13034-87-2Relevant 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.
Studies on the kinetics of tripropylammonium fluorochromate oxidation of some aromatic alcohols in non-aqueous media
Mansoor, S. Sheik,Shafi, S. Syed
experimental part, p. 85 - 90 (2011/10/18)
The oxidation of benzyl alcohol (BnOH) and a few para-substituted benzyl alcohols by tripropylammonium fluorochromate (TriPAFC) in dimethylsulphoxide (DMSO) leads to the formation of corresponding aldehydes. The reaction is first order each in TriPAFC and the alcohols. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence has the form: kobs = a + b[H +]. The oxidation of α α′-dideuterio benzyl alcohol exhibited a substantial primary kinetic isotope effect (kH/k D = 5.45 at 303 K). Oxidation of benzyl alcohol was studied in 19 different organic solvents. The solvent effect has been analysed using Kamlet's and Swain's multiparametric equation. A mechanism involving a hydride ion transfer via chromate ester is proposed.
Substituent Dependence of the ?-Acceptor Induced Bond Cleavage Reactions of Benzyl Phenyl Ethers
Penn, John H.,Lin, Zhe
, p. 1554 - 1559 (2007/10/02)
The relative C-O bond cleavage reaction rates (krel) of eight substituted benzyl phenyl ethers (BPE's) have been measured.These C-O bond cleavage reactions were thermally initiated by 2,3-dichloro-5,6-dicyanoquinone (DDQ).The equilibrium constants (K) for charge-transfer complex formation of these BPE's with the electron acceptors DDQ and TCNE in the solvent methylene chloride have also been determined at room temperature.The best correlation of log krel for DDQ reactions has been observed in these reactions.From this data, hydride transfer to DDQ is the rate-determining step of the reaction.
