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1.
α‐Hydroxylamino phosphonates are synthesised in a one‐pot operation by three‐component coupling reactions of aldehydes, hydroxylamines and diethyl phosphite using 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF4) or 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim]PF6) ionic liquids under mild and neutral conditions. The recovered ionic liquids can be recycled for four to five runs without loss of activity. 相似文献
2.
Aziridines undergo ring opening smoothly with various arylamines in 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF4) or 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim]PF6) ionic liquids under mild and neutral conditions to afford the corresponding vicinal‐diamines in excellent yields with high regioselectivity. The recovered activated ionic liquids are recycled for four to five runs with no loss of activity. 相似文献
3.
Indoles react smoothly with carbonyl compounds in 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF4) or 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim]PF6) ionic liquids under mild reaction conditions to afford the corresponding bis‐indolylmethanes in excellent yields. These ionic liquids can be recovered and recycled in subsequent reactions without any apparent loss of activity. 相似文献
4.
Linghao He Jing Sun Xiuxin Wang Chuandao Wang Rui Song Yongmei Hao 《Polymer International》2013,62(4):638-646
In this study, a facile and efficient protocol to enhance the β‐phase content of poly(vinylidene fluoride) (PVDF) is developed, in which the effect of room temperature ionic liquids (RTILs), including [1‐butyl‐3‐methylimidazolium (bmim)][PF6], [bmim][BF4], [bmim][FeCl4] and [bmim][Cl], on the crystallization behavior of PVDF is investigated. The resulting PVDF/RTIL hybrids are characterized by Fourier transform infrared (FTIR) spectroscopy, XRD, polarized optical microscopy (POM) and DSC. The FTIR spectroscopy and XRD results show that the fraction of β‐phase, F(β), is significantly enhanced by the incorporation of RTILs, specifically from 49.2% for neat PVDF to 92.6% for hybrid filled with 15 wt% [bmim][PF6]. The analysis of the crystallization behavior based on the DSC tests reveals that the degree of crystallinity increases with incorporation of RTILs, implying that RTILs could act as directing agents to facilitate the crystallization process, which is further evidenced by the POM results. In addition, the non‐isothermal crystallization kinetics of PVDF and PVDF/RTIL composites are investigated by means of DSC and the results indicate that the addition of the RTILs significantly influences the mechanism of nucleation and growth of PVDF crystallites. © 2013 Society of Chemical Industry 相似文献
5.
Haixia Shan Zaijun Li Ming Li Guoxia Ren Yinjun Fang 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2008,83(6):886-891
BACKGROUND: Enzymes may exhibit enhanced activity, stability and selectivity in ionic liquids, depending on the properties of the liquid. The physical–chemical properties of ionic liquids, however, may be modified by altering the anion or cation in the ionic liquid. This feature is a key factor for realizing successful reactions. In this work, a new ionic liquid, 1‐isobutyl‐3‐methylimidazolium hexafluorophosphate (abbreviated as [i‐C4mim][PF6]), was synthesized and investigated as a novel medium for the transesterification reaction of 2‐phenylethanol with vinyl acetate catalyzed by pseudomonas capaci lipase. As contrasts, the reaction was also carried out in two reference solvents; the isomeric ionic liquid [i‐C4mim][PF6], 1‐butyl‐3‐methylimidazolium hexafluorophosphate (abbreviated as [C4mim][PF6]), and hexanes. RESULTS: As reaction medium, [i‐C4mim][PF6] was best among the three solvents. The initial reaction rate, the equilibrium conversion of 2‐phenylethanol and the half‐lifetime of the lipase in [i‐C4mim][PF6] medium were about 1.5, 1.2 and 3‐fold that obtained in [C4mim][PF6] medium, respectively. The lipase in [i‐C4mim][PF6] medium was recycled 10 times without substantial diminution in activity. CONCLUSION: The ionic liquid [i‐C4mim][PF6] has good biocompatibility, and can be used widely as green media in various biocatalysis reactions to improve the activity and stability of enzymes. Besides hydrophobicity and nucleophilicity, the spatial configuration of ionic liquids is also considered a key factor effecting the behaviour of the enzyme in ionic liquids. Copyright © 2008 Society of Chemical Industry 相似文献
6.
Alkenes undergo smooth cyclopropanation with ethyl diazoacetate using a catalytic amount of rhodium acetate dimer, Rh2(OAc)4, immobilized in the air‐ and moisture‐stable 1‐butyl‐3‐methylimidazolium hexafluorophosphate ionic liquid, [bmim]PF6, to afford cyclopropanecarboxylates in excellent yields with high trans‐selectivity. The recovery of the catalyst is facilitated by the hydrophobic nature of [bmim]PF6. The recovered ionic liquid containing Rh2(OAc)4 can be reused for three to five subsequent runs with only a gradual decrease in activity. 相似文献
7.
