Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammonium tribromide

Journal of Chemical Sciences

Seema Kothari¹  Garima Goswami¹  Kalyan K Banerji1¹ 

[1]Department of Chemistry, JNV University, Jodhpur 342 005, Indi$$

关键词: Diols;    benzyltrimethylammonium tribromide;    oxidation;    kinetics;    mechanism;    kinetic isotope effect.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (𝑣/𝑣) acetic acid-water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give the hydroxycarbonyl compounds. The reaction is first-order with respect to BTMAB. Michaelis-Menten type kinetics is observed with respect to diol. Addition of benzyltrimethylammonium chloride does not affect the rate. Tribromide ion is postulated to be the reactive oxidizing species. Oxidation of [1,1,2,2-2H4] ethanediol shows the absence of a kinetic isotope effect. The reaction exhibits substantial solvent isotope effect. A mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidized by a hydride ion transfer to the oxidant, as are the monohydric alcohols.

【 授权许可】

Unknown