{"title":"研究环己醇与 CO 发生环己烯烷氧基羰基化的速率与对甲苯磺酸一水合物浓度和温度的关系","authors":"N. T. Sevostyanova, S. A. Batashev","doi":"10.1134/s0965544124040042","DOIUrl":null,"url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The effects of the <i>p</i>-toluenesulfonic acid monohydrate (TsOH∙H<sub>2</sub>O) concentration on the alkoxycarbonylation of cyclohexene over a Pd(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>–PPh<sub>3</sub>–TsOH∙H<sub>2</sub>O catalytic system were quantified at 363–383 K. Within this temperature range, the correlation between the cyclohexyl cyclohexanecarboxylate production rate and the TsOH∙H<sub>2</sub>O concentration was found to be similar to an S-shaped curve. Based on these data, as well as previous findings with regard to the effects of water and TsOH∙H<sub>2</sub>O concentrations on the cyclohexene methoxycarbonylation rate, the hydride mechanism for the alkoxycarbonylation process was updated by adding relevant ligand exchange reactions between <i>ballast</i> palladium complexes, specifically reactions that produce a palladium aqua complex. The accordingly-modified kinetic equation for cyclohexene alkoxycarbonylation with cyclohexanol and CO was found to be consistent with the experimental data. Effective constants were evaluated for the modified kinetic equation over the studied temperature range. 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引用次数: 0
摘要
摘要 在 363-383 K 的温度范围内，定量研究了对甲苯磺酸一水合物（TsOH∙H2O）浓度对 Pd(PPh3)2Cl2-PPh3-TsOH∙H2O 催化体系上环己烯烷氧基羰基化的影响。根据这些数据以及之前关于水和 TsOH∙H2O 浓度对环己烷甲氧基羰基化速率影响的研究结果，更新了烷氧基羰基化过程的氢化物机理，增加了压载钯络合物之间的相关配体交换反应，特别是产生钯水络合物的反应。相应修改后的环己烯与环己醇和 CO 进行烷氧基羰基化的动力学方程与实验数据一致。在所研究的温度范围内，对修正动力学方程的有效常数进行了评估。根据活化配合物理论，进一步评估了一些相关参数，即 Pd(PPh3)2(C6H11OH)2 和 Pd(PPh3)2(H2O)2 配合物之间配体交换过程中的有效活化能以及焓、熵和吉布斯自由能的变化。结果发现，在 373 K 时，该反应接近平衡。
Investigation of the Dependence of the Rate of Cyclohexene Alkoxycarbonylation with Cyclohexanol and CO on the p-Toluenesulfonic Acid Monohydrate Concentration and Temperature
Abstract
The effects of the p-toluenesulfonic acid monohydrate (TsOH∙H2O) concentration on the alkoxycarbonylation of cyclohexene over a Pd(PPh3)2Cl2–PPh3–TsOH∙H2O catalytic system were quantified at 363–383 K. Within this temperature range, the correlation between the cyclohexyl cyclohexanecarboxylate production rate and the TsOH∙H2O concentration was found to be similar to an S-shaped curve. Based on these data, as well as previous findings with regard to the effects of water and TsOH∙H2O concentrations on the cyclohexene methoxycarbonylation rate, the hydride mechanism for the alkoxycarbonylation process was updated by adding relevant ligand exchange reactions between ballast palladium complexes, specifically reactions that produce a palladium aqua complex. The accordingly-modified kinetic equation for cyclohexene alkoxycarbonylation with cyclohexanol and CO was found to be consistent with the experimental data. Effective constants were evaluated for the modified kinetic equation over the studied temperature range. A number of relevant parameters—namely, the effective activation energy and the changes in enthalpy, entropy, and Gibbs free energy during the ligand exchange between the complexes Pd(PPh3)2(C6H11OH)2 and Pd(PPh3)2(H2O)2—were further evaluated in light of the activated complex theory. This reaction was found to be nearly equilibrium at 373 K.
期刊介绍：
Petroleum Chemistry (Neftekhimiya), founded in 1961, offers original papers on and reviews of theoretical and experimental studies concerned with current problems of petroleum chemistry and processing such as chemical composition of crude oils and natural gas liquids; petroleum refining (cracking, hydrocracking, and catalytic reforming); catalysts for petrochemical processes (hydrogenation, isomerization, oxidation, hydroformylation, etc.); activation and catalytic transformation of hydrocarbons and other components of petroleum, natural gas, and other complex organic mixtures; new petrochemicals including lubricants and additives; environmental problems; and information on scientific meetings relevant to these areas.
Petroleum Chemistry publishes articles on these topics from members of the scientific community of the former Soviet Union.
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