Asymmetric Catalytic Hydroamination of Activated Olefins in Ionic Liquids

The addition of a series of both aliphatic and aromatic amines to electron‐poor olefins was investigated using [Ni(Pigiphos)(THF)]²⁺ as catalyst (with different counterions) in various ionic liquids based on imidazolium‐ and picolinium‐salt derivatives. The catalysts gave rise to selectivities comparable to those obtained when the reaction was conducted in neat organic solvents (ee up to 66%), but significant higher activities, with a total turnover number (TON) of up to 300.     

Synthesis,Characterization, Thermal Analyses,and Spectroscopic Properties of Novel Naphthyl-Functionalized Imidazolium Ionic Liquids

A series of novel ionic liquids based on naphthyl-functionalized imidazolium cation have been prepared. Their structure was characterized by NMR. The thermal stabilities of the prepared liquids were studied by thermal gravimetric analysis. The new ionic liquids containing NTf^-₂ anion display significantly higher thermal stabilities (>400°C). Anion exchange to PF^-₆, BF^-₄, and Br^– decreases the thermal stabilities of such ionic liquids. Fluorescence and UV–Vis absorption spectroscopy were used to study the spectroscopic properties of the ionic liquids. Compared with common ionic liquids, the described ionic liquids provide robust fluorescence properties and remarkably increased UV–Vis absorption. This research may enrich the field of functionalized ionic liquids and provide a platform for extension of ionic liquid applications.     

Solubility and Thermodynamic Properties of Ammonium-Based Gemini Ionic Liquids in Pure Solvents

Journal of Solution Chemistry - Asymmetrical ammonium-based gemini ionic liquids, 1-trimethylammonium-3-(1-methylpiperidinium)propane dibis[(trifluoromethyl)sulfonyl]imide ([N111C3MPip][NTf2]2) and...     

Novel Cyclic Sulfonium‐Based Ionic Liquids: Synthesis,Characterization, and Physicochemical Properties

A new series of ionic liquids composed of three cyclic sulfonium cations and four anions has been synthesized and characterized. Their physicochemical properties, including their spectroscopic characteristics, ion cluster behavior, surface properties, phase transitions, thermal stability, density, viscosity, refractive index, tribological properties, ion conductivity, and electrochemical window have been comprehensively studied. Eight of these salts are liquids at room temperature, at which some salts based on [NO₃]^? and [NTf₂]^? ions exhibit organic plastic crystal behaviors, and all the saccharin‐based salts display relatively high refractive indices (1.442–1.594). In addition, some ionic liquids with the [NTf₂]^? ion exhibit peculiar spectroscopic characteristics in FTIR and UV/Vis regions, whilst those salts based on the [DCA]^? ion show lower viscosities (34.2–62.6 mPa s at 20 °C) and much higher conductivities (7.6–17.6 mS cm^?1 at 20 °C) than most traditional 1,3‐dialkylimidazolium salts.     

新型乙醇胺型离子液体的合成与表征

由乙醇胺,二乙醇胺和三乙醇胺提供阳离子,由有机酸(甲酸,乙酸和丙酸)提供阴离子,合成了8种新型乙醇胺型离子液体,其结构经1H NMR,IR和元素分析表征.熔点、电导率等测定结果表明,他们均具有离子液体的特征.     

Characterization of a Novel Organic Solvent Tolerant Protease from a Moderately Halophilic Bacterium and Its Behavior in Ionic Liquids

