离子液体[BMIm]BF_4对莪术醇手性环氧异构体的拆分

利用莪术醇环氧手性异构体在离子液体1-丁基-3-甲基咪唑四氟硼酸盐中形成复合物的溶解度不同,以22%的(10R)-10,14-环氧莪术醇(E1)收率(99%ee)和49%的(10S)-10,14-环氧莪术醇(E2)收率(92%ee)完成了对莪术醇环氧手性异构体的拆分.离子液体可以回收利用,回收后的离子液体分离效果不受影响.     

吉非替尼的合成新工艺研究

以6-羟基-7-甲氧基喹唑啉-4-酮(1)为起始原料,在离子液体催化下与N-(3-氯丙基)吗啉(2)醚化,然后经氯代再与3-氯-4-氟苯胺进行亲核取代反应,得到目标产物吉非替尼,三步反应总收率为68.7%。通过改变反应物配比、离子液体用量和反应温度,得到了关键中间体3的优化制备工艺条件:n(1)∶n(2)=1.0∶1.2;离子液体四氟硼酸1-甲基-4-丁基咪唑鎓用量为原料1的质量的5%;95℃下反应5h。在此条件下,醚化收率约93.6%。该路线具有反应条件温和、分离简单、路线短和总收率较高的特点,为吉非替尼的工业化生产提供了实验依据。     

离子液体中乙酸异山梨醇酯的合成

以1-丁基-3-甲基咪唑六氟磷酸盐离子液体为溶剂,对新一代长效抗心绞痛药物单硝酸异山梨酯中间体异山梨醇进行了萃取分离,避免了使用高真空高温蒸馏;以酸性离子液体N-甲基咪唑硫酸氢盐为溶剂和催化剂,合成了中间体2-乙酸异山梨醇酯,产物结构经红外光谱确证.异山梨醇收率80%,2-乙酸异山梨醇酯收率86%.     

吡咯烷酮酸性离子液体的合成及其对酯化反应的催化活性

合成并表征了 2-吡咯烷酮硫酸氢盐([Hnhp]HSO4)、 1-甲基-2-吡咯烷酮硫酸氢盐([Hnmp]HSO4)、 1-甲基咪唑硫酸氢盐([Hmim]HSO4)、 1-(3-磺酸基)-丙基-3-甲基咪唑硫酸氢盐([C3SO3Hmim]HSO4)和1-(3-磺酸基)-丙基-2-吡咯烷酮硫酸氢盐([C3SO3Hnhp]HSO4)等以HSO-4为阴离子的质子酸离子液体,并以乙酸和正丁醇的酯化反应考察了这些离子液体的催化活性.结果表明,当n(n-BuOH):n(MeCO2H):n([C3SO3Hnhp]HSO4)=1.2:1:0.005,反应温度为120 ℃和反应时间为 1 h 时,酯收率可达99%以上;反应结束后离子液体与酯产物可分成两相,而且该离子液体重复使用8次,催化活性没有明显下降.探讨了阳离子结构及Brnsted酸性对催化活性的影响,考察了离子液体与酯化反应相关组分的互溶性.结果表明,离子液体的分相性能对催化效果有较大的影响,离子液体的催化活性与其酸性、溶解性密切相关.     

磺酸功能化双核离子液体催化合成双酚F

合成并表征了4种具有Brnsted酸性的磺酸功能化咪唑类离子液体催化剂,考察了其在催化苯酚、甲醛合成双酚F反应中的催化活性.结果表明磺酸功能化双核离子液体双-(3-磺酸丙基-1-咪唑)亚丁基硫酸氢盐([DPSIM][HSO4]2)不仅催化活性最佳,还提高了4,4’-双酚F异构体的含量.以[DPSIM][HSO4]2为催化剂,在苯酚与甲醛摩尔比30∶1、离子液体催化剂质量浓度6.8%、反应温度90℃、反应时间60 min的优化条件下,双酚F收率可达94.1%,同时提出了其催化合成双酚F的反应机理.该离子液体催化剂腐蚀性低,易分离回收,在重复使用6次后,双酚F收率仍在70%以上.     

酸性离子液体催化脂肪酸甲酯聚合制备二聚酸甲酯

 以 Brönsted-Lewis 酸性离子液体为催化剂, 用于催化生物柴油中不饱和脂肪酸甲酯聚合制备二聚酸甲酯反应, 考察了催化剂种类、催化剂用量、反应温度和时间等因素对聚合反应性能的影响, 得到较佳的反应条件. 结果表明, 当以 1-(3-磺酸)-丙基-3-甲基咪唑氯锌酸盐[HO3S-(CH2)3-mim]Cl-ZnCl2 (ZnCl2 摩尔分数为 0.67) 为催化剂, 生物柴油 15 g, m(生物柴油):m(离子液体) = 15:1, 于 240 oC 下反应 6 h 时, 二聚酸甲酯收率为 63.2%, 其中三聚体含量小于 5%. 另外, 该催化剂重复使用 5 次后, 二聚酸甲酯收率仍超过 63%, 表明其具有较好的重复使用性能. 离子液体的 Brönsted 和 Lewis 酸位的协同效应显著提高了其催化活性.     

