Recombination of Photogenerated Lophyl Radicals in Imidazolium‐Based Ionic Liquids

Laser flash photolysis is applied to study the recombination reaction of lophyl radicals in ionic liquids in comparison with dimethylsulfoxide as an example of a traditional organic solvent. The latter exhibits a similar micropolarity as the ionic liquids. The ionic liquids investigated are 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ( 1 ), 1‐hexyl‐3‐methylimidazolium hexafluorophosphate ( 2 ), and 1‐butyl‐3‐methylimidazolium tetafluoroborate ( 3 ). The recombination of the photolytic generated lophyl radicals occur significantly faster in the ionic liquids than expected from their macroscopic viscosities and is a specific effect of these ionic liquids. On the other hand, this reaction can be compared with the macroscopic viscosity in the case of dimethylsulfoxide. Activation parameters obtained for lophyl radical recombination suggest different, anion‐dependent mechanistic effects. Quantum chemical calculations based on density functional theory provide a deeper insight of the molecular properties of the lophyl radical and its precursor. Thus, excitation energies, spin densities, molar volumes, and partial charges are calculated. Calculations show a spread of spin density over the three carbon atoms of the imidazolyl moiety, while only low spin density is calculated for the nitrogens.     

Cationic polymerization of styrene involving ionization of the C?Cl bond in ionic liquid/SO2 mixture

There has been a recent upsurge in interest in use of ionic liquids as reaction media for various chemical processes. Until recently, ionic liquids were considered as highly polar solvents. Our earlier investigation indicated that cationic polymerization of styrene initiated by aryl (alkyl) chlorides in ionic liquids may proceed even in the absence of coinitiator (Lewis acid). Polymerization, however, did not conform to controlled polymerization scheme. More recently, it has been claimed that ionic liquids are not as polar as it was previously assumed. Independently, high solubility of sulfur dioxide in ionic liquids was noticed. As sulfur dioxide displays a high ionizing power toward organic halides, we applied ionic liquid/sulfur dioxide mixture as a solvent in cationic polymerization of styrene initiated by aryl (alkyl) chlorides. Results show that in this reaction medium ionization of the C? Cl bond is facilitated, and the contribution of chain transfer reaction can be reduced as compared with polymerization in ionic liquid alone. Ionization of the C? Cl bond, however, is still not sufficiently fast to ensure conditions of controlled polymerization. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5251–5257, 2009     

High viscosity of ionic liquids causes rate retardation of Diels-Alder reactions

Second order rate constants, k2 have been determined for three bi-molecular Diels-Alder reactions to demonstrate that the high viscosity of ionic liquids can be a detrimental property in carrying out Diels-Alder reactions, if ionic liquids are employed as solvent media. It is possible to enhance the reaction rates of the reaction if a co-solvent is mixed in pure ionic liquid used as a solvent.     

Ionic Liquids for the Chemical Recycling of Polymeric Materials and Control of Their Solubility

Plastics are wonderful materials that have modernized our daily life; however, importance of effective recycling of plastics is gradually recognized widely. In this account, we describe our discovery of new and efficient methods for the chemical recycling of plastics using ionic liquids (ILs). Since the chemical recycling usually requires high temperature conditions to breakdown chemical bonds in polymeric materials, we thought that less-flammability and non-volatility of ionic liquids are the most suitable physical properties for this purpose. Ionic liquids successfully depolymerized polyamides and unsaturated polyesters smoothly and corresponding monomeric materials were obtained in good yields. To the best of our knowledge, this was the first use of Ionic liquids for such reactions. However, we encountered another difficult problem-separation. To solve the problem, we developed solubility-switchable ionic liquids, a new type of ionic liquids in which solubility is readily changed using the chemistry of protective groups. Conversion between hydrophilic and lipophilic forms was readily achieved using a simple chemical treatment under mild conditions, and the complete separation of products was achieved by liquid-liquid-extraction. The robustness of either form unlocks their wide use as reaction solvents.     

Understanding chemical reaction mechanisms in ionic liquids: successes and challenges

The focus of this article is an examination of chemical reaction mechanisms in ionic liquids. These mechanisms are compared with those pertaining to the same reactions carried out in conventional solvents. In cases where the mechanisms differ, attempts to provide an explanation in terms of the chemical and physicochemical properties of the reactants and of the components of the ionic liquids are described. A wide range of reactions from different branches of chemistry has been selected for this purpose. A sufficient background for student readers has been included. This tutorial review should also be of interest to kineticists, and to both new and experienced investigators in the ionic liquids field.     

