Oxidation of α,β-Unsaturated Alcohols by Quinaldinium Fluorochromate

Abstract

The kinetics of oxidation of α,β-unsaturated alcohols (allyl alcohol, Crotyl alcohol, Cinnamyl alcohol) by quinaldinium fluorochromate has been studied in aqueous acid medium at 313 K. α,β-unsaturated alcohols were converted to the corresponding acrolein, crotonaldehyde and cinnamaldehyde. The reaction is first order each in oxidant, substrate and H+. The decrease in dielectric constant of the medium increases the rate of the reaction. Increase in ionic strength by the addition of sodium perchlorate has no effect on the rate constant. There is no polymerization with acrylonitrile. The reaction has been conducted at four different temperatures and activation parameters were calculated. From the observed kinetic results a suitable mechanism consistent with rate law has been proposed. The relative reactivity order was found to be Cinnamyl alcohol > Crotyl alcohol > Allyl alcohol.