1-戊基-3-甲基咪唑类离子液体的合成

以1-氯戊烷和N-甲基咪唑为原料合成了室温离子液体1-戊基-3-甲基咪唑四氟硼酸盐(PMIMBF4)和六氟磷酸盐(PMIMPF6),通过考察各种影响因素对中间产物氯代咪唑盐(PMIMCl)的影响得出合成1-戊基3-甲基咪唑离子液体的最佳条件为:原料N-甲基咪唑与1-氯戊烷的投料比为1.2∶1,反应温度为70-75℃,反应时间为24 h。最终产物的收率为92%-94%。产物结构用FT-IR和1HNMR光谱进行表征。     

离子负载的羟基(对甲苯磺酰氧基)碘苯对α,β-查耳酮及其衍生物的加成产物用于1,4,5-三芳基吡唑的合成

以对碘甲苯为原料,经过自由基溴代得到4-溴甲基碘苯,接着与吡啶发生亲核取代反应,随后在水溶液中和六氟磷酸钾发生阴离子交换,合成了N-(4-碘苯甲基)吡啶六氟磷酸盐,最后经氧化制备了N-[(4-羟基对甲苯磺酰氧基碘)苯甲基]吡啶六氟磷酸盐新试剂。利用该试剂成功地合成了α,β-二(对甲苯磺酰氧基)查耳酮及其衍生物,然后和苯肼发生环合反应制备了1-苯基-4,5-二芳基吡唑。回收后的离子负载的碘苯容易再生成试剂,而再生试剂和查耳酮及其衍生物的加成反应活性几乎保持不变。化合物结构用1HNMR、13CNMR、IR、MS、元素分析表征。     

碘帕醇的合成工艺研究

以L-乳酸为原料,经两步反应,以55%的收率得到S-2-乙酰氧基丙酰氯。以5-氨基-2,4,6-三碘-1,3-苯二甲酸为原料,使用二氯亚砜转化得到5-氨基-2,4,6-三碘-1,3-苯二甲酰氯,再与S-2-乙酰氧基丙酰氯反应得到5-[(2S)-(2-乙酰氧基)丙酰胺基]-2,4,6-三碘-1,3-苯二甲酰氯,接着与2-氨基-1,3-丙二醇反应得到N,N′-双[2-羟基-(1-羟甲基)乙基]-5-[(2S)(2-乙酰氧基)丙酰胺基]-2,4,6-三碘-1,3-苯二甲酰胺,在碱性条件下脱乙酰基,得到非离子型X射线造影剂碘帕醇,这四步反应收率为50%。     

1-丁基-3-甲基咪唑四氟硼酸盐的合成研究

以1-溴丁烷和N-甲基咪唑为原料合成了中间体溴化1-丁基-3-甲基咪唑,以中间体与NaBF4进行复分解反应制备了离子液体1-丁基-3-甲基咪唑四氟硼酸盐。探讨了投料比、反应时间、反应温度对中间体和1-丁基-3-甲基咪唑四氟硼酸盐产率的影响,确定了最佳合成条件。在此工艺条件下,1-丁基-3-甲基咪唑四氟硼酸盐产率可达85%以上。     

1-乙基-3-甲基咪唑四氟硼酸盐的合成研究

以溴乙烷和N-甲基咪唑为原料合成了中间体溴化1-乙基-3-甲基咪唑,以中间体与NaBF4进行复分解反应制备了离子液体1-乙基-3-甲基咪唑四氟硼酸盐。探讨了投料比、反应时间、反应温度对中间体和1-乙基-3-甲基咪唑四氟硼酸盐产率的影响,确定了最佳合成条件。在此工艺条件下,1-乙基-3-甲基咪唑四氟硼酸盐产率可达94%以上。     