An extracellular protease was purified from a novel moderately halophilic bacterium Salinivibrio sp. strain MS-7 by the combination of an acetone precipitation (40–80 %) step and a DEAE-cellulose anion exchange column chromatography. Kinetic parameters of the enzyme exhibited V _max and K _m of 130 U/mg and 1.14 mg/ml, respectively, using casein as a substrate. The biochemical properties of the enzyme revealed that the 21-kDa protease had a temperature and pH optimum of 50 °C and 8.0, respectively. The enzyme was strongly inhibited by phenylmethylsulfonyl fluoride, Pefabloc SC, chymostatin, and also EDTA, indicating that it belongs to the class of serine metalloproteases. Interestingly, Ba²⁺ and Ca²⁺ (2 mM) strongly enhanced the enzyme activity, while Fe²⁺ and Mg²⁺ activated moderately and Zn²⁺, Ni²⁺, and Hg²⁺ decreased the enzyme activity. The effect of organic solvents with different logP on the purified protease revealed complete stability in toluene, ethyl acetate, chloroform, and n-hexane at 10 and 50 % (v/v) and moderate stability even in 50 % of DMSO and ethanol. The behavior of the MS-7 protease in three imidazolium-based ionic liquids exhibited suitable activity in these green solvent systems, especially in 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆MIM][PF₆]). Comparison of the purified protease with other previously reported proteases suggests that strain MS-7 secrets a novel organic solvent-tolerant protease with outstanding activity in organic solvents and imidazolium-based ionic liquids, which could be applied in low water synthetic section of industrial biotechnology.     

Synthesis,Characterization, and Catalytic Behavior of Methoxy- and Dimethoxy-substituted Pyridinium-Type Ionic Liquids

Synthesis of methoxy-substituted pyridinium-type ionic liquids from a nontoxic and easy method is described. Catalytic behaviors of synthesized ionic liquids were investigated with various concentrations for the Mannich reaction. We have observed that methoxy- and dimethoxy-substituted pyridinium bromides showed better catalytic behavior than other ionic liquids.     

Improving Catalytic Performance of Burkholderiacepacia Lipase by Chemical Modification with Functional Ionic Liquids

Various imidazolium and choline-based functional ionic liquids(ILs) comprising different cations and anions were grafted onto Burkholderiacepacia lipase(BCL) through surface amino acids coupling. The catalytic activity, thermostability, organic solvent tolerance and adaptability to temperature and pH changes of the modified BCL were then evaluated in olive oil hydrolysis reaction. The results showed that different combinations of cations and anions in ILs had important influence on the catalytic performance of the modified lipases. BCL modified with IL[Choline] [H₂PO₄] was the most improved lipase, in which increases by 1.2 folds in relative activity, 2.5 folds in typical proton solvent(10% methanol, volume fraction), and 1.4 folds in thermostability(after incubation at 70℃ for 2 h) were achieved in relative toits native form. BCL modified with[HOOCEPEG₃₅₀IM] [BF₄] had higher optimal tempe-rature and pH, and better thermosability compared with the native and other modified BCLs. The conformational changes of BCLs were also confirmed by fluorescence spectroscopy and circular dichroism spectroscopy.     

Aggregation Influence of Polyethyleneglycol Organic Solvents with Ionic Liquids BMIBF4 and BMIPF6

Polyethyleneglycol (PEG, M_w = 200, 300, 400) and polyethyleneimine (PEI, M_w = 423) are used to investigate the ion‐ion interactions in liquids and physicochemical properties after the addition of PEG (or PEI) to ionic liquids 1‐butyl‐3‐methylimidazole tetrafluoroborate (BMIBF₄) or 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIPF₆). Nuclear magnetic resonance is used to investigate the effects of solvent content (x = 0.05, 0.1, 0.2, 0.3, 0.4, 0.5) and temperature (303–338 K) on the diffusion coefficient, chemical shift, and two dimensional NOESY, HOESY spectra. HOESY spectra show that a hydrogen bond forms between the alkyl hydrogen of PEG and the ¹⁹F atom of BF₄⁻ and PF₆⁻. After the addition of PEG to BMIBF₄ (or BMIPF₆), the aggregation is the dominant effect for the diffusion coefficient result. When the molecular weight and the concentration of PEG increase, the effect of coving generates larger clusters involving PEG, BMI⁺ and its counter anion. The BF₄⁻ group of the BMIBF₄/PEG system is smaller than PF₆⁻, it's easier to generate clusters in the BMIBF₄/PEG system than it is in the BMIPF₆/PEG system.     

Synthesis and Characterization of Benzimidazolium Salts as Novel Ionic Liquids and their Catalytic Behavior in the Reaction of Alkylation

A new series of ionic liquids have been prepared containing benzimidazolium cation (abbreviated as Bim). These salts were characterized by DSC, NMR, elemental analysis and thermogravimetric analysis. They showed different properties compared to imidazolium cation due to the introduction of benzene ring. The alkylation of benzene/diphenyl ether with 1-dodecene was carded in C4eBimBr-AlCl3 ionic liquids showing high catalytic activity when the mole ratio of C4eBimB:AlCl3 was 1:2.     

