aqueous solvent. Oxidation resulted in the formation of ketonic compounds. The reaction showed first order kinetics both in BIFC and in the alcohols. Hydrogen ions were used to catalyze the reaction. We selected four different temperatures to carry out our study. The correlation within the activation parameters like enthalpies and entropies was in accordance with the Exnerʼs criterion. The deuterated benzhydrol (PhCDOHPh) oxidation exhibited an important primary kinetic isotopic effect (kH / kD = 5.76) at 298 K. The solvent effect was studied using the multiparametric equations of Taft and Swain. There was no effect of addition of acrylonitrile on the oxidation rate. The mechanism involved sigmatropic rearrangement with the transfer of hydrogen ion taking place from alcohol to the oxidant via a cyclic chromate ester formation.

The kinetics of oxidation of diols by morpholinium fluorochromate (MFC) has been studied in dimethyl sulfoxide (DMSO). Corresponding hydroxy carbonyl compounds are the main product of oxidation. The reaction is first order in MFC and follows Michaelis-Menten type of kinetics with respect to diols. The reaction is catalyzed by H+ ions. The hydrogen ion dependence has the form: kobs =a+ b[H+]. Oxidation of deuterated ethylene glycol showed substantial primary kinetic isotopic effect (kH / kD = 5.750 at 298 K). Thermodynamic parameters like enthalpy, entropy and free energy of activation are discussed and validity of the isokinetic relationships also established. We have used nineteen different organic solvents for carrying out our analysis. Taft and Swain’s multiparametric equations have been used for the solvent effect analysis. In our experiments rate constants have showed excellent correlation with Taft's Σσ* values along with negative values for the reaction constant ρ*. A suitable mechanistic pathway for the chromate ester formation has also been suggested.