羟基与酯基官能团化离子液体的合成

以溴代或氯代醇或酯和吡啶为原料合成三个离子液体前体即溴化N-羟乙基吡啶、氯化N-羟己基毗啶和N-甲氧羰乙基吡啶氯代盐;分别将它们与四氟硼酸钠进行复分解反应得到相应的离子液体即N-羟乙基毗啶四氟硼酸盐、N-羟己基毗啶四氟硼酸盐和N-甲氧羰乙基毗啶四氟硼酸盐。利用核磁共振波谱对三个离子液体进行了表征。     

N,N-二甲基吡咯烷鎓类离子盐在超级电容器中应用

两步法合成了N,N-二甲基吡咯烷鎓双(三氟甲基磺酰)亚胺(DMPTFSI)、N,N-二甲基吡咯烷鎓四氟硼酸盐(DMPBF4)二种离子盐,研究了这两种离子盐在乙腈中电导率性能。对所制备出超级电容器进行3. 0V,100C,15 000周循环充放电性能研究,发现N,N-二甲基吡咯烷鎓四氟硼酸盐(DMPBF4)体系电解液在电容及内阻方面表现突出。     

离子液体催化的萘并吡喃的合成研究

以碱性离子液体1-甲基-3-二甲氨基丙基咪唑四氟硼酸盐[Dmnpmim]BF4为催化剂,不同的芳香醛、1-萘酚和丙二腈为底物,合成了一系列萘并吡喃类衍生物。     

离子液体合成含溴1，3，4-噻二唑的研究

采用无溶剂一锅法合成了1-丁基-3-甲基咪唑四氟硼酸盐离子液体([bmim]BF4),反应原料N-甲基咪唑、溴代正丁烷和四氟硼酸钾在水浴中搅拌反应3 h,收率为91.8%。然后以1-丁基-3-甲基咪唑四氟硼酸盐离子液体催化合成含溴1,3,4-噻二唑类化合物,反应条件为:反应温度95～100℃,反应时间2 h,收率为58.3%。用减压蒸馏的简单方法将离子液体分离出来。研究结果表明,用离子液体[bmim]BF4合成含溴1,3,4-噻二唑的方法比传统方法即用浓硫酸作催化剂的方法的收率高6.7%。     

1-(3-(N-胱胺)丙基)-3-甲基咪唑溴离子液体的合成与表征

以1,3-二溴丙烷与N-甲基咪唑为原料,制备1-溴丙基-3-甲基咪唑溴盐离子液体。采用二叔丁基二碳酸酯保护胱胺的单侧氨基,然后再与1-溴丙基-3-甲基咪唑溴盐发生取代反应生成1-(3-(N-胱胺)丙基)-3-甲基咪唑溴离子液体;分别用核磁、红外对中间体和产物进行表征,结果表明我们成功合成了新型氨基功能化离子液体。     

Novel homogeneous gel fibers and capillaries from blend of titanium tetrabutoxide and siloxane functionalized ionic liquid

The preparation of ionogels by sol–gel processing has attracted much attention, because the final ceramic materials combine properties of both inorganic matrix (thermal and mechanical stability) and the ionic liquid (ionic conductivity). The aim of this study was to combine different imidazolium based ionic liquids (1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄], 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF₄], 1-decyl-3-methylimidazolium tetrafluoroborate [DMIM][BF₄] and 1-methyl-3-[3′-(triethoxysilyl)propyl]imidazolium chloride MTICl) with titanium(IV) butoxide to prepare homogenous hybrid fibers through aqueous sol–gel reaction. The study showed that ionic liquid miscibility with metal alkoxide plays an important role in the preparation of homogenous fibers. Unlike simple imidazolium salts functionalized ionic liquid was dispersed homogenously in fibers, but the main advantage is derived from its chemical structure. New stable ionic liquid can be involved in sol–gel processes through ethoxy groups and as a result it associates with titanium alkoxide network by covalent bonding providing non-leaking ceramic hybrid material. Indirect and direct characterization studies of the product were carried out by energy-dispersive X-ray spectroscopy (EDX), silicon-29 nuclear magnetic resonance spectroscopy (²⁹Si NMR), scanning electron microscopy (SEM) and optical microscopies; also infrared spectra (IR) were recorded. Thermal analyses were performed by differential scanning calorimetry (DSC).     