己内酰胺功能化离子液体的合成及其催化酯化性能的研究

以价格低廉的己内酰胺为原料,制备和表征了4种己内酰胺功能化离子液体:1-(3-磺丙基)己内酰胺硫酸氢盐([C3SO3HCP]HSO4)、1-(3-磺丙基)己内酰胺对甲苯磺酸盐([C3SO3HCP]PTSA)、1-(3-磺丙基)己内酰胺磷酸氢盐([C3SO3HCP]H2PO4)、1-(3-磺丙基)己内酰胺四氟硼酸盐([C3SO3HCP]BF4).以乙酸和乙醇的酯化反应考察4种酸性离子液体的催化活性,并与3种具有不同氮杂环的SO3H-功能化离子液体和浓硫酸相对照.结果表明:当n(C2H5OH)∶n(CH3COOH)=1∶1.5,催化剂[C3SO3HCP]HSO4用量为酸醇总质量的5%,反应温度80℃,反应时间6 h,酯收率可达93.8%,离子液体经真空干燥重复使用10次后,仍具有较高的催化活性,而且对奥氏体316 L不锈钢试样的腐蚀率不到浓硫酸的1/6.还考察了以[C3SO3HCP]HSO4为催化剂催化合成系列乙酯也获得了较高的酯收率,且离子液体均能与酯产物自动分相.与传统硫酸催化酯化相比,此类离子液体催化酯化具有生产成本低、过程清洁、腐蚀率低、使用周期长等优点,具有替代传统浓硫酸催化醇酸酯化反应的潜力.     

吗啡啉功能化酸性离子液体的合成、表征及其催化酯化性能

制备和表征了三种新型质子酸离子液体: 吗啡啉硫酸氢盐([Hnhm]HSO4)、4-甲基吗啡啉硫酸氢盐 ([Hnmm]HSO4)和SO3H-功能化的4-(3-磺丙基)吗啡啉硫酸氢盐([C3SO3Hnhm]HSO4). 以氯乙酸(CAA)和乙醇合成氯乙酸乙酯的酯化反应考察了它们的酸性和催化活性, 并与1-(3-磺酸基)丙基-3-甲基咪唑硫酸氢盐、1-(3-磺丙基)吡啶硫酸氢盐、1-(3-磺丙基)-2-吡咯烷酮硫酸氢盐等三种具有不同氮杂环的SO3H-功能化酸性离子液体以及浓硫酸相对照. 结果表明, 上述SO3H-功能化离子液体对酯化反应的催化性能比非SO3H-功能化的[Hnhm]HSO4和[Hnmm]HSO4都高, 等同甚至优于浓硫酸. 当反应条件为: n(EtOH)∶n(CAA)∶n([C3SO3Hnhm]HSO4)＝1.3∶1∶0.2, 反应温度80 ℃, 反应时间3 h, 酯收率可达93.4%. 而且离子液体经真空干燥重复使用9次, 催化活性仍无明显下降. 以[C3SO3Hnhm]HSO4催化乙酸和不同醇的酯化反应获得较高的酯收率和选择性, 离子液体跟酯产物均能自动分相. 还考察了SO3H-功能化酸性离子液体对奥氏体316不锈钢的腐蚀性. 尽管SO3H-功能化离子液体与硫酸的酸性相近, 但对钢试样的腐蚀率不到硫酸的1/3.     

离子液体阴阳离子协同催化芳香胺与碳酸丙烯酯反应

以离子液体1-丁基-3-甲基咪唑乙酸盐([bmim]OAc)为催化剂,以芳香胺和碳酸丙烯酯为原料,一步合成了5-甲基-3-芳基噁唑烷-2-酮.系统考察了反应温度、反应时间以及催化剂用量对反应性能的影响.在优化的反应条件下,5-甲基-3-苯基噁唑烷-2-酮的收率可达99％.研究了离子液体阴阳离子结构对反应性能的影响,发现...     

离子液体催化合成苯并哒嗪酮类葡萄糖苷化合物

在室温离子液体1-正丁基-3-甲基咪唑四氟硼酸盐中合成了一系列1-取代-6-羰基苯并哒嗪酮-3-四乙酰葡萄糖苷类化合物,旋光度分别为(+)24.6°、(+)11.0°、(+)13.6°和(+)20.3°,其均为右旋糖苷. 讨论了反应时间、反应物摩尔比、不同离子液体及离子液体的重复使用对反应的影响,用IR与1H NMR测试技术对标题化合物的结构进行了表征.结果表明,合成反应具有条件温和,副反应少,环境友好,收率较高,离子液体可重复使用等优点.     

