本文主要探讨了溶剂在反应控制相转移催化反应中的影响。反应控制相转移催化体系兼具均相催化与多相催化的优点,既解决了均相催化中催化剂难以回收的问题又克服了多相催化中反应速率慢、反应时间较长、活性组分易流失以及选择性较低的缺点。催化剂在反应体系中所表现出来的反应控制相转移特性不仅和本身的阴离子、阳离子组成有关,还和体系中溶剂的种类密切相关。合适的溶剂不但可以提高底物的转化率以及产物的产率,同时还有利于催化剂的回收。本文就溶剂在多种反应控制相转移催化体系中的影响进行了综述,包括烯烃环氧化、醇氧化制备醛/酮、酯化、烯/醇氧化制备二元羧酸、缩醛反应、氧化脱硫、羟基化反应以及Se催化还原等体系。最后,对目前催化体系中存在的问题提出了可能的解决方案并对反应控制相转移催化体系在其他方面的潜在应用和发展进行了展望。
The paper mainly discusses the effects of solvents on reaction-controlled phase-transfer catalysis which possesses the advantages of both homogeneous and heterogeneous catalysis. The reaction-controlled phase-transfer catalysis system not only realizes the catalyst recovery from the product over homogeneous catalysis but also avoids the low reaction rate, long reaction time, leaching of the active species and low selectivity in heterogeneous catalysis. For a reaction-controlled phase-transfer catalyt,its characteristic is affected not only by its composition including anion and cation but also by the used solvent during the reaction. A suitable solvent can increase the conversion rate of the substrate and the yield of product, and benefits the recovery of the catalyst. The effects of solvents on reaction-controlled phase-transfer catalysis systems including epoxidation of olefins, oxidation of alcohols to prepare aldehydes or ketones, esterification, oxidative cleavage of olefins or alcohols to prepare dicarboxylic acid, acetalation, oxidative desulfurization, hydroxylation reaction and catalytic reduction by Se, are presented in this paper. Finally, some possible measures to overcome the shortcomings in the present catalytic system are put forward and the future research prospects are discussed.
Contents
1 Introduction
2 Principle of the reaction-controlled phase-transfer catalysis
3 Effects of solvents on reaction-controlled phase-transfer catalysis
3.1 Epoxidation of olefins
3.2 Oxidation of alcohols to prepare aldehydes or ketones
3.3 Esterification
3.4 Oxidative cleavage of olefins or alcohols to prepare dicarboxylic acid
3.5 Acetalation
3.6 Oxidative desulfurization
3.7 Hydroxylation reaction
3.8 Catalytic reduction by Se
4 Conclusion and outlook
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