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Kinetics and structure reactivity correlation in the oxidation of some para- substituted benzhydrols by benzimidazolium dichromate

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Title Kinetics and structure reactivity correlation in the oxidation of some para- substituted benzhydrols by benzimidazolium dichromate
 
Creator Panday, Dinesh
 
Subject Benzhydrols
Kinetics
Mechanism
Oxidation
Correlation
Benzimidazolium dichromate
 
Description 372-379
The oxidation of some para-substituted benzhydrols by benzimidazolium dichromate (BIDC) in dimethyl sulfoxide
(DMSO) medium, results in the formation of corresponding diphenyl ketone. The reaction has been investigated on the
condition of pseudo-first order. In terms of both BIDC and hydrogen-ion, the reaction is first order. In the case of
benzhydrols, however, Michaelis-Menten type kinetics is observed. At different temperatures, the formation constants and
rates of breakdown of benzhydrol-BIDC complexes have been determined. Complex formation thermodynamic parameters
and activation parameters for complex decomposition have been computed. The kinetic isotope effect found in the oxidation
of benzhydrol ((kH/kD = 5.93 at 293 K) shows that the rate-determining step involved α-C-H bond fission. For the kinetic
analysis of the reaction, nineteen organic solvents have been utilized. The solvent impact have been investigated, and found
that cation-solvation plays a significant role. A suitable mechanism is proposed based on the kinetic data, solvent effect
analysis, and results of various non-kinetic parameters.
 
Date 2023-04-17T10:12:18Z
2023-04-17T10:12:18Z
2023-04
 
Type Article
 
Identifier 2583-1321 (Online); 0019-5103 (Print)
http://nopr.niscpr.res.in/handle/123456789/61771
https://doi.org/10.56042/ijc.v62i4.410
 
Language en
 
Publisher NIScPR-CSIR, India
 
Source IJC Vol.62(04) [Apr 2023]