Immobilization of Pd（Ⅱ）Catalysts for Cyclopropanation in Ionic Liquid

Cyclopropanation of styrene with ethyl diazoacetate catalyzed by Pd(Ⅱ） in ionic liquid [omim][BF4] was investigated.Palladium catalysts can be effectively immobilized in ionic liquid.The catalysts PdCl2 and cyclopalladated complex 2 contained in ionic liquid could be recycled for 6 and 7 times,respectively,without losing the efficiency.     

N-alkyl-4-boronopyridinium salts as thermally stable and reusable amide condensation catalysts

[reaction: see text] N-Alkyl-4-boronopyridinium salts are highly effective and reusable catalysts for the dehydrative amide condensation reaction between equimolar mixtures of carboxylic acids and amines. N-Alkylboronopyridinium salts are thermally stabilized in the order N-alkyl-2-boronopyridinium salt < N-alkyl-3-boronopyridinium salt < N-alkyl-4-boronopyridinium salt. Homogeneous catalysts, such as 4-borono-N-methylpyridinium iodide, are more effective in the presence of ionic liquid and can be recovered by extraction with ionic liquid. In contrast, heterogeneous catalysts, such as polystyrene-bound 4-boronopyridinium salts, are effective even in the absence of ionic liquid and can be recovered by filtration.     

温和条件下液态醇催化氧化制醛、酮

本文对温和条件下液态醇催化氧化制醛或酮的研究进展进行了全面评述,介绍了均相催化剂、液固多相催化剂、有机相-水相两相催化剂、氟两相催化剂和离子液相催化剂,着重讨论了以O_2为氧源的催化体系.     

Synthesis of Tetrahydrofuran and Tetrahydropyran Derivatives Catalyzed by Tungstophosphoric Acid in Ionic Liquid

Synthesis of tetrahydrofuran and tetrahydropyran derivatives catalyzed by tungstophosphoric acid （H3PW12040） were conveniently performed with high yield from the corresponding unsaturated alcohols in ionic liquid. Sufuric acid （H2SO4）, trifluoromathanesulfonic acid （TfOH） and p-toluenesulfonic acid （TsOH） were also explored for preparing these products in ionic liquid. The catalysts and ionic liquid can be easily recovered and reused.     

In situ generation of carbenes: a general and versatile platform for organocatalytic living polymerization

A metal-free, organocatalytic approach to living polymerization using N-heterocyclic carbenes as nucleophilic catalysts generated and used in situ in a single-pot process is detailed. The N-heterocyclic carbene catalyst platform is extremely versatile, as the nature of the substituents has a pronounced effect of catalyst stability and activity toward different substrates. The generation of imidazolium- and thiazaolium-based carbenes was accomplished from the reaction of the corresponding salts with the appropriate bases. This allowed the rapid screening of libraries of catalysts that provided a basic understanding of catalyst structure (sterics, electronics, etc.) with the polymerization rate, control, substrate, and range of molecular weights. The imidazole-based catalysts were significantly more active toward ROP than the thiazolium-based analogues. No appreciable differences between imidazol-2-ylidene and imidazolin-2-ylidene catalysts were observed. Less sterically demanding carbenes were found to be more active toward ring-opening polymerization (ROP) than their sterically encumbered analogues for lactone polymerization. These data prompted the investigation of ionic liquid as a precatalyst reservoir in a phase-transfer polymerization with an immiscible THF solution of monomer and initiator. In situ activation of the ionic liquid generates carbene that migrates to the organic phase effecting living ROP. Precatalyst (ionic liquid) regeneration terminates polymerization. This simple reaction/recycle protocol readily allows repetitive ROPs from the ionic liquid using commercially available materials.     

