US EPA

7890812 

Journal Article 

Correlation analysis of reactivity in the oxidation of substituted benzyl alcohols by benzimidazolium dichromate - A kinetic and mechanistic aspects 

Kumar, P; Panday, D; Kothari, S 

2018 

Yes 

Journal of the Indian Chemical Society
ISSN: 0019-4522 

Scientific Publishers 

95 

10 

1207-1215 

English 

WOS:000454185600009 

The oxidation of a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, leads to the formation of the corresponding benzaldehydes. The reaction is first order with respect to each BIDC and alcohol. The reaction is catalyzed by hydrogen ions and the dependence has the form kobs = a + b[H+]. The oxidation of [1,1-2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect. The rates of the oxidation of meta-substituted benzyl alcohols correlated best with Taft's σ1 and σR0 constants. The para-substituted compounds exhibited excellent correlation with σ1 and σRBA values. The polar reaction constants are negative. The rate of oxidation of benzyl alcohol was determined in nineteen organic solvents. An analysis of the solvent effect by multiparametric equations indicated the greater importance of the cation-solvating power of the solvents. Suitable mechanisms have been discussed. © 2018 Scientific Publishers. All rights reserved. 

Kinetics; mechanism; correlation analysis; oxidation; benzyl alcohol; benzimidazolium dichromate