离子液体中烷基化反应研究进展

综述了离子液体中的C、O、N、S的烷基化反应研究,表明离子液体作为一种新型的绿色溶剂有效地促进了烷基化反应,显著地提高了反应的选择性和收率。     

离子液体中缩合反应研究进展

综述了离子液体中Knoevenagel、Aldol、Wittig、Pechmann、Paal-Knorr、Benzoin、Biginelli等各种缩合反应,表明离子液体作为一种新型的绿色溶剂有效地促进了缩合反应的进行,显著地提高了反应的选择性和收率。     

离子液体中偶联反应的研究进展

综述了近年来离子液体作为反应介质在Suzuki偶联、Heck偶联、Sonogashira偶联、碳-杂原子交叉偶联和Negishi偶联等反应中的研究进展。     

四膦配体/钯体系催化无铜Sonogashira偶联反应

以环己二胺为骨架的含氮四膦配体N,N,N',N'-四[(二苯基膦)甲基]环己二胺和钯组成的催化体系用于苯乙炔和芳卤的Sonogashira反应,该催化体系对卤代芳烃显示了良好的官能团容忍性。结果显示空间位阻的影响大于电子效应,通常能与金属配位使得金属催化剂失活而难以顺利反应的含N杂环化合物,3-溴喹啉以99%的收率获得相应的产物,活性较低的氯代底物,3-氯吡啶的目标产物产率为90%。     

咪唑类离子液体及其催化C-C偶联反应

离子液体作为一种新型绿色溶剂,具有许多独特的物理化学性质,近年来逐渐被人们所认知,并发现可用在许多重要领域.本文简单介绍离子液体的种类和特点,重点介绍在咪唑类离子液体中的Michael、Heck、Suzuki、Witting、Baylis-Hillman和Aldol等重要的C-C偶联反应.     

离子液体中氧化反应研究进展

离子液体用作氧化反应的溶剂,已经显示了许多潜在的优点。该文对在不同离子液体中进行氧化反应的类型、催化剂种类、达到的效果进行了评述,指出了存在的问题和发展方向。引用文献34篇。     

铜催化Sonogashira交叉偶联反应的研究进展

过渡金属催化的Sonogashira反应是合成碳碳叁键的重要方法,此反应已广泛应用于天然产物、活性中间体和材料化学等。近年来,使用廉价的铜盐来代替钯做催化剂取得了明显的进展,对铜催化的Sonogashira反应的最新进展进行了总结和讨论。     

离子液体的纯化

目前,室温离子液体作为一种新型的绿色溶剂受到了广泛的关注.由于离子液体本身所固有的性质,使得我们不能用常规的纯化方法对离子液体进行纯化.本文简单介绍了室温离子液体及其发展历史、种类、合成方法,详细介绍了离子液体中常见杂质的去除方法以及AlCl3型离子液体、由离子交换而形成的离子液体、由普通阳离子和阴离子组成的离子液体的纯化方法.     

离子液体催化合成苯基硫代膦酰二氯的研究

研究了以含三氯化铝的离子液体催化苯基二氯化磷(DCPP)的硫化制备苯基硫代膦酰氯(DCPPS)的反应特点，结果表明，离子液体对反应有较好的催化活性，较传统催化方式表现出催化剂用量少、分离方式简便、原料可回收、催化剂可回收等特点，这些特点综合地解决了传统反应中产品难分离、污染重的缺点，为DCPPS的绿色合成提供了新的方法。     

离子液体中酶催化反应的研究进展

讨论了近年来离子液体作为酶催化反应介质的应用发展。说明了不同类别的酶在离子液体或水合离子液体两相体系中具有催化活性，尤其是脂肪酶，在无水的离子液体介质反应体系中不仅能保持很好的活性，其手性选择性和操作稳定性往往优于传统介质中的表现。指出了离子液体的环境相容性使其成为绿色生物反应工程新的应用溶剂。对不适于在传统溶剂体系中进行的生物催化再生和产物回收研究，离子液体溶剂已经逐渐表现出其优势。     

Highly Active Palladium Catalyst for the Sonogashira Coupling Reaction of Unreactive Aryl Chlorides

This communication reports on the β‐diketiminatophosphane palladium‐catalyzed copper‐free Sonogashira coupling of aryl chlorides with alkynes. A catalyst loading of 0.5 mol% is sufficient to achieve high performance under relatively mild reaction conditions. Furthermore, dialkynylbenzenes are efficiently prepared by one‐pot double Sonogashira couplings of aryl dichlorides.     

A Convenient High Activity Catalyst for the Sonogashira Coupling of Aryl Bromides

A mixture of Na₂PdCl₄, CuI and (t‐Bu)₃PH⁺BF₄⁻ (molar ratio 4 : 3 : 8) dispersed in H₂N(i‐Pr)₂⁺Br⁻ can be used as a “single source” precatalyst for the Sonogashira coupling of aryl bromides with various aryl‐ and alkylacetylenes in HN(i‐Pr)₂ solvent. Arylacetylenes require just 0.005 mol % of Pd catalyst at 80 °C, with TOFs ranging between 3,200 and 10,000 h⁻¹.     

