KINETICS OF BAEYER-VILLIGER REACTION OF BENZALDEHYDES WITH PERBENZOIC ACID IN AQUOORGANIC SOLVENTS

The Baeyer-Villiger reaction of benzaldehydes with perbenzoic acid to give ultimately phenols and or benzoic acids has been studied kinetically in aquoorganic solvents at various pH's. The rate in acidic media increases with increasing pH and exhibits general base catalysis but not acid catalysis. The rate at pH > 10 is independent of pH with some kind of aldehydes, while the rate for others decreases with increasing pH. The effect of substituent in benzaldehydes on hydride shift affording benzoic acids gives a p value of 1.1-1.8. These results, together with solvent and temperature effects, are discussed in terms of a mechanism containing formation, ionization, and rearrangement of an addition intermediate between the carbonyl group and peracid. © 1969, American Chemical Society. All rights reserved.