Kinetics of N-Alkyl Side Chain Oxidations. Oxidation of N,N-Dimethylaniline by Alkaline Hexacyanoferrate(III)

The oxidation of N,N-dimethylaniline by alkaline hexacyanoferrate( III), at constant ionic strength, gave N-methylformanilide. The rate of the reaction was dependent on the first powers of the\u27 concentrations of substrate and oxidant, but was independent of the concentration of alkali in the range studied (0.01 M to 0.10 M). The mechanistic pathway involved an electron abstraction from the amine, giving a radical intermediate which was detected by ESR spectroscopy as a three-line spectrum with a peak height of 1 : 2 : 1

Kinetics of Oxidation of Heterocyclic Compounds by Quinolinium Dichromate

Quinolinium dichromate in sulfuric acid oxidized heterocyclic aldehydes (to the corresponding acids) and heterocyclic carboxylic acids (to the corresponding hydroxy-substituted acids) in acetic acidwater medium (vol. ratio, v(water)/v(acetic acid) = 50:50). The kinetic results supported a mechanistic pathway proceeding via a rate-determining decomposition of the chromate ester

Kinetics of Oxidation of Heterocyclic Compounds by Quinolinium Dichromate

Quinolinium dichromate in sulfuric acid oxidized heterocyclic aldehydes (to the corresponding acids) and heterocyclic carboxylic acids (to the corresponding hydroxy-substituted acids) in acetic acidwater medium (vol. ratio, v(water)/v(acetic acid) = 50:50). The kinetic results supported a mechanistic pathway proceeding via a rate-determining decomposition of the chromate ester

Quinolinium Dichromate Oxidation of Aliphatic Aldehydes: A Kinetic Study

Kinetic data on the rates of quinolinium dichromate oxidation of a series of aliphatic aldehydes have been determined and discussed with reference to aldehyde hydration equilibria. Kinetic results support a pathway proceeding via a rate-determining oxidative decomposition of a chromate ester of an aldehyde hydrate. A cyclic transition state is suggested; being a Hückel-type system (4n + 2), this would be an allowed process. The deuterium isotope effect for the oxidation of acetaldehyde (kH / kD = 6.4) indicated a carbon-hydrogen cleavage rather than a carbon-carbon cleavage

Kinetics of Oxidation of Benzylamines by Alkaline Hexacyanoferrate(III)

The reaction of benzylamine with alkaline hexacyanoferrate(III), at constant ionic strength, in aqueous methanol, has been investigated. The rate of the reaction was first order in each, substrate and oxidant, but was independent of the concentration of alkali, in the range studied (0.01 M to 0.1 M). The mechanistic pathway involved the formation of a radical intermediate, which was characterized by a value of (! = - 1.0, kn/kD = 6.3, and by ESR spectroscopy as four sets of 1 : 2 : 1 triplets

Kinetics of Oxidation of Unsubstituted & Substituted Diphenylamines by Alkaline Hexacyanoferrate(III)

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