Preparation of Ni/SiO catalyst in ionic liquids for hydrogenation

A series of silica supported nickel catalysts were prepared from nickel nitrate and tetraethyl orthosilicate by the sol-gel method with the imidazolium type ionic liquids as solvents. The catalysts were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Their catalytic performances for the selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde were investigated. The results show that the Ni/SiO₂ catalyst prepared with 1-(2-hydroxyethyl)-3-methyl-imidazole tetrafluoroborate ionic liquid as solvent exhibits the highest catalytic activity for the reaction. Under the optimal conditions of catalyst dosage (based on the mass of cinnamaldehyde used) 10%, reaction pressure 2 MPa, temperature 373 K and reaction time 2 h, the conversion of cinnamaldehyde and the selectivity to hydrocinnamaldehyde can reach 97.6% and 98.8%, respectively.     

亲水性咪唑鎓偶氮苯基离子液体的合成及光控离子传导应用

光响应偶氮苯基离子液体因其偶氮苯基异构可调控性质而备受关注。研究合成了一种新型偶氮苯基离子液体,1-丁基-3-(4-苯基偶氮苄基)咪唑四氟硼酸酯([Azo][BF_4]),其结构经FT-IR、~1H NMR表征,并测试其水溶液在不同光照条件下的传导性能。结果表明:[Azo][BF_4]水溶液可通过光调控微观结构变化影响宏观离子传导率,为离子液体自组装研究提供基础。     

Preparation of Ni/SiO2 catalyst in ionic liquids for hydrogenation

A series of silica supported nickel catalysts were prepared from nickel nitrate and tetraethyl orthosilicate by the sol-gel method with the imidazolium type ionic liquids as solvents. The catalysts were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Their catalytic performances for the selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde were investigated. The results show that the Ni/SiO₂ catalyst prepared with 1-(2-hydroxyethyl)-3-methylimidazole tetrafluoroborate ionic liquid as solvent exhibits the highest catalytic activity for the reaction. Under the optimal conditions of catalyst dosage (based on the mass of cinnamaldehyde used) 10%, reaction pressure 2 MPa, temperature 373 K and reaction time 2 h, the conversion of cinnamaldehyde and the selectivity to hydrocinnamaldehyde can reach 97.6% and 98.8%, respectively. __________ Translated from Petrochemical Technology, 2007, 36(1): 9–14 [译自:石油化工]     

微波法制备咪唑类离子液体

运用常规两步法和微波法制备了离子液体1-丁基-3-甲基咪唑四氟硼酸盐([bmim]BF4)以及1-羟乙基-3-甲基咪唑四氟硼酸盐([C2OHmim]BF4),并通过红外光谱表征以及密度和溶解度等物理性质的检测,对两种制备方法进行了比较。实验结果表明,不需使用任何溶剂,选择N-甲基咪唑和溴代正丁烷(2-氯乙醇)的配比为1∶1.1,[bmim]Br([C2OHmim]Cl)和NaBF4的配比为1∶1,在微波炉功率为350 W的条件下反应,[bmim]BF4和[C2OHmim]BF4的产率分别达70.0%和76.9%。反应采取微波间歇加热的方式,方法简单高效、无溶剂污染,但产率偏低,其制备条件还需进一步研究与完善。     

Brnsted酸离子液体催化合成2-芳基-2,3-二氢-4(1H)-喹啉酮

制备了3种Brnsted酸离子液体:1-甲基-3-(3-磺丙基)咪唑硫酸氢盐([SO3H-pmim]HSO4)、1-(3-磺丙基)吡啶硫酸氢盐([SO3H-ppy]HSO4)、N-(3-磺丙基)三乙基铵硫酸氢盐([SO3H-ptea]HSO4),用于催化邻氨基苯乙酮和芳香醛的反应一锅法合成2-芳基-2,3-二氢-4(1H)-喹啉酮,考察了它们的催化活性和重复使用性能。结果表明,3种离子液体对邻氨基苯乙酮和芳香醛的反应均具有较高的催化活性,以[SO3H-ptea]HSO4催化性能更好。在60℃和无溶剂条件下,[SO3H-ptea]HSO4可以有效催化邻氨基苯乙酮和不同芳香醛反应,以68.3%～95.1%的收率得到目标化合物。离子液体经真空干燥重复使用5次,催化活性无明显下降。     

