13034-96-3Relevant academic research and scientific papers
Correlation analysis of reactivity in the oxidation of substituted benzyl alcohols by benzimidazolium dichromate - A kinetic and mechanistic aspects
Kumar, Pravesh,Panday, Dinesh,Kothari, Seema
, p. 1207 - 1215 (2020/06/27)
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.
Structure-Reactivity correlation in the oxidation of substituted benzaldehydes by tetraethylammonium chlorochromate
Gehlot,Prasadrao,Sharma
experimental part, p. 1173 - 1178 (2012/01/05)
Oxidation of 36 monosubstituted benzaldehydes by tetraethylammonium chlorochromate in dimethyl sulphoxide, leads to the formation of corresponding benzoic acids. The reaction is of first order with respect to chlorochromate and aldehydes. The reaction is promoted by H+; the H+ dependence has the form kobs = a + b[H+]. The oxidation of duteriated benzaldehyde exhibits substantial primary kinetic isotope effect. The reaction was studied in 19 different organic solvents and the effect of solvent was analyzed using Taft's and Swain's multiparametric equations. The rates of the oxidation of para- and meta-substituted benzaldehydes showed excellent correlation in terms of Charton's triparametric LDR equation, whereas the oxidation of ortho-substituted benzaldehydes were correlated well with tetraperametric LDRS equation. The oxidation of para-substituted benzaldehydes is more susceptible to the delocalized effect than is the oxidation of ortho- and meta- substituted compounds, which display a greater dependence on the field effect. The positive value of h suggests the presence of an electron-deficient reaction centre in the rate-determining step. The reaction is subjected to steric acceleration by the orthosubstituents. A suitable mechanism has been proposed.
Kinetics and Mechanism of the Oxidation of Substituted Benzyl Alcohols by Lead Tetraacetate
Bhatia, Indu,Banerji, Kalyan K.
, p. 1076 - 1092 (2007/10/02)
The kinetics of the oxidation of benzyl alcohol to benzaldehyde by lead tetraacetate have been studied in benzene solution both in the absence and presence of pyridine.The values of the reaction constant ρ for the reactions in the absence and presence of pyridine at 303 K are -1.13 and -1.92 respectively.The activation enthalpies and entropies of the nine compounds are linearly related.The oxidation of α,α-dideuteriobenzyl alcohol indicated presence of a primary kinetic isotope effect.The reaction does not induce polymerisation of acrylonitrile.Probable mechanisms have been suggested.