Influence of water on the surface of the water-miscible ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate: a sum frequency generation analysis

Sum frequency generation spectroscopy (SFG) was used to study the influence of water on the surface of the water-miscible ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate. The orientation of the cation at the gas-liquid interface was analyzed as a function of ionic liquid concentration in water for concentrations from 0 to 1 mole fraction of the ionic liquid. The cation was found to be oriented with the imidazolium ring nearly parallel to the surface plane with a tilt angle > or = 70 degrees when the ionic liquid was dry. Furthermore, no noticeable change in the orientation was observed when high concentrations of water were mixed with the ionic liquid. The cation butyl chain is projecting into the gas phase with a CH(3) tilt angle of 54 +/- 2 degrees when the ionic liquid is dry and 46 +/- 4 degrees when mixed with water. Water is oriented at the surface only for concentration < or = 0.02 mole fraction of the ionic liquid. At higher ionic liquid concentrations (mole fractions > or = 0.05) the gas-liquid interface resembles that of the pure ionic liquid.     

Ni2＋的引入对离子液体烷基化催化性能的影响

Thealkylationofisobutanewithbuteneisanim portantprocessforthe productionofhigh qualitypetroleum .In placeofconcentratedsulfuricacid ,Et3NHCl/AlCl3ionicliquidhasbeenusedinthereac tionwithfairlygoodeffect[1] ,butthereisstillabigdifferencecomparedwiththeresultsofconcentratedsulfuricacid .TheC8contentinthealkylatesobtainedwithconcentratedsulfuricacidwas 72 1% [2 ] ,butitwasonly 5 6 %withtheionicliquid .ThekeyreactioninthealkylationishydrogentransferfromC+8toC08[3] ,andthisisthemainreasonforth…     

[Bmim]Cl/FeCl3离子液体催化α-生育酚与β-D-五乙酰葡萄糖的糖基化反应

以[Bmim]Cl/FeCl₃(三氯化铁/氯化丁基甲基咪唑)离子液体作为反应介质和催化剂, 考察了离子液体的酸度、反应温度及反应时间对α-生育酚与β-D-五乙酰吡喃型葡萄糖糖基化反应的影响. 结果表明, 离子液体的催化活性与其酸强度密切相关, 离子液体的酸性越强, 其对此糖基化反应催化活性越高. 在FeCl₃与[Bmim]Cl物质的量比为2的[Bmim]Cl/FeCl₃离子液中, α-生育酚与β-D-五乙酰吡喃型葡萄糖在45 ℃下反应3 h, 可以得到较高的转化率, α-生育酚的转化率最高可达70.2%. 同有机溶剂作为反应介质相比, 反应条件温和, 反应时间短, 室温离子液体具有更好的催化活性, 所得产物与离子液体不溶, 便于分离, 催化体系可循环使用, 且对环境友好.     

Characterization of PVdF(HFP) gel electrolytes based on 1-(2-Hydroxyethyl)-3-methyl imidazolium ionic liquids

Poly(vinylidenefluoride)-hexafluoropropylene (PVdF(HFP))-ionic liquid gel electrolytes were prepared using ionic liquids based on 1-(2-hydroxyethyl)-3-methyl imidazolium tetrafluoroborate and 1-(2-hydroxyethyl)-3-methyl imidazolium hexafluorophosphate. A conventional metathesis reaction was used to prepare these ionic liquids, which have high purity and exhibit a liquid state at room temperature. The prepared polymer-ionic liquid gel proved to be a free-standing and rubbery film in which the degree of transparency differed according to the ratio and type of ionic liquid used. TGA and FTIR analyses confirmed that the solvent, N,N-Dimethylacetamide (DMAC), used for mixing PVdF(HFP) polymer with ionic liquid was almost totally removed during the gelling and drying processes. SEM photographs were taken of the surface structure of the PVdF(HFP)-ionic liquid gel in order to evaluate the morphology of the film's surface according to the mixing ratio and the nature of the ionic liquid. The thermal behaviors of PVdF(HFP)-ionic liquid gels were observed to be similar to those of neat ionic liquids through DSC analysis, and the compatibility between the polymer and ionic liquid was investigated by XRD analysis. The ionic conductivities of all the gels were 10(-3)-10(-5) S cm(-1) in a temperature range of 20-70 degrees C.     

不同离子液体中三氯化铁的电化学行为

本文采用循环伏安法研究了FeCl3在五种不同的离子液体(包括疏水性和亲水性的离子液体)中的电化学行为,计算了不同离子液体中FeCl4的扩散系数.实验结果表明:Fe3+在离子液体中的氧化还原过程是一个具有较高可逆性的扩散控制过程.离子液体的阴、阳离子的结构及大小对Fe3+的电化学响应有影响,且离子液体的阴离子的影响较阳离子更大一些.     