Silica-gel-confined ionic liquids: a new attempt for the development of supported nanoliquid catalysis

A new concept of designing and synthesizing highly dispersed ionic-liquid catalysts was developed through physical confinement or encapsulation of ionic liquids (with or without metal complex) in a silica-gel matrix through a sol-gel process. We studied ionic liquids such as EMImBF4, BuMImBF4, DMImBF4, CMImBF4, BuMImPF6, either with or without [Pd(PPh3)2Cl2] and [Rh(PPh3)3Cl], in a silica-gel matrix (E = ethyl, Bu = butyl M = methyl, D = decyl, C = cetyl and Im = imidazolium). The contents of ionic liquids and loadings of Pd or Rh were 8-53 wt % and 0.1 approximately 0.15 wt %, respectively. Analyses of FT-Raman spectra showed that abnormal Raman spectra of the confined ionic liquids were observed in comparison with the bulk and pure ionic liquids. EMImBF4 and BuMImBF4 ionic liquids could be completely washed out from the silica-gel matrix under vigorous reflux conditions, but ionic liquids with larger molecular size, for example, DMImBF4 or CMImBF4, could be confined into the silica-gel nanopores relatively firmly. These results suggested that the ionic liquids were physically confined or encapsulated into the silica gel. The N2 adsorption measurements indicated that the silica-gel skeleton was mesoporous with 50-110 A pore size after the BuMImBF4 ionic liquid was removed completely. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis showed that the silica-gel matrix was amorphous and non-uniformly mesoporous. Carbonylation of aniline and nitrobenzene for synthesis of diphenyl urea, carbonylation of aniline for synthesis of carbamates, and oxime transformation between cyclohexanone oxime and acetone were used as test reactions for these catalysts. Catalytic activities were remarkably enhanced with much lower amounts of ionic liquids needed with respect to bulk ionic-liquid catalysts or silica-supported ionic-liquid catalysts prepared with simple impregnation, in which the ionic liquid may be deposited as a thin layer on the support. Such unusual enhancement in catalytic activities may be attributed to the formation of nanoscale and high-concentration ionic liquids due to the confinement of the ionic liquid in silica gel; this results in unusual changes in the symmetry and coordination geometry of the ionic liquids.     

An ionic liquid-tagged second generation Hoveyda-Grubbs ruthenium carbene complex as highly reactive and recyclable catalyst for ring-closing metathesis of di-, tri- and tetrasubstituted dienes

A second generation Hoveyda-Grubbs ruthenium carbene complex bearing an ionic liquid tag was prepared and shown to be a highly reactive catalyst for the ring-closing metathesis of di-, tri- and tetrasubstituted diene and enyne substrates in minimally ionic solvent systems ([Bmim]PF₆/CH₂Cl₂, 1:9-1:1 v/v). Both the catalyst and the ionic liquid can be conveniently recycled and repeatedly reused (up to 17 cycles) with only a very slight loss of activity. The ionic liquid tag is crucial to the high level of recyclability of the catalyst since the original second generation Grubbs and Hoveyda-Grubbs catalysts rapidly lose their activity when recycled in the ionic liquid layer.     

Development of Ionic Liquids as Green Reaction Media and Catalysts

A brief review of the work carried out at Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences for development of ionic liquid as green reaction media and catalysts is presented. This includes the processes of ionic liquid to be used as catalyst, reaction media, development of functional ionic liquid and methods for synthesis of immobilized ionic liquid. In the end, some prospects for development of ionic liquid are also addressed.     

Cobalt‐Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity

By taking inspiration from the catalytic properties of single‐site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon‐nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability.     

Facile preparation and reactivity of bifunctional ionic liquid-supported hypervalent iodine reagent: a convenient recyclable reagent for catalytic oxidation

Novel, efficient, and recyclable bifunctional catalysts bearing ionic liquid supported (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and iodoarene moieties were developed and used for environmentally benign catalytic oxidation of alcohols. The reactions using peracetic acid as a green and practical co-oxidant afforded the corresponding carbonyl compounds in high yields under mild conditions and convenient work-up. Furthermore, these ionic liquid supported bifunctional catalysts could be simply recovered and reused.     

