Kinetics of Oxidation of Substituted Benzyl Alcohols by Quinolinium Dichromate

Article abstract of DOI:10.1021/jo00310a015

Quinolinium dichromate (QDC) oxidizes benzyl alcohol and substituted benzyl alcohols smoothly in dimethyl formamide, in the presence of acid.The reaction has unit dependence on each of the alcohol, QDC, and acid concentrations.Electron-releasing substituents accelerate the reaction, whereas electron-withdrawing groups retard the reaction, and the rate data obey Hammett's relationship.The reaction constant ρ was -1.67 +/- 0.08 at 313 K.The kinetic isotope effect, k_H/k_D, was 5.89 at 313 K.The reaction does not induce polymerization of acrylonitrile.The observed experimental data have been rationalized in terms of a hydride ion transfer in the rate-determining step.