STRUCTURE-REACTIVITY CORRELATION IN THE OXIDATION OF SUBSTITUTED BENZYL ALCOHOLS BY IMIDAZOLIUM FLUOROCHROMATE

Abstract

Normal 0 Oxidation of benzyl alcohol and some ortho -, meta - and para -monosubstituted ones by imidazolium fluorochromate (IFC) in dimethyl sulphoxide (DMSO) leads to the formation of corresponding banzaldehydes. The reaction is first order each in both IFC and the alcohol. The reaction is promoted by hydrogen ions; the hydrogen‑ion dependence has the form k obs = a + b [H + ]. Oxidation of a , a ‑dideuteriobenzyl alcohol (PhCD 2 OH) has exhibited a substantial primary kinetic isotope effect (k H /k D = 5.86 at 298 K). The reaction has been studied in nineteen organic solvents and the effect of solvent analysed using Taft's and Swain's multi-parametric equations. The rates of oxidation of para ‑ and meta ‑substituted benzyl alcohols have been correlated in terms of Charton’s triparametric LDR equation whereas the oxidation of ortho -substituted benzyl alcohols with tetraperametric LDRS equation. The oxidation of para -substituted benzyl alcohols is more susceptible to the delocalization effect than that of ortho - and meta - substituted compounds, which display a greater dependence on the field effect. The positive value of h suggests the presence of an electron-deficient reaction centre in the rate-determining step. The reaction is subjected to steric acceleration by the ortho -substituents. A suitable mechanism has been proposed.