CORRELATION ANALYSIS OF REACTIVITY IN THE OXIDATION OF SUBSTITUTED BENZALDEHYDES BY BIS[DIPYRIDINESILVER(I)]DICHROMATE

Abstract

Oxidation of thirty six monosubstituted benzaldehydes by bis[dipyridinesilver (I)] dichromate (BDSD) in dimethylsulphoxide (DMSO), leads to the formation of corresponding benzoic acids. The reaction is of first order with respect to BDSD. A Michaelis-Menten type kinetics was observed with respect to the reactants. The reaction is promoted by hydrogen ions; the hydrogen‑ion dependence has the form k obs = a + b [H + ]. The oxidation of [ 2 H]benzaldehyde (PhCDO) exhibited a substantial primary kinetic isotope effect. The reaction was studied in nineteen different organic solvents and the effect of solvent was analysed using Taft's and Swain's multi-parametric equations. The rates of the oxidation of para‑ and meta‑substituted benzaldehydes showed excellent correlation in terms of Charton’s triparametric LDR equation, whereas the oxidation of ortho-substituted benzaldehydes were correlated well with tetraperametric LDRS equation. The oxidation of para-substituted benzaldehydes is more susceptible to the delocalized effect than is the oxidation 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.