Quantum chemical studies on the simultaneous interaction of thiophene and pyridine with ionic liquid
The simultaneous interaction of thiophene and pyridine with different ionic liquids:1‐butyl‐1‐methylpyrrolidinium tetrafluoroborate([BPYRO][BF4]),1‐butyl‐1‐methylpyrrolidinium hexafluoro‐phosphate ([BPYRO][PF6]), 1‐butyl‐4‐methylpyridinium tetrafluoroborate ([BPY][BF4]), 1‐butyl‐4‐methylpyridinium hexafluorophosphate ([BPY][PF6]) and 1‐benzyl‐3‐methylimidazolium tetrafluoroborate ([BeMIM][BF4]) were investigated using quantum chemical calculations. A three‐tier approach comprising of partial charges, interaction energies and sigma profile generation using conductor‐like screening model for real solvents (COSMO‐RS) was chosen to study the systems. A quantitative attempt based on the CH‐π interaction in ionic liquid; thiophene–pyridine complexes gave the interaction energies of ILs in the order: [BPY][BF4] > [BPYRO][PF6] > [BeMIM][BF4] > [BPY][PF6] > [BPYRO][BF4]. An inverse relation was observed between the activity coefficient at infinite dilution predicted via COSMO‐RS–based model and interaction energies. The dominance of CH‐π interaction was evident from the sigma profiles of ionic liquid together with thiophene and pyridine. © 2010 American Institute of Chemical Engineers AIChE J, 2011 相似文献
8.
Effect of the ionic liquid [bmim]PF6 on the nonisothermal crystallization kinetics behavior of poly(ether‐b‐amide)
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Blending ionic liquid with crystalline polymer permits the design of new high‐performance composite materials. The final properties of these materials are critically depended on the degree of crystallinity and the nature of crystalline morphology. In this work, nonisothermal crystallization behavior of poly(ether‐b‐amide) (Pebax®1657)/room temperature ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate, [bmim]PF6) was investigated by differential scanning calorimetry. The presence of [bmim]PF6 can retard the nucleation of Pebax®1657 and lead to the crystallization depression of the PA block and the crystalline disappearance of the PEO block. However, the dilution effect of the IL results in a higher growth rate of crystallization of PA block. The influence of [bmim]PF6 content and cooling rate on crystallization mechanism and spherulitc structures was determined by the Avrami equation modified by Jeziorny and Mo's methods, whereas the Ozawa's approach fails to describe the nonisothermal crystallization behavior of Pebax®1657/[bmim]PF6 blends. In the modified Avrami analysis, the Avrami exponent of PA blocks, n > 3, for pure Pebax®1657, while 3 > n > 2 for Pebax®1657/[bmim]PF6 blends testifies the transformation of crystallization growth pattern induced by [bmim]PF6 from three‐dimensional growth of spherulites to a combination of two‐ and three‐dimensional spherulitic growth. Further, lower activation energy for the nonisothermal crystallization of PA blocks of Pebax®1657 can be observed with the increase of [bmim]PF6 content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42137. 相似文献
9.
Stefanie Baum Fred van Rantwijk Andreas Stolz 《Advanced Synthesis \u0026amp; Catalysis》2012,354(1):113-122
The conversion of benzaldehyde and cyanide into mandelic acid and mandeloamide by a recombinant Escherichia coli strain which simultaneously expressed an (S)‐hydroxynitrile lyase (oxynitrilase) from cassava (Manihot esculenta) and an arylacetonitrilase from Pseudomonas fluorescens EBC191 was studied. Benzaldehyde exhibited a pronounced inhibitory effect on the nitrilase activity in concentrations ≥25 mM. Therefore, it was tested if two‐phase systems consisting of a buffered aqueous phase and the ionic liquid 1‐butyl‐1‐pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMpl NTf2) or 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMim PF6) could be used for the intended biotransformation. The distribution coefficients of the substrates, intermediates and products of the reaction were determined and it was found that BMpl NTf2 and BMim PF6 were highly efficient as substrate reservoirs for benzaldehyde. The recombinant E. coli strain was active in the presence of BMpl NTf2 or BMim PF6 phases and converted benzaldehyde and cyanide into mandelic acid and mandeloamide. The two‐phase systems allowed the conversion of benzaldehyde dissolved in the ionic liquids to a concentration of 700 mM with product yields (=sum of mandelic acid and mandeloamide) of 87–100%. The cells were slightly more effective in the presence of BMpl NTf2 than in the presence of BMim PF6. In both two‐phase systems benzaldehyde and cyanide were converted into (S)‐mandeloamide and (S)‐mandelic acid with enantiomeric excesses ≥94%. The recombinant E. coli cells formed, in the two‐phase systems with ionic liquids and increased substrate concentrations, higher relative amounts of mandeloamide than in a purely aqueous system with lower substrate concentrations. 相似文献
10.
