重铬酸苯并咪唑在非水介质中氧化糠醛的动力学和机理

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL
R. Kalal, D. Panday
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引用次数: 0

摘要

重铬酸苯并咪唑(BIDC)在二甲亚砜中氧化糠醛(2-呋喃醛),生成2-呋喃酸。对于BIDC和氢离子,反应是一级反应。然而,在糠醛方面观察到Michaelis-Menten型动力学。测定了糠醛- bidc配合物在不同温度下的形成常数及其分解速率。计算了配合物形成的热力学参数和配合物分解的活化参数。在298 K时观察到的糠醛氧化的氘同位素效应(kH/kD = 6.23)表明,在速率决定步骤中α-C-H键断裂。在19种有机溶剂中对该反应进行了研究。溶剂效应分析表明,阳离子溶剂化的作用是主要的。根据动力学数据、溶剂效应分析和一些非动力学参数的结果,提出了配合物通过氢化物-离子的循环过渡态转移进行速率决定氧化分解的机理,并给出了相应的产物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Kinetics and mechanism of the oxidation of furfural by benzimidazolium dichromate under non aqueous medium
The oxidation of furfural (2-furaldehyde), by benzimidazolium dichromate (BIDC) in dimethyl sulfoxide, leads to the formation of 2-furoic acid. The reaction is first order with respect to BIDC and hydrogen-ion. However, Michaelis–Menten type kinetics was observed with respect to furfural. The formation constants of furfural-BIDC complexes and the rates of their decomposition have been evaluated at different temperatures. Thermodynamic parameters of the complex formation and activation parameters for the decomposition of the complexes have been calculated. The deuterium isotope effect observed in the oxidation of furfural (kH/kD = 6.23 at 298 K) indicated an α-C-H bond cleavage in the rate-determining step. The reaction has been studied in 19 organic solvents. The analysis of the solvent effect showed that the role of cation-solvation is major. Based on the kinetic data, analysis of the solvent effect and the result of some non-kinetic parameters, a mechanism involving rate-determining oxidative decomposition of the complex, through hydride-ion transfer via a cyclic transition state, to give the corresponding product is suggested.
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来源期刊
CiteScore
2.10
自引率
0.00%
发文量
5
审稿时长
2.3 months
期刊介绍: The journal covers the fields of kinetics and mechanisms of chemical processes in the gas phase and solution of both simple and complex systems.
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