用于烷基化反应的离子液体催化剂研究进展

介绍了烷基化催化剂的特点及发展历程,概述了离子液体催化剂的分类和优点,讨论了离子液体催化烷基化的研究情况,包括异构烷烃与烯烃烷基化和芳香烃烷基化,最后,展望了离子液体催化剂在烷基化反应中的应用前景。     

PdCl2(P(OPh)3)2 Catalyzed Coupling and Carbonylative Coupling of Phenylacetylenes with Aryl Iodides in Organic Solvents and in Ionic Liquids

Efficient cross-coupling and carbonylative coupling of terminal alkynes with aryl iodides catalyzed by PdCl₂(P(OPh)₃)₂ in the presence of NEt₃ in toluene and in ionic liquids is described. In imidazolium ionic liquids, [bmim]PF₆ or [mokt]PF₆ (bmim = 1-butyl-3-methyl imidazolium cation, mokt = 1-methyl-3-octyl imidazolium cation) catalyst was recycled and used in four concecutive catalytic cycles with high activity. In the absence of aryl iodide the same catalytic system catalyzed head-to-tail dimerization of phenylacetylene to the 1,3-diphenyl enyne, trans-PhC ≡ C–C(Ph)=CH₂, with a yield of 85%.     

纤维膜负载铜催化剂的性能及其制备

通过静电纺丝和热交联技术、以聚乙烯醇(PVA)作为载体制备了一种新颖的电纺纤维膜负载铜催化剂。利用扫描电镜(SEM)和全反射红外光谱(FT-IR/ATR)对其微观结构和化学结构进行了表征。SEM结果显示:PVA纤维膜纤维之间粘接比较明显,热处理可以改善纤维膜的形貌、降低纤维直径。FT-IR/ATR结果表明热处理可以促使醚键的生成,从而提高纤维膜的稳定性。催化结果显示该纤维膜负载铜催化剂可以有效地催化剂碘苯与苯炔的Sonogashira交叉偶联反应。     

Sonogashina偶联法合成芳基末端炔的工艺改进

以对二溴苯(Ⅰa)、1,3,5-三溴苯(Ⅰb)和2-甲基-3-丁炔-2-醇(Ⅱ)为原料,在PdC l2、PPh3和CuI的催化作用下进行Sonogash ina偶联反应,偶联产物在KOH作用下发生消去反应,分别得到对溴苯乙炔(Ⅳa)、对二乙炔基苯(Ⅳa′)、1,3,5-三乙炔基苯(Ⅳb)。研究发现,在合成中间体1,4-二(3-羟基-3-甲基-1-丁炔)苯时,选择n(Ⅰa)∶n(Ⅱ)=1∶3较为适合;共催化剂n(CuI)∶n(Ⅱ)≈0.01时产率较高;水对偶联反应无影响。粗产物经硫酸铜溶液萃取、硅胶过滤、重结晶、真空升华进行分离提纯得到纯产品。3种产物的收率分别为75%、72%、70%。产物用IR、GC-MS、1HNMR进行了确证。     

Palladium-Catalyzed Heck Reaction in the Multi-Functionalized Ionic Liquid Compositions

In the multi-functionalized ionic liquid compositions (MFILC), composed of 1-n-butyl-2-diphenylphosphino-3-methylimidazolium hexafluorophosphate, [BDPPMIM]PF6), 1-(2-piperid-1-yl-ethyl)-3-methylimidazolium hexafluorophosphate, [PEMIM]PF6), and 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), PdCl2 served as an efficient catalyst for Heck reactions of aryl iodides and bromides. The built-up PdCl2-MFILC, including stoichiometrically consumed base of [PEMIM]PF6, could be reused at least for seven cycles without activity loss. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Separation of Ionic Liquid Dispersions in Centrifugal Solvent Extraction Contactors

Abstract

Separations of dispersions formed by mixing immiscible organic room‐temperature ionic liquids (IL)/hydrocarbon/and aqueous systems using a centrifugal solvent‐extraction contactor have been successfully demonstrated in proof‐of‐concept testing. This accomplishment is significant in that physical property factors that are typical of ionic liquid systems (e.g., similar densities of the bulk phases, low interfacial tensions, and high viscosities) are typically unfavorable for dispersion separation, particularly in continuous processes. Efficient separation of dispersions containing ionic liquid solvents is essential for utilization of these compounds in liquid‐liquid extraction applications to maximize both solute transfer efficiency and solvent recovery. Efficient solvent recovery is of particular concern in IL applications because of the high cost of most IL solvents.

This paper presents the results of initial experiments with three hydrophobic ionic liquids to determine how their physical properties affect phase mixing and phase disengagement in contact with an aqueous solution using a centrifugal contactor. While the results of the reported work are promising, additional work is needed to optimize existing mathematical models of contactor hydraulics to address special considerations involved in IL‐based processes and to optimize the equipment itself for IL applications.