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Ionic Liquids

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本发明涉及一种环氧化合物与二氧化碳环加成制备环状碳酸酯的方法。使用NaOH,Na2CO3,KOH或K2CO3修 饰的强碱性苯乙烯离子交换树脂或大孔强碱性苯乙烯离子交换树脂担载金为催化剂,在反应温度为40-200℃,反应压力1atm-60atm,反应时间 1-48小时条件下催化环氧化合物与二氧化碳环加成制相应环状碳酸酯。该方法的主要特点是催化剂活性高,操作简便,产物分离和催化剂回收容易且可重复使 用。

邓友全,石峰,郭术,等. 环氧化合物与二氧化碳环加成制备环状碳酸酯的方法. Cn1789258. 2007.

209.56 KB

本发明公开了一种环境友好的担载金催化剂制备方法。该方法将载体铁盐溶液与金盐溶液混合均匀,在20~80℃、搅拌下用碳酸钠作为沉淀剂进行沉淀,调节最 终pH值为7~10,继续搅拌1.5~4小时,静置2.5~6小时,过滤,20~80℃干燥4~24小时。不需洗涤,不需焙烧。该方法的主要特点是催化剂 制备操作简单,节水节能,环境友好,催化剂抗Cl-毒害能力强。

邓友全,乔波涛,李雪礼. 环境友好的担载金催化剂制备方法. Cn1795985. 2007.

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本发明公开了一种多氨基甲酸酯的制备方法。具体的讲,采用离子液体为催化剂,多胺与碳酸二甲酯通过催化制相应多氨基甲酸酯的方法。本发明催化剂简单,除离 子液体外不加入其它溶剂和催化剂;产品以晶体形式析出,分离简单、纯度高;离子液体可以循环使用,属于环境友好的生产过程;反应所需条件简单,易于工业化 生产;反应时间短,反应在常压下进行,操作安全。

邓友全,周瀚成,石峰,等. 一种多氨基甲酸酯的制备方法. Cn1778793. 2007.

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本发明涉及一种以N-质子化己内酰胺为阳离子基团的Brφnsted酸性离子液体为催化剂和反应介质的催化环己酮肟经Beckmann重排反应制备ε-己 内酰胺的方法。在温和的反应温度和较短的反应时间内高转化率高选择性地生成ε-己内酰胺,而且该酸性离子液体可以重复使用。本发明由于使用以质子化的该反 应的产物为阳离子基团的酸性离子液体作为催化剂和反应介质,因而产物不再与酸性离子液体结合,反应结束后无需加碱中和,反应体系简单,不会造成环境污染, 酸性离子液体不腐蚀设备,离子液体的制备成本低,节约资源,具有很好的工业应用前景。

邓友全,郭术,杜正银,等. 催化环己酮肟重排制备ε-己内酰胺的方法. Cn1781908. 2007.

余学军 / 邓友全
253.20 KB

Microwave enhanced syntheses of 9-boronobenzyladenine derivatives by the reaction of adenine with the corresponding bromomethylphenylboric acid were reported. Microwave irradiation reduced the overnight reaction time of conventional thermal methods to 10 min, provided the desired products and increased the yields up to three times. Preliminary in vitro pharmacological tests were also described.

Keywords: 9-boronobenzyladenines, anti-inflammatory, antitumor, microwave-asisted synthesis

★★★☆☆ Yu XJ,Liu W,Hu WD,et al. Microwave Assisted Synthesis And Biological Activities Of 9-boronobenzyladenine Derivatives[J]. Journal Of Chemical Research,2007:347-349.

张庆华 / 邓友全
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A series of ionic liquids (ILs) based on nitrile-functionalized imidazolium, pyridinium, and quaternary ammonium as cations and chlorides and tetrafluoroborate, hexafluorophosphate, dicyanamide, and bis- (trifluoromethanesulfonyl)imide as anions have been prepared and characterized. The physicochemical properties such as spectroscopic, thermal, solubility, surface, electrochemical, tribological, and toxic properties were comparatively studied. The results showed that the incorporation of a CN group to cations could result in remarkable changes in these properties. The reason resulting in such remarkable differences in the properties may be attributed to the conformational changes in the imidazolium groups caused by the interaction between the CN group with other neighboring cations or anions and the enhancement in hydrogen-bonding interactions due to the incorporation of a CN group.

★★★☆☆ Zhang QH,Li ZP,Zhang J,et al. Physicochemical Properties Of Nitrile-functionalized Ionic Liquids[J]. J. Phys. Chem. B,2007,111(11):2864-2872.