Development in the green synthesis of cyclic carbonate from carbon dioxide using ionic liquids

This brief review presents the recent development in the synthesis of cyclic carbonate from carbon dioxide (CO₂) using ionic liquids as catalyst and/or reaction medium. The synthesis of cyclic carbonate includes three aspects: catalytic reaction of CO₂ and epoxide, electrochemical reaction of CO₂ and epoxide, and oxidative carboxylation of olefin. Some ionic liquids are suitable catalysts and/or solvents to the CO₂ fixation to produce cyclic carbonate. The activity of ionic liquid is greatly enhanced by the addition of Lewis acidic compounds of metal halides or metal complexes that have no or low activity by themselves. Using ionic liquids for the electrochemical synthesis of the cyclic carbonate can avoid harmful organic solvents, supporting electrolytes and catalysts, which are necessary for conventional electrochemical reaction systems. Although the ionic liquid is better for the oxidative carboxylation of olefin than the ordinary catalysts reported previously, this reaction system is at a preliminary stage. Using the ionic liquids, the synthesis process will become greener and simpler because of easy product separation and catalyst recycling and unnecessary use of volatile and harmful organic solvents.     

Green and Efficient Protocol for the Synthesis of N-(2-Hydroxyethyl)anilines by the Alkylation Reaction in Ionic Liquid

A green and efficient protocol for the synthesis of N-(2-hydroxyethyl)anilines by the selective alkylation reaction in ionic liquid [BMIM]BF₄ (1-butyl-3-methylimidazolium tetrafluoroborate) has been developed, eliminating the need for toxic and expensive catalysts and volatile organic solvents. The effects of the amount of ionic liquid, temperature, time, and substrate structure on the reaction were investigated. The conversion and selectivity of N-(2-hydroxyethyl)anilines obtained in ionic liquid [BMIM]BF₄ are significantly increased in comparison to those traditional methods. Furthermore, the ionic liquid could be easily separated and reused at least five times. It provided a simple and efficient alternative way for the industrial synthesis of N-(2-hydroxyethyl)anilines.     

Selective oxidation of sulfide catalyzed by peroxotungstate immobilized on ionic liquid-modified silica with aqueous hydrogen peroxide

Two kinds of catalysts of peroxotungstates immobilized on ionic liquid-modified silica have been synthesized and characterized. By comparing with other heterogeneous catalysts, the most characteristic of these heterogeneous catalysts is the catalyst formed from the combination of catalytic active center peroxotungstate with an ionic liquid. Thereinto, ionic liquid-modified supported catalysts provide the hydrophobic environment for organic reactions. We presume that the heterogeneous catalyst would display excellent catalytic ability depending on the additive effect of an ionic liquid and peroxotungstate. Their catalytic properties in oxidation of sulfides to sulfoxides and sulfones were investigated with 30% aqueous hydrogen peroxide at room temperature. These recoverable catalysts both exhibit high catalytic activities in the oxidation reaction of sulfoxides and provide excellent chemselectivities towards sulfur groups with unsaturated double bonds when the aqueous hydrogen peroxide was greatly in excess. The yields of methyl phenyl sulfoxide were still satisfied when the catalyst was reused for a sixth time.     

离子液体中手性催化剂回收研究

近年来,贵重的手性催化剂的回收与再利用越来越引起化学工作者的关注,而离子液体在催化剂回收方面有其独特的优势.本文综述了离子液体在手性催化反应中的应用,在回收催化剂的同时,也能一定程度上提高催化剂的催化效率:着重介绍了新型含咪唑盐手性催化剂及其在不对称催化中的应用,由于它在离子液体和有机溶剂的显著差异可以很容易地得到回收,并且能一定程度地稳定催化剂,提高催化效率,这对我们设计合成新型可回收的催化剂具有重要的借鉴意义.     

