CORRELATION ANALYSIS OF REACTIVITY IN THE OXIDATION OF SUBSTITUTED BENZALDEHYDES BY QUINOLINIUM FLUOROCHROMATE

Jagrity Khatri, Anurag Choudhary, P Purohit, R Kumbhat, Vinita Sharma

Abstract


Oxidation of thirty six monosubstituted benzaldehydes by quinolinium fluorochromate (QFC) in dimethylsulphoxide (DMSO), leads to the formation of corresponding benzoic acids. The reaction is of first order with respect to QFC. 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 kobs=a +b[H+]. The oxidation of [2H]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.

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DOI: http://dx.doi.org/10.17628/ecb.2012.1.49-57

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