温控液/液两相催化进展*

本文以作者在温控水/有机两相及温控非水液/液两相催化领域的研究工作为主线,对这一领域的研究进展作一评述,重点是环绕经典水/有机两相催化体系存在“应用范围受底物水溶性限制”的根本问题展开。特别是对“温控相转移催化”作了较为详细的介绍,同时,按体系介质不同,对氟两相体系、PEG两相体系、离子液体两相体系等非水液/液两相体系以及温控相分离催化分别作了阐述。     

液/液两相催化新进展--温控非水液/液两相催化

温控非水液/液两相催化,是指一类由两种或多种液态有机物组成的催化反应体系,其特点是体系的相态变化可通过温度来调控,即体系在高温时相互混溶呈均相,低温不溶分成两相,催化剂和产物分别处于两相,从而为解决均相催化剂分离难的问题开拓了一个新方向,是液/液两相催化研究领域最引人注目的进展之一.首次以"温控"为主线将氟两相催化作为温控液/液两相催化的一个特定类型纳入"温控非水液/液两相催化"范畴,并与其它通过温度来调控的有机液/液两相和作者提出的温控相分离催化串在一起作一较为详细的评述.     

温控配体与液／液两相催化

 以作者近年的研究工作为主，对液／液两相催化研究领域取得的进展做一综述．着重介绍了以温控配体为基础的新型液／液两相催化过程温控相转移催化（thermoregulatedphasetransfercatalysis，TRPTC）和温控相分离催化（thermoregulatedphase－separablecatalysis，TPSC）的基本原理及其在高碳烯烃氢甲酰化、芳香硝基化合物的CO选择性还原及烯烃加氢等反应中的应用．基于温控配体在水中的“浊点”特性而提出的温控相转移催化概念，为从根本上解决水／有机两相催化 的适用范围受底物水溶性限制的问题提供了一条新途径．而利用温控配体在某些有机溶剂中存在临界溶解温度（CST）的特性而实现的温控相分离催化，则使在高于临界溶解温度的反应温度时为均相的反应体系，在低温（＜CST）时则分成两相，催化剂自成一相，形成一种具有“均相反应、两相分离”特色的液／液两相催化新体系．     

两相催化——均相催化多相化新进展*

评述了水溶性膦配体和两相催化研究领域的进展, 探讨了固载水相催化、温控相转移催化和氟两相体系等新型两相催化体系。两相催化在烯烃的氢甲酰化反应、不饱和化合物的加氢反应以及其它有机反应中获得了广泛的应用。     

金属络合物的相转移催化分析与分离

以可简单分离回收、可反复使用为目标，详细介绍了相转移催化的变化发展过 程．通过对溶剂的选择，使得催化剂选择性地溶解在某一液相中，而使产物溶解在 另一液相中，如水-有机两相催化体系；通过温度的变化，简单地实现了在较高温 度下反应为均相体系以提高催化剂的活性，而在较低温度下实现了催化剂与产物不 相溶使得催化剂得以简单分离，如温控型水-有机两相催化体系、氟-有机两相催化 体系、温控型含氟催化剂、温控型有机金属催化剂等．     

液/液两相催化高碳烯烃氢甲酰化反应

结合作者近年来的研究工作 ,对液/ 液两相催化高碳烯烃氢甲酰化的研究进展作一综述 ,针对经典的水/有机两相体系不能用于高碳烯烃氢甲酰化的问题 ,全面介绍了适用于高碳烯烃水/有机两相氢甲酰化的温控相转移催化等 6种改进方法。同时 ,对 90年代以来发展迅速的氟两相、离子液体两相、超临界流体等非水液/液两相体系中的高碳烯烃氢甲酰化作了系统阐述 ,对它们的应用前景进行了评较。     

温控相转移纳米铑催化高碳烯烃氢甲酰化反应

 基于温控配体 Ph₂P(CH₂CH₂O)₁₆CH₃ 稳定的 Rh 纳米催化剂在水/1-丁醇两相体系中具有温控相转移功能, 将其用于高碳烯烃氢甲酰化反应中. 在优化的反应条件下, 1-辛烯转化率和醛收率分别达 98% 和 96%, 对其它高碳烯烃氢甲酰化反应也具有较高的催化性能. 催化剂和产物通过简单的相分离即可分开, 连续使用 3 次后, 催化剂性能未见明显降低.     

温控两相酸性聚合型离子液体催化胺醛缩合反应

为降低催化剂流失率,以聚乙二醇为主链、双键取代咪唑型离子液体为交联剂,采用自由基聚合方式设计合成出酸性聚合型离子液体。该离子液体可与甲苯形成优良的温控两相体系,并用于苯胺和苯甲醛的缩合反应。结果表明,聚合离子液体具有催化活性高、流失量小、回收方便的优点。产物N-亚苄基苯胺收率93.4%,离子液体平均单次流失率约2.5%。底物拓展试验表明,该温控体系对含不同取代基的芳胺和芳醛缩合反应具有良好的普适性,产物收率57.2%~82.9%。     

N-Boc-氨基噻吩的相转移催化N-烷基化

N-Boc-氨基噻吩的相转移催化N-烷基化;N-Boc-氨基;噻吩;N-烷基化;相转移催化     

N-Boc-氨基噻吩的相转移催化N-烷基化

N-Boc-氨基噻吩的相转移催化N-烷基化;N-Boc-氨基;噻吩;N-烷基化;相转移催化     

温控相转移配体及催化(Ⅴ)——单,双-对聚氧乙烯基三苯基膦的合成及其催化性能研究

近年来,水／有机两相催化已成为均相催化多相化研究的主流［１］．其中,新型水溶性膦配体的合成和两相催化新体系的设计尤为引人关注［２］．最近我们发现［３］,聚醚型水溶性膦－铑催化剂在高温下可溶入有机相对反应进行催化,而在冷却后又重返水相和产物分离．本文通...     