Yi‐Ning Wang Bukuo Ni AllanD. Headley Guigen Li 《Advanced Synthesis \u0026amp; Catalysis》2007,349(3):319-322
The 2‐Ns‐based aminohalogenation of α,β‐unsaturated ketones has been achieved in an ionic liquid, 1‐n‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide {[bmim][N(SO2CF3)2]}. [Bmim][N(SO2CF3)2] was found to be superior not only to classical organic solvents but also to its counterpart, [bmim][BF4], which was proven to be successful in the TsNCl2‐based aminohalogenation but failed to give any product for this reaction. The present process takes the advantage of 2‐NsNCl2 as the stable nitrogen/halogen source in a one‐pot operation without the use of any metal catalysts, it is convenient to perform without special protection of inert gases. Eight examples were examined with good to excellent stereoselectivity (1:5 to one isomer) and modest to good chemical yields (53–72 %). 相似文献
11.
Room‐temperature ionic liquids (ILs), including 1‐butyl‐3‐methylimidazolium hexafluorophosphate, [bmim+][PF6?], were investigated as replacements for volatile organic compounds in the free‐radical solution polymerization of poly(methyl methacrylate) (PMMA). The latter was synthesized in benzene and [bmim+][PF6?] at 70 °C via a free‐radical process and the degree and rate of polymerization were compared based on the solvent used. The degree of polymerization was found to be five times higher in [bmim+][PF6?] than in benzene, while the rate of reaction was approximately four times faster in [bmim+][PF6?]. The results indicate the potential for using ILs to produce high‐molecular‐weight polymers and block structures based on the increased free‐radical stability in ILs. Copyright © 2004 Society of Chemical Industry 相似文献
12.
Qian Wang Xingmei Lu Xueyuan Zhou Minli Zhu Hongyan He Xiangping Zhang 《应用聚合物科学杂志》2013,129(6):3574-3581
Series of 1‐allyl‐3‐methylimidazolium halometallate ionic liquids (ILs) were synthesized and used to degrade poly(ethylene terephthalate) (PET) as catalysts in the solvent of ethylene glycol. One important feature of these new IL catalysts is that most of them, especially [amim][CoCl3] and [amim][ZnCl3], exhibit higher catalytic activity under mild reaction condition, compared to the traditional catalysts [e.g., Zn(Ac)2], the conventional IL catalysts (e.g., [bmim]Cl), Fe‐containing magnetic IL catalysts (e.g., [bmim][FeCl4]), and metallic acetate IL catalysts (e.g., [Deim][Zn(OAc)3]). For example, using [amim][ZnCl3] as catalyst, the conversion of PET and the selectivity of bis(hydroxyethyl) terephthalate (BHET) reach up to 100% and 80.1%, respectively, under atmospheric pressure at 175°C for only 1.25 h. Another important feature is that BHET can be easily separated from the catalyst and has a high purity. Finally, based on the experimental phenomena, in ‐situ infrared spectra, and experimental results, the possible mechanism of degradation with synthesized IL is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
13.
Silica supported dendrimer encapsulated ruthenium nanoparticles were prepared and evaluated as catalysts in the hydrogenation of citral. The dendrimer encapsulated nanoparticles were prepared using the generation 4 (G4), generation 5 (G5) and generation 6 (G6) hydroxyl-terminated poly(amidoamine) (PAMAM-OH) dendrimers as templating agents with different Ru metal:dendrimer ratios. The effects of ionic liquids as catalyst coatings on the catalytic activity were investigated for the ionic liquids [BMIM][NTf2], [OMIM][NTf2], [BMIM][BF4], [BMIM][PF6], [EMIM][OcS] and [EMIM][EtS]. An enhancement in catalytic activity was observed when utilising [BMIM][NTf2] as an ionic liquid coating with selectivity towards citronellal. 相似文献
14.
Phase Transitions of Nonionic Surfactant C18:1E10 in Mixed Media of Water with Ionic Liquids
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Complicated temperature‐induced phase transitions were shown in two hexagonal liquid crystal mesophases constructed by nonionic surfactant C18:1E10 in the media of water with ionic liquids, 1‐butyl‐3‐methylimidazolium tetrofluoroborate (bmim‐BF4) and 1‐butyl‐3‐methylimidazolium hexafluorophosphate (bmim‐PF6), respectively. Detailed phase transition information was extracted from rheological, polarized optical microscopy, deuterium magnetic resonance spectroscopy and small‐angle X‐ray scattering measurements, with good agreement among these techniques. It is shown that the order‐to‐disorder phase transition occurred in a narrow range of temperatures for both the two hexagonal mesophases. In particular, the mesophases experienced a biphasic hexagonal‐lamellar coexisting before completely melting, which was not found in the corresponding aqueous hexagonal system of the same surfactant concentration. Of most importance, the two target mesophases exhibited some clearly different behaviors. The phase transition temperature is much higher (ca. 10 °C) in a (water + bmim‐BF4) system than in a (water + bmim‐PF6) system. After melting, a fast transition from elastic micelle to Newtonian fluid was observed in the (water + bmim‐BF4) system, while the micelle related to the (water + bmim‐PF6) system remained elastic over a relatively wide temperature region. The results obtained give a better insight of how the mixed solvents support mesophase formation and modulate the phase transition. 相似文献
15.
