Mechanistic and kinetic aspects of the direct electrochemical oxidation of 4-t-butyltoluene

The direct electrochemical oxidation of 4-t-butyltoluene at graphite electrodes in methanol, using NaClO4 as electrolyte, as been investigated in order to obtain an insight into the mechanism and kinetics of the anodic reactions taking place. It is shown that an increase in current density affects the product distribution, leading to a better yield of the target product 4-t-butylbenzaldehyde dimethyl acetal and a lower percentage of unknowns at the expense of an increase in electrical charge. It is suggested that oxidation takes place by two mechanisms : a direct one involving oxidation of the substrate at the electrode, and an indirect one where a pool of solvent radicals assists in the oxidation process. Further evidence is provided for reaction mechanisms in studies where the substrate loading is varied, and also where the ratio of substrate to solvent is varied ; when the concentration of the substrate is high, there is evidence of the formation of dimers and other unknowns. Under certain conditions, these anodic reactions can be regarded as parallel consecutive second order reactions. The role played by the solvent is confirmed by kinetic data.