Thermoregulated Liquid/Liquid Biphasic Catalysis and Its Application

A brief overview of our recent research results of thermoregulated liquid/liquid biphasic catalysis is presented. Emphasis is given to the general principles of thermoregulated phase-transfer catalysis (TRPTC) and thermoregulated phase-separable catalysis (TPSC). In addition, the applications of TRPTC and TPSC in biphasic catalysis are also discussed. The introduction of TRPTC to biphasic system is free from the shortcomings of classical aqueous/organic two-phase catalysis, in which the application scope is restrained by the water solubility of the substrate. Meanwhile, TPSC provides a very simple and reliable way to deal with the separation of catalyst in homogeneous catalysis. The common advantages of TRPTC and TPSC are characterized by homogeneous catalysis coupled with convenient biphasic separation.     

非离子水溶性膦配体的合成及其应用进展

按非离子水溶性膦配体的发展特点,就羟基取代膦配体、天然碳水化合物为母体的膦配体、聚醚基取代的膦配体、具手性中心的膦配体、高分子负载型膦配体、温控相转移膦配体、环糊精改性的膦配体等类型的非离子水溶性膦配体的合成及其在两相催化中的应用作一综述。     

Recent advances in water-mediated multiphase catalysis

Water is the most sustainable solvent, making it the obvious choice to replace organic solvents in various synthesis techniques. However, its applications in the chemical and pharmaceutical industries are often restricted by the low solubility of organic compounds in water. Essentially, the reactions of organic compounds in water are multiphase systems. Therefore, this review classifies aqueous-phase organic reactions into liquid–liquid, liquid–solid and gas–liquid–solid phase from the perspective of phase interfaces of multiphase reactions, and summarizes the research progress and breakthroughs in recent years, including the application of micellar catalysis, Pickering emulsion catalysis, micro-nanobubble/foam catalysis and “dry water” catalysis, as well as the unique advantages of using water as a medium. Finally, we point out the current challenges and future perspectives on multiphase catalysis in aqueous-phase reactions.     

Stimuli-triggered phase transfer of polymer-inorganic hybrid hairy particles between two immiscible liquid phases

Polymer brush-grafted particles (i.e., hairy particles) capable of undergoing direct, especially reversible, phase transfer from one liquid phase to another immiscible liquid phase in response to environmental changes have received growing interest due to their great potential in a wide variety of applications. This article is intended to review recent exciting advances in stimuli-triggered phase transfer of hairy particles in liquid-liquid biphasic systems. We start with a discussion of the mechanism of particle transfer across a liquid-liquid interface and progress to the synthesis of polymer brushes grafted on particles and the transfer of hairy particles between two immiscible liquid phases induced by various external stimuli, including temperature, pH, ionic strength, light, and solvents. The applications of thermally triggered phase transfer of hairy particles in catalysis (thermoregulated phase transfer catalysis) are discussed, followed by a summary and our perspective on future development. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1600–1619     

Cloud Points of Water—soluble Polyether Phosphites and Their Application in the Biphasic Hydroformylation of Higher Olefins

Wate-soluble polyether phosphites alkyl polyethylene glycol ophenylene phosphite(APGPPS)were alcoholysis of phosphorus chloride with plyoxyethylene alkyl ether.With appropriate HLB(hydrophile-lypophile balance),the phosphites possess clear cloud points below 100℃，Addition of some inorganic salts decreases cloud points of the phosphites.When the phosphiites have long polyether chain binding to short-chain alkyl group,their cloud points could be extrapolated from figure of dependece of cloud points on addition of inorganic salts.Utilizing octylpolyglycol-phenylene-phosphite(OPGPP)(APGPP,R:Octyl)/Rh complex formed in situ as catalyst,over 90% conversion of 1-decene was obtained ,avoiding the limitation of water insolubility of substrates.Preliminary results indicated that micellar catalysis and thermoregulated phase-transfer catalysis(TRPTC)coexist in the reaction system.Below cloud point,micellar catalysis induced by plyether phosphites may be existed.When temperature is increased to above cloud point of the phosphies,this reaction works mainly in TRPTC.The catalysts could be easily spearated by simple decantation,but followed by considerable loss in activity after three successive reaction runs.Preliminary results indicated hydrolysis of OPGPP happened during the reaction.which may explain for the bad loss in activity.The catalyst was reused up to seven times with-out clear decrease in activity when OPGPP/Rh ratio was increased to 50.