Recent progress in studies on polarity of ionic liquids

Although many ionic liquids have been reported, their polarity is not completely understood. Different empirical polarity scales for molecular solvents always lead to different polarity orders when they are applied on ionic liquids. Based on a literature survey, this review summarizes the recent polarity scales of ionic liquids according to the following 4 classes: (1) equilibrium and kinetic rate constants of chemical reactions; (2) empirical polar parameters of ionic liquids; (3) spectral properties of probe molecules; (4) multiparameter approaches. In addition, their interrelations are presented. A systematic understanding of the relationship between different polarity parameters of ionic liquids is of great importance for finding a universal set of parameters that can be used to predict the polarities of ionic liquids quantitatively. The potential utilization of the electron paramagnetic resonance in this field is also addressed.     

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.     

一类新型二价离子液体的合成及其结构和性质关系的初步研究

设计合成了一类新型的二价离子液体, 并对其结构和性质之间的关系进行探讨.     

咪唑类离子液体中的有机氧化反应

简要概括了离子液体的种类和特点,重点介绍了咪唑类离子液体中的Baeyer-Villiger、Corey-Chayk-ovsky、醇、芳香烃、烷烃及含硫化合物的氧化反应.指出作为新型绿色溶剂的离子液体具有许多独特的物理化学性质,在多个领域具有重要的应用价值.     

Ionic Liquids-New "Solutions" for Transition Metal Catalysis

Ionic liquids are salts that are liquid at low temperature (<100 degrees C) which represent a new class of solvents with nonmolecular, ionic character. Even though the first representative has been known since 1914, ionic liquids have only been investigated as solvents for transition metal catalysis in the past ten years. Publications to date show that replacing an organic solvent by an ionic liquid can lead to remarkable improvements in well-known processes. Ionic liquids form biphasic systems with many organic product mixtures. This gives rise to the possibility of a multiphase reaction procedure with easy isolation and recovery of homogeneous catalysts. In addition, ionic liquids have practically no vapor pressure which facilitates product separation by distillation. There are also indications that switching from a normal organic solvent to an ionic liquid can lead to novel and unusual chemical reactivity. This opens up a wide field for future investigations into this new class of solvents in catalytic applications.     

Influence of Guanidinium Salts and Other Ionic Liquids on the Three‐Component Aza‐Diels?Alder Reaction

The three‐component reaction of aniline, benzaldehyde, and dienophiles such as 2,3‐dihydrofuran, ethyl vinyl ether, 2,3‐dihydropyran, and cyclopentadiene can be promoted by ionic liquids like imidazolium salts and guanidinium salts under thermal as well as microwave conditions. The chemical yield as well as the diastereoselectivity of the Povarov reaction strongly depend on the ionic liquid employed. The guanidinium salts can be recycled and reused several times without loss of reactivity.     

离子液体中电生成CoIL催化行为研究

在离子液体中, 研究了CoL(钴希夫碱配合物)的电化学行为, 并进一步探讨了其对氯苄还原以及PhCH₂Cl与CO₂反应的催化特性. CoL在离子液体中呈现一对由扩散控制的单电子可逆氧化还原峰. 通过电化学行为研究发现, 其氧化还原峰电位不易随金属有机配合物的配体和离子液体阴离子的变化而变化, 并求得了相应的扩散系数. 同时, 循环伏安图表明该体系能对PhCH₂Cl的还原起催化作用, 反应经历一个ECE过程. 另外, 该体系还能催化PhCH₂Cl与CO₂反应, 通过恒电位电解得到(PhCH₂)₂CO, 说明常温常压下, CO₂可以通过CoL催化在离子液体中进行固定, 得到新的有机化合物.     

胍盐离子液体的研究进展

胍盐离子液体由于具有较高的热稳定性、化学稳定性和催化活性而受到关注. 总结了近年来胍盐离子液体的合成、性质和应用三个方面的研究进展.     

离子液体中电生成CoL催化行为研究

在离子液体中,研究了CoL(钴希夫碱配合物)的电化学行为,并进一步探讨了其对氯苄还原以及PhCH_2Cl与CO_2反应的催化特性.CoL在离子液体中呈现一对由扩散控制的单电子可逆氧化还原峰,通过电化学行为研究发现,其氧化还原峰电位不易随金属有机配合物的配体和离子液体阴离子的变化而变化,并求得了相应的扩散系数.同时,循环伏安图表明该体系能对PhCH_2Cl的还原起催化作用,反应经历一个ECE过程,另外,该体系还能催化PhCH_2Cl与CO_2反应,通过恒电位电解得到(PhCH_2)_2CO,说明常温常压下,CO_2可以通过CoL催化在离子液体中进行固定,得到新的有机化合物。     

吗啉基功能化酸性离子液体催化苯酚-叔丁醇选择性烷基化反应

研究了吗啉基磺酸功能化离子液体催化苯酚与叔丁醇的烷基化反应.考察不同的功能化离子液体、反应时间、反应温度、苯酚与叔丁醇的摩尔比以及离子液体的用量等反应条件对烷基化反应的影响,并考察了离子液体的循环使用.研究结果表明离子液体用量为20%苯酚时,在最佳优化条件下苯酚的转化率和选择性分别为92.4%和64.1%;离子液体重复使用三次,其催化活性不变.     

