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Kinetics of oxidation of hydrocarbons by quinolinium dichromate
Author(s) -
Sarma G. C.,
Mahanti M. K.
Publication year - 1991
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610040404
Subject(s) - chemistry , phenanthrenes , hydride , photochemistry , acrylonitrile , inorganic chemistry , kinetic isotope effect , kinetics , phenanthrene , decalin , reaction rate , organic chemistry , catalysis , hydrogen , polymer , physics , deuterium , quantum mechanics , copolymer
Abstract Quinolinium dichromate (QDC) oxidizes hydrocarbons (toluenes and phenanthrenes) smoothly in dimethylformamide in the presence of acid. The rate of the reaction was first order in each substrate, oxidant and acid. The effects of variations in solvent composition and temperature were studied. The rate data obeyed Hammett's relationship and the values of ρ were −0.20 for toluenes and −1.79 for phenanthrenes. Induced polymerization of acrylonitrile and the reduction of mercury(II) chloride were not observed. For the oxidation of toluenes, a kinetic isotope effect, k H / k D = 5.13, was observed. The initial reaction for the oxidation of toluenes involved hydrogen abstraction, forming an intermediate which was rapidly converted to the product, the corresponding aldehyde. For the oxidation of phenanthrene, the experimental data have been rationalized in terms of a hydride ion transfer in the ratedetermining step.