Ionic Liquid–Catalyzed Internal Redox Esterification Reaction

The internal redox esterification of α,β-unsaturated aldehydes and alcohols was carried out using different ionic liquids (ILs) as catalysts and reaction solvents. The basic ionic liquid, 1-butyl-3-methylimidazolium acetate ([bmim]OAc), exhibited the best activity for this reaction. The influences of the amount of ionic liquid catalyst and reaction time on yield of saturated ester have been investigated. The results showed that ionic liquid anions have a crucial effect on the redox esterification of α,β-unsaturated aldehydes and alcohols. The nucleophilic carbenes generated in situ from the ionic liquid cation were believed to be actual active species for this reactions.     

Oxidative homocoupling of alkynes using supported ionic liquid phase (SILP) catalysts--systematic investigation of the support influence

Supported Ionic Liquid Phase (SILP) catalysts have been prepared by effective immobilization of [Cu(TMEDA)(OH)]Cl in a nano-metric film of an ionic liquid on various oxidic support materials. The catalysts were tested for the oxidative homocoupling of 1-alkynes to the corresponding diynes in in a combined high throughput and conventional batch reaction approach. Among the screened support materials silica based materials performed best. The results indicate that for the specific reaction the thickness of the ionic liquids layer and therefore the mobility of the homogeneous copper complex within the ionic liquid layer as deduced from solid state nmr measurements have major impact on the catalytic performance. The optimized catalysts could be recycled up to four times without any loss of activity.     

功能性离子液体支载液相有机合成研究进展

阐述了功能性离子液体支载液相有机合成的概念、特点及其在小分子杂环化合物、多肽、寡糖合成等有机反应中的应用, 以及功能性离子液体支载的催化剂和试剂在液相有机合成中的应用. 研究表明功能性离子液体作为一种新型的高负载量的可溶性载体可以广泛应用于液相有机合成中, 有效地促进了反应的进行, 简化了分离手段, 显著地提高了反应的选择性和收率.     

非均相离子液体催化CO2环加成反应研究进展

二氧化碳（CO2）是一种来源丰富的C1资源,在温和条件下实现CO2的资源化利用是当前研究的热点之一。CO2环加成反应制备环状碳酸酯是CO2资源化利用的重要途径之一。环状碳酸酯是电池电解液的优良介质,可承受较恶劣的光、热及化学变化;同时也是聚氨酯、聚碳酸酯等精细化工中间体,广泛应用于医药、化工、纺织、印染等领域。非均相离子液体催化剂具有化学和热稳定性好、合成过程简单和可重复使用等优势。本文重点总结了近年来非均相离子液体催化剂在CO2和环氧化物环加成反应中的应用,并对非均相离子液体催化CO2环加成反应的发展进行展望。     

Catalytic Performance of Ruthenium‐Supported Ionic‐Liquid Catalysts in Sustainable Synthesis of Macrocyclic Lactones

Thirteen‐ to eighteen‐membered lactones were synthesized by ring‐closing olefin‐metathesis reactions of bis‐olefins with heterogeneous Grubbs‐supported ionic‐liquid catalysts (SILCs), in which homogeneous Grubbs catalysts were confined in pores of alumina with the aid of an ionic liquid. The Grubbs‐SILCs exhibited higher catalytic performance than their homogeneous counterparts and could be repeatedly recovered by simple filtration and re‐used several times.     

离子液体超酸清洁催化苯的烷基化反应

研究了在具有Lewis酸性的离子液体体系中进行的苯与烯烃及卤代烃的烷基化反应.以氯化1-甲基-3-乙基咪唑(MEIC)、氯化1-丁基吡啶(BPC)、氯化l-甲基-3-丁基咪唑(MBIC)及盐酸三甲胺(TMHC)季铵盐分别与AlCl3原位合成法制备离子液体催化体系.结果表明:以上各种离子液体均有很高的催化活性,反应转化率在较短的时间内达到100%.其中TMHC-A1Cl3离子液体单烷基化选择性达98.6%.与AlCl3相比,催化活性显著提高,生成烷基化产物不溶于离子液体,因而易于分离,催化剂可重复使用.