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首页> 外文期刊>European Chemical Bulletin >KINETICS AND MECHANISM OF OXIDATION OF SECONDARY ALCOHOLS BY MORPHOLINIUM FLUOROCHROMATE
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KINETICS AND MECHANISM OF OXIDATION OF SECONDARY ALCOHOLS BY MORPHOLINIUM FLUOROCHROMATE

机译:氟铬酸铵氧化次醇的动力学和机理

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摘要

Oxidation of several?secondary alcohols by morpholinium fluorochromate (MFC) in DMSO leads to the formation of corresponding ketones. The reaction is first order each in MFC and acidity. The reaction exhibited Michaelis-Menten kinetics with respect to alcohols. The oxidation of 2-propanol- d 2 (MeCDOHMe) exhibited a substantial primary kinetic isotope effect ( k H / k D = 5.16 at 298 K). The oxidation of 2-propanol has been studied?in?nineteen?different organic solvents. The solvent effect has been analysed using Taft's and Swain's multiparametric equations. The reaction was subject to both polar and steric effects of the substituents. A mechanism involving transfer of hydride ion from alcohol to the oxidant, via a chromate ester, has been proposed.
机译:DMSO中的氟铬酸吗啉鎓(MFC)氧化几种仲醇会导致形成相应的酮。该反应在MFC和酸度中均为一级。该反应相对于醇表现出Michaelis-Menten动力学。 2-丙醇-d 2(MeCDOHMe)的氧化显示出基本的一级动力学同位素效应(在298 K时k H / k D = 5.16)。已经在十九种不同的有机溶剂中研究了2-丙醇的氧化。已使用塔夫脱(Taft)和斯文(Swain)多参数方程分析了溶剂效应。该反应经受取代基的极性和空间作用。已经提出了一种机制,该机制涉及通过铬酸酯将氢化物离子从醇转移至氧化剂。

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