N,N-二甲基色胺衍生物合成研究

以四氢呋喃和对氰甲基盐酸苯肼 (Ⅹ )为主要原料合成了色胺衍生物N ,N 二甲基 2 { 5 [(3 氨基 1,2 ,4 口恶二唑 5 基 )甲基 ] 1 氢 吲哚 3 基 }乙胺 (Ⅶ )。四氢呋喃和氯化氢反应 ,得到4 氯丁醇 ( ) ,产率为 6 2 % ;用氯铬酸吡啶盐氧化得 4 氯丁醛 ( ) ,产率为 6 1% ;经缩醛化得 4 氯丁醛缩甲醇 ( ) ,产率为 5 6 % ;用二甲胺取代得 4 (N ,N 二甲胺基 )丁醛缩甲醇(Ⅸ ) ,产率为 86 % ;Ⅸ与Ⅹ经环化得N ,N 二甲基 2 [5 (氰甲基 ) 1氢 吲哚 3 基 ]乙胺 (Ⅺ ) ,产率为 76 % ;Ⅺ经酯化得N ,N 二甲基 2 [5 (乙酯甲基 ) 1氢 吲哚 3 基 ]乙胺 (Ⅻ ) ,产率为 82 % ;Ⅻ与羟基硫酸胍缩合得产物 (Ⅶ ) ,产率为 6 6 %。     

Dehydration of fructose into 5-hydroxymethylfurfural in the presence of ionic liquids

The acid-catalyzed dehydration of fructose was performed in a microbatch reactor at 80 °C using two commercially available ionic liquids, a hydrophilic one, 1-butyl 3-methyl imidazolium tetrafluoroborate (BMIM⁺BF₄⁻), and a hydrophobic one, 1-butyl 3-methyl imidazolium hexafluorophosphate (BMIM⁺PF₆⁻). When the reaction is carried out in 1-butyl 3-methyl imidazolium tetrafluoroborate as solvent and Amberlyst-15 as catalyst, a yield up to 50% in 5-hydroxymethylfurfural (HMF) is obtained within around 3 h. When the reaction is carried out now in 1-butyl 3-methyl imidazolium tetrafluoroborate and in 1-butyl 3-methyl imidazolium hexafluorophosphate as solvents and Amberlyst-15 as catalyst, DMSO is used as a co-solvent, in order, in particular, to solubilize fructose in the hydrophobic ionic liquid. Under these conditions, both ionic liquids allow the reaction to work more rapidly than in DMSO alone and with yields in HMF close to 80% within 24 h.     

1，3-二烷基咪唑类离子液体的合成研究

通过N-烷基化反应制备了中间产物氯化-1-丁基-3-甲基咪唑[BMIM]Cl离子液体,得到较佳的制备条件。引入微波辅助改进了[BMIM]Cl合成方法。同时在超声波辅助下,通过离子交换制备了亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸盐[BMIM]BF4以及憎水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐[BMIM]PF6。结果发现,微波辅助和超声波辅助可以加速反应速度。产物结构用IR和1H NMR进行表征。     

咪唑类离子液体溶解纤维素的研究进展

综述了1-丁基-3-甲基咪唑氯盐、1-烯丙基-3-甲基咪唑氯盐、1-(2-羟乙基)-3-甲基咪唑氯盐等咪唑类离子液体对纤维素的溶解性能,咪唑类离子液体/纤维素溶液的流变性能以及咪唑类离子液体在纤维素纤维及薄膜加工中的应用;咪唑类离子液体均能较好地溶解纤维素,咪唑类离子液体/纤维素溶液均为切力变稀流体;指出选择合适的阴、...