The kinetics of oxidation of cyclanols, viz., cyclohexanol, cyclopentanol, cycloheptanol and cyclooctanol by quinaldinium fluorochromate has been studied in aqueous acid medium at 313 K (±0.1 K). The cyclanols were converted to the corresponding cyclic ketones. The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations. Increase in the percentage of acetic acid increases the rate of reaction. The reaction mixture shows the absence of any free radicals in the reaction, which has ruled out the possibility of a one-electron transfer during the addition of acrylonitrile. The reaction has been studied at four different temperatures and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed. The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol. This was explained on the basis of I-strain theory.

中文翻译：

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环醇对氟铬酸醌氧化的反应性

已经在 313 K (±0.1 K) 的酸性水溶液中研究了氟铬酸喹哪啶氧化环醇，即环己醇、环戊醇、环庚醇和环辛醇的动力学。环烷醇被转化为相应的环酮。发现反应的顺序就氧化剂而言是一个顺序，而就底物和氢离子浓度而言，反应顺序是一个顺序。乙酸百分比的增加会增加反应速率。反应混合物显示反应中不存在任何自由基，这排除了在添加丙烯腈期间发生单电子转移的可能性。该反应在四种不同的温度下进行了研究，并计算了活化参数。根据观察到的动力学结果，提出了一种合适的机制。发现相对反应性顺序是环己醇 < 环戊醇 < 环庚醇 < 环辛醇。这是在 I 应变理论的基础上解释的。