Catalytic Activity of Polyfunctional Ionic Liquids in Oxidation of Model Sulfur Organic Compounds

Russian Journal of Applied Chemistry - Ionic liquids based on 1-methylimidazole were synthesized. The liquids contain Bronsted acid centers in the cation and a transition metal atom in the anion....     

Synthesis and Characterization of 1,2-Dimethyl Imidazolium Ionic Liquids and Their Catalytic Activities

The synthesis of substituted imidazolium-type ionic liquids via a simple method is described. Our synthesized ionic liquids are more useful in the catalytic behavior of the Mannich reaction.     

Ionic Liquids Beyond Simple Solvents: Glimpses at the State of the Art in Organic Chemistry

Within the last 25 years ionic liquids have written a tremendous success story, which is documented in a nearly uncountable amount of original research papers, reviews, and numerous applications in research and industry. These days, ionic liquids can be considered as a mature class of compounds for many different applications. Frequently, they are used as neoteric solvents for chemical tansformations, and the number of reviews on this field of research is huge. In this focused review, though, we are trying to evaluate the state of the art of ionic liquid chemistry beyond using them simply as solvents for chemical transformations. It is not meant to be a comprehensive overview on the topic; the choice of emphasis and examples rather refects the authors’ personal view on the field. We are especially highlighting fields in which we believe the most fundamental developments within the next five years will take place: biomass processing, (chiral) ionic liquids from natural sources, biotransformations, and organic synthesis.     

脂肪酶在有机溶剂中催化酯合成和酯交换反应

报道了猪胰脂肪酶在冻干时的pH值、有机溶剂的极性、反应系统的含水量、温度以及底物碳链的长度和支链对酶在有机相中催化活性的影响规律。利用该酶合成了具有玫瑰香味的月桂酸香茅酯和辛酸香茅酯。     

以Schiff碱为阳离子的新型离子液体的制备与表征

Two novel ionic liquids, N,N＇-disalicylideneethylenediaminium acetate and N,N＇-disalicylideneethylenediaminium trifluoroacetate, were prepared and characterized by IR, ^1H NMR, DTA-TG and elemental analysis. The experimental results indicate that the new ionic liquids possess lower melting point and higher electrical conductivity. It is noteworthy that the ionic liquids reported herein are the first member of the ionic liquid family with the Schiff base functional group in the cation.     

以N为中心的阴离子离子液体的合成、表征及应用

首次通过不同阴离子的钾盐和不同的季铵化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的阴离子功能化离子液体。通过红外、核磁共振、质谱对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现功能化离子液体具有良好的热稳定性,其分解温度在224-289℃范围内。将功能化离子液体[EMIm][N(CN)COC2H5]作为配体应用于无膦配体的Suzuki偶联反应,发现在反应中加入功能化离子液体[EMIm][N(CN)COC2H5]可以使反应收率提高10-20%。     

复合离子液体中纤维素的催化分解

通过将酸性功能化离子液体与对纤维素具有溶解作用的离子液体进行复合, 构建了一类新型的高效催化纤维素分解的体系, 并采用热重(TG)分析方法, 研究了复合离子液体中纤维素的分解行为. 结果表明: 复合离子液体中纤维素的分解温度明显降低, 溶于离子液体中的纤维素可被酸性离子液体原位催化分解. 纤维素的分解温度受离子液体催化剂的酸性及纤维素在复合离子液体中的溶解度影响明显: 酸性越强, 溶解度越大, 纤维素的分解温度越低.     

Terpenes to Ionic Liquids: Synthesis and Characterization of Citronellal-Based Chiral Ionic Liquids

A series of new chiral ionic liquids have been prepared and characterized starting from a simple, economical, and commercially available monoterpene, citronellal. The aldehyde functionality in citronellal is converted into a Schiff base using an amine, followed by reduction with Raney nickel to give the desired quaternary amine. Most of the ionic liquids generated using this procedure are found to be liquids at room temperature.