负载型氨基功能化离子液体吸附CO2性能差异研究

以Al₂O₃、SiO₂和活性炭为载体,采用浸渍法制备了负载型离子液体（[NH₂p-mim]X:X= Br-,PF₆-,BF₄-,NTf₂-）CO₂吸附剂,利用红外光谱（FT-IR）、元素分析(EA)、热重差热分析（TG-DTA）等技术对负载型离子     

Effect of ionic liquid organizing ability and amine structure on the rate and mechanism of base induced elimination of 1,1,1-tribromo-2,2-bis(phenyl-substituted)ethanes

The kinetics of the elimination reaction of 1,1,1-tribromo-2,2-bis(phenyl-substituted)ethanes into the corresponding 1,1-dibromo-2,2-bis(phenyl-substituted)ethenes induced by amines were studied in three room temperature ionic liquids ([BMIM][BF₄], [BMIM][PF₆], [BdMIM][BF₄]). In order to have information about reagent-ionic liquid interactions, the reaction was carried out over the temperature range (293.1-313.1 K). To study the effect of the amine on the rate and occurrence of the elimination reaction, several primary, secondary and tertiary amines with different structure (cyclic and acyclic), basicity and steric requirements were used. The data collected show that the reaction occurs faster in ionic liquids than in other conventional solvents. Furthermore, ionic liquids seem to be able to induce, for the studied reaction, a shift of mechanism from E1_cb (in MeOH) versus E2 (in ionic liquid).     

离子液体中固定化光合细菌催化不对称还原反应的研究

采用苯乙酮为模式底物,选用了3种典型的离子液体作为反应介质系统研究了离子液体与缓冲液构成的均相及两相体系中固定化光合细菌催化不对称还原反应的特性．通过对构建的离子液体反应体系进行条件优化,发现与水相及有机相相比,离子液体作为生物催化反应介质更有利于还原反应的进行,并且离子液体及固定化细胞易回收重复利用．研究结果表明,在...     

水饱和离子液体中萘普生的酶法拆分

 考察了五种水饱和离子液体反应介质中固定化脂肪酶催化外消旋萘普生甲酯的水解. 结果表明,这些具有不同阴阳离子组合的咪唑基离子液体作为反应介质都能促进水解反应的有效进行,但在水饱和1-正丁基-3-甲基咪唑六氟磷酸盐(［bmim］PF6)中,反应进行得更快,转化率更高. 这些离子液体对脂肪酶均有一定的溶解作用并使溶解的脂肪酶失活. 脂肪酶在离子液体中的溶解度与其剩余活性之间有一定的相关性. 为了解决脂肪酶在离子液体中的溶解问题,使用非极性、高比表面积的无定形多孔硅胶YWG-C6H5对脂肪酶进行了固定化. 在水饱和［bmim］PF6中使用固定化脂肪酶催化反应,反应72 h的转化率为28.3%, 产物的对映体过量值为98.2%, 继续进行反应,转化率将增加,但产物的对映体过量值明显下降. 利用离子液体有别于传统有机溶剂的特性,对离子液体的循环使用、产物的回收和水的补充方法进行了研究. 在反复批式反应中,固定化脂肪酶连续使用五次,活性仅略微下降.     

Effect of stationary phase polarity on the retention of ionic liquid cations in reversed phase liquid chromatography

Chromatographic analysis of ionic liquids on different types of packings offers interesting possibility to determine their retention mechanism. As a consequence, the major interactions between stationary phase ligands and analyzed chemical entities can be defined. The main aim of this work was to analyze cations of ionic liquids on chemically bonded stationary phases with specific structural properties. The attempt to predict the main interactions between positive ions of ionic liquids and stationary phase ligands was undertaken. For that purpose, butyl, octyl, octadecyl, phenyl, aryl, mixed, alkylamide, and cholesterolic packings were chosen and applied to the analysis of six most commonly used ionic liquids' cations. Obtained results indicate mainly dispersive and pi-pi type of interaction part in the retention mechanism of analyzed compounds.