杨静 / 邓友全
462.95 KB

A novel series of ionic liquids (ILs) based on N-alkyl- -caprolactam as cations [Cn-CP]+ (Cn ) alkyl with different numbers of C atoms; n ) 6, 8, 10, 12, 16, or 18) containing toluene-p-sulfonate [TS]- and methanesulfonate [MS]- as anions have been synthesized via a one-step atom-economic reaction. Characterizations of these ILs by differential scanning calorimetry, polarizing optical microscopy, variabletemperature powder X-ray diffraction, etc., were conducted. The results showed that the caprolactambased ILs (n≥8) were enantiotropic thermotropic liquid crystals, except for C18-CPMS (monotropic), and displayed smectic A phases. Some properties, such as higher transition enthalpies (e.g., ΔH=83.1 kJ/mol for C18-CPTS), higher specific heat capacities (e.g., Cp=2.85 J/g·K for C16-CPTS) and higher heat storage densities (e.g., sensible heat storage density Es=262.8l MJ/m3 for C16-CPTS; latent heat storage density El=146.0 MJ/m3 for C18-CPTS), were observed. Fluorescence measurements showed that the homologous Cn-CPTS ILs exhibited strong fluorescence behavior. Finally, the test of acute toxicity toward rats showed that these new ILs were less toxic than the popular [BMIm]BF4 IL.

★★★★☆ Yang J,Zhang QH,Zhu LY,et al. Novel Ionic Liquid Crystals Based On N-alkylcaprolactam As Cations[J]. Chem. Mater.,2007,19:2544-2550.

周瀚成 / 邓友全
203.18 KB

Selective synthesis of carbamates from amines and dimethyl carbonate were studied in the presence of various ionic liquids as catalysts. The –SO3H-functionalized ionic liquid was found to be the most active catalyst among the applied ionic liquids, and nearly 100% conversion and 95% selectivity were achieved when using 1,6-hexanediamine as reactant. The acid functional ionic liquid catalyst system is also readily separable and reusable after reaction.

Keywords: Green chemistry; Ionic liquid; Carbamates; Amine; Non-phosgene

★★★☆☆ Zhou HC,Shi F,Tian X,et al. Synthesis Of Carbamates From Aliphatic Amines And Dimethyl Carbonate Catalyzed By Acid Functional Ionic Liquids[J]. Journal Of Molecular Catalysis A: Chemical,2007,271:89-92.

张娟 / 邓友全
119.82 KB

The solubilities of C2H4 and CO2 and the interactions of polar and nonpolar solutes with the novel ionic liquids (ILs) 1-butyronitrile-3-methylimidazolium bis(trifluoromethylsulfonyl) imidate (CpMIm[NTf2]), 1-butyronitrile-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl) imidate (CpMMIm[NTf2]), 1-butyronitrile-3-methylimidazolium dicyanamide (CpMIm[N(CN)2]), 1-butyronitrile-2,3-dimethylimidazolium dicyanamide (CpMMIm-[N(CN)2]), 1-butyl-3-methylimidazolium palmitate (BMIm[n-C16H33COO]), and 1-butyl-3-methylimidazolium stearate (BMIm[n-C18H35COO]) were studied by gas chromatography at infinite dilution at T ) (303.15, 313.15, 323.15, and 333.15) K. Henry’s law constant kH of C2H4 and CO2 gas, infinite dilution activity coefficient γ∞, molar enthalpies of solution ΔsolH∞, and partial molar excess enthalpies of solution ΔHE∞ and of Gibbs energies ΔGE∞ were determined for polar and nonpolar solutes in these novel ILs. Compared with the 1,3-dialkylimidazolium ILs, cyano functional group substitution on the alkyl chain results in a remarkable decrease of the interactions of hydrocarbons. BMIm[n-C16H31OO] and BMIm[n-C18H35OO] demonstrate strong solubilization for both polar and nonpolar solutes. Straight lines of ln Vg versus 1/T and ln γ∞ versus 1/T were obtained for the majority of solutes in the temperature range. BMIm[NTf2] and 1-octyl-3-methylimidazolium tetrafluoroborate (OMIm[BF4]) show much better solubility for thiophene and are better solvents for the separations of thiophene from hydrocarbons.

★★★☆☆ Zhang J,Zhang QH,Qiao BT,et al. Solubilities Of The Gaseous And Liquid Solutes And Their Thermodynamics Of Solubilization In The Novel Room-temperature Ionic Liquids At Infinite Dilution By Gas Chromatography[J]. J. Chem. Eng. Data,2007,52:2277-2283.