Kinetics and mechanism of the oxidative regeneration of carbonyl compounds from oximes by quinolinium bromochromate

Geeta Bishnoi, R. S. Sindal, Pallavi Mishra, Pradeep K. Sharma
2007 Zenodo  
Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India E-mail : Manuscript received 26 September 2006, revised 6 March 2007, accepted 14 March 2007 The oxidative deoximination of several aldo- and keto-oximes by quinolinium bromochromate (QBC), in dimethylsulphoxide (DMSO), exhibited a first order dependence on both the oxime and QBC. The oxidation of ketoximes is slower than that of aldoximes. The rates of oxidation of aldoximes correlated well in
more » ... ms of Pavelich-Taft dual substituent-parameter equation. The low positive value of polar reaction constant indicated a nucleophilic attack by a chromate-oxygen on the carbon. The reaction is subject to steric hindrance by the alkyl groups. The reaction of acetaldoxime has been studied in nineteen different organic solvents. The solvent effect has been analysed by multiparametric equations. A mechanism involving the formation of a cyclic intermediate, in the rate-determining step, has been proposed.
doi:10.5281/zenodo.5819677 fatcat:e3t5kz3bfzebpirlwnsa2k2qyu