98018-42-9Relevant 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.
Kinetics and Mechanism of the Oxidation of Substituted Benzylamines by N-Chlorosuccinimide
Banerji, Kalyan K.
, p. 1015 - 1020 (2007/10/02)
The oxidation of ortho-, meta-, and para-substituted benzylamines by N-chlorosuccinimide (NCS), to the corresponding benzaldehydes, is first-order with respect to NCS and the amine.The pH dependence of the reaction rate suggests that the unprotonated benzylamine is the reductant.There is no effect of added succinimide.NCS itself has been postulated as the reactive oxidising species.The oxidation of benzylamine exhibited a substantial primary kinetic isotope effect (kH/kD=6.20).The rates of oxidation of the meta- and para-substituted benzylamines were separately correlated in Taft and Swain's dual substituent parameter equations.For the para-substituted compounds, the best correlation is obtained with ?I and ?R+ values; meta-substituted compounds correlate with ?I and ?R0 values.The reaction constants have negative values.The oxidation rates of the ortho-substituted compounds yield an excellent correlation in a triparametric equation involving Taft's ?I and ?R+ values and Charton's steric parameter, V.A mechanism involving transfer of a hydride ion from the amine to the oxidant in the rate-determining step is proposed.
