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首页> 外文期刊>European Chemical Bulletin >OXIDATION OF SOME ALIPHATIC ALDEHYDES BY QUINOLINIUM CHLOROCHROMATE: A KINETIC AND MECHANISTIC STUDY
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OXIDATION OF SOME ALIPHATIC ALDEHYDES BY QUINOLINIUM CHLOROCHROMATE: A KINETIC AND MECHANISTIC STUDY

机译：氯代铬酸铵氧化某些脂肪醛的动力学及机理研究

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The Oxidation of six aliphatic aldehydes by quinolinium chlorochromate (QCC) in dimethyl sulfoxide (DMSO) leads to the formation of corresponding carboxylic acids. The reaction is first order each in QCC. A Michaelis-Menten type of kinetics is observed with respect to the aldehydes. The reaction is catalysed by hydrogen ions, the hydrogen?ion dependence has the form: k obs =?a + b[H + ]. The oxidation of deuteriated acetaldehyde, MeCDO, exhibited a substantial primary kinetic isotope effect (k H /k D = 5.78 at 298 K). The oxidation of acetaldehyde has been studied in nineteen different organic solvents. The solvent effect has been analysed using Taft's and Swain's multiparametric equations. The rate constants correlate well with Taft’s s * values; reaction constants being negative. A mechanism involving transfer of hydride ion has been suggested.
机译：氯铬酸喹啉鎓（QCC）在二甲基亚砜（DMSO）中氧化六种脂肪族醛会导致形成相应的羧酸。该反应在QCC中均为一级反应。就醛而言，观察到迈克尔斯-门腾（Michaelis-Menten）类型的动力学。该反应由氢离子催化，氢离子依赖性的形式为：k obs ＝Δa+ b [H +]。氘代乙醛MeCDO的氧化表现出明显的一级动力学同位素效应（在298 K时k H / k D = 5.78）。已在十九种不同的有机溶剂中研究了乙醛的氧化。已使用塔夫脱（Taft）和斯文（Swain）多参数方程分析了溶剂效应。速率常数与Taft的*值具有很好的相关性;反应常数为负。已经提出了涉及氢化物离子转移的机理。

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