过渡金属离子液体EMIFeCl3的性质研究

在干燥高纯氩气氛的手套箱内, 直接将摩尔比为1∶1的高纯无水FeCl3与氯化1-甲基-3-乙基咪唑(EMIC)混合, 得到棕色透明的离子液体EMIFeCl4. 在293.15~343.15 K温度范围内测定了该离子液体的密度和表面张力. 利用Glasser经验方程和空隙模型研究了EMIFeCl4的性质, 并与离子液体EMIAlCl4进行比较, 指出空隙模型具有一定的合理性.     

Noncovalent approach to one-dimensional ion conductors: enhancement of ionic conductivities in nanostructured columnar liquid crystals

Noncovalent design of new liquid-crystalline (LC) columnar assemblies based on an ionic liquid has shown to be useful to achieve anisotropic high ionic conductivities. An equimolar mixture of an ionic liquid, 1-butyl-3-methylimidazolium bromide, and 3-[3,4,5-tri(octyloxy)benzoyloxy]propane-1,2-diol, which is partially miscible with the ionic liquid, exhibits an LC hexagonal columnar phase from -4 to 63 degrees C. This columnar supramolecular assembly forming the nanostructures shows the one-dimensional (1D) ionic conductivity of 3.9 x 10(-3) S cm(-1) at 50 degrees C along the column, which is more than 700 times higher than that of the corresponding covalent-type columnar ionic liquid, 1-methyl-3-[3,4,5-tri(octyloxy)benzyl]imidazolium bromide, which is 5.3 x 10(-6) S cm(-1) at 50 degrees C. This significant enhancement of the ionic conductivity is attributed to the increase of the mobility of the ionic part.     

Heterogeneous electron transfer kinetics at the ionic liquid/metal interface studied using cyclic voltammetry and scanning electrochemical microscopy

The electrochemical behavior of a redox-active, ferrocene-modified ionic liquid (1-ferrocenylmethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) in acetonitrile and in an ionic liquid electrolyte (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) is reported. Reversible electrochemical behavior was observed in each electrolyte with responses typical of those for unmodified ferrocene observed in each medium. In the ionic liquid electrolyte, the diffusion coefficient of the redox-active ionic liquid increased by a factor of 5 upon increasing the temperature from 27 to 90 degrees C. The kinetics of electron transfer across the ionic liquid/electrode interface were studied using cyclic voltammetry, and the standard heterogeneous electron transfer rate constant, k (0) was determined to be 4.25 x 10 (-3) cm s (-1). Scanning electrochemical microscopy was then also used to probe the heterogeneous kinetics at the interface between the ionic liquid and the solid electrode and conventional kinetic SECM theory was used to determine k (0). The k (0) value obtained using SECM was higher than that determined using cyclic voltammetry. These results indicate that SECM is a very useful technique for studying electron transfer dynamics in ionic liquids.     

新型碱性离子液体催化酯交换合成生物柴油

两步法合成了吗啉阴离子型碱性离子液体1-丁基-3-甲基吗啉盐Im,经 ¹H-NMR和FT-IR分析确认了离子液体中间体的结构,并通过阴离子交换得到碱性离子液体,对该离子液体在酯交换制备生物柴油反应中的催化性能进行了研究。结果表明,该碱性离子液体Im具有较高的酯交换催化活性,在60 ℃、催化剂用量为3%、醇油物质的量比为6.5：1.0、反应2 h的条件下,产物脂肪酸甲酯（FAME）含量可达95.80%。而且该离子液体的催化稳定性较好,重复使用5次后仍有较高的催化活性。     

Effects of ionic liquid as additive and the pH of the mobile phase on the retention factors of amino benzoic acids in RP-HPLC

As an organic salt, ionic liquids are widely used as new solvent media. In this paper, three positional isomers, such as o-amino benzoic acid, m-amino benzoic acid, and p-amino benzoic acid are separated with four different ionic liquids as additives to the mobile phase using reversed-phase (RP) high-performance liquid chromatography (HPLC). Amino benzoic acids are biologically active substances; the p-isomer is present in a group of water-soluble vitamins and is widely known as a sunscreen agent. The ionic liquids used are 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium methylsulfate, and 1-octyl-3-methylimidazolium methylsulfate. The effects of the length of the alkyl group on the imidazolium ring and its counterion, the concentrations of the ionic liquid, and the effect of the pH of the mobile phase on the retention factor of the amino benzoic acid isomers are studied. Separation with the ionic liquid in the eluent was better than the separation without the ionic liquid. The pH mainly affected the retention and elution order of the solutes in RP-HPLC.