Enhanced electrical conductivity of polyindole prepared by electrochemical polymerization of indole in ionic liquids
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The in situ electrical conductivity (resistance) of electrochemically prepared polyindole (PIn) in ionic liquids was found to be strongly dependent on the nature of the solvents, size of ionic liquid counter ions and preparation technique. Accordingly, the conductivity can be enhanced by about one order of magnitude when using a 1‐butyl‐3‐methylimidazolium tetrafluoroborate [BMIm] [BF4‐] or 1‐butyl‐3‐methylimidazolium hexafluorophosphate [BMIm] [PF6?] in comparison to acetonitrile (ACN). Moreover, the growth of polyindole in ionic liquid on gold electrode surface is faster than growth of polymer in acetonitrile. Additionally, a significant enhancement of the conductivity by using ionic liquids during the polymerization could be achieved. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40094. 相似文献
16.
Yun Zhang Xirong Huang Yuezhong Li 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2008,83(9):1230-1235
BACKGROUND: [bmim][PF6] is a hydrophobic ionic liquid which could be considered as an environmentally friendly solvent for biocatalysis. In pure [bmim][PF6], however, alcohol dehydrogenase from yeast (YADH) has no catalytic activity. The aim of the present work was (1) to quantitatively study the negative effect of [bmim][PF6] on the catalytic activity of YADH and the related mechanism and (2) to made an attempt to lessen the negative effect of [bmim][PF6] on YADH by microemulsifying [bmim][PF6]. RESULTS: The activity of YADH in the homogeneous solution formed by H2O, CH3CH2OH and [bmim][PF6] decreased rapidly with the increase of the molar fraction of [bmim][PF6]. The inhibitory effect of [bmim][PF6] on YADH was probably caused by the competition of the imidazole group of [bmim][PF6] with the coenzyme NAD+ for the binding sites on YADH. In a water‐in‐[bmim][PF6] microemulsion, YADH was catalytically active due to the formation of the interfacial membrane of the nonionic surfactant TritonX‐100, which separated YADH from [bmim][PF6] and avoided the direct inactivation of [bmim][PF6] on YADH. Under optimal conditions, the activity of YADH was as high as 51 µmol L?1 min?1. CONCLUSION: [bmim][PF6] was an inhibitor of YADH and its negative effect on YADH could be lessened by its microemulsification. Copyright © 2008 Society of Chemical Industry 相似文献
17.
Effect of small amount of water on the dynamics properties and microstructures of ionic liquids
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Jing Zhou Xiaomin Liu Suojiang Zhang Xiangping Zhang Guangren Yu 《American Institute of Chemical Engineers》2017,63(6):2248-2256
A series of systems of 1‐butyl‐3‐methylimidazolium acetate ([Bmim][Ac]), 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim][BF4]), and 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][Tf2N]) with a small amount of water were simulated. Viscosities of systems were obtained by nonequilibrium molecule dynamics simulation and the results show that the viscosities change in different ways: for [Bmim][BF4] and [Bmim][Tf2N], viscosities decrease rapidly in the first stage, and then decrease slowly with the increase of water content. But for [Bmim][Ac], the viscosities increase first and then decrease. The unique phenomenon of [Bmim][Ac] can be attributed to the formation of chain‐like structure of anion???water???anion???. Hydrogen bond (HB) interaction between ion pairs is weakened, but the number of HB between water and anions increases with increase of water content. Besides, the microstructures of water in ionic liquids‐water systems were compared and found that the distribution of water is more concentrated in [Bmim][Tf2N]‐H2O system, while it is isotropy in [Bmim][Ac]‐H2O system. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2248–2256, 2017 相似文献
18.
In this article, multiscale simulation methods were used to study structural and transport properties of Nafion–ionic liquid composite membranes that are novel proton conducting materials for fuel cells. Coarse‐grained model for 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim][BF4]) ionic liquid was first developed in the framework of BMW‐MARTINI force field. Coarse‐grained simulation results of bulk [bmim][BF4] ionic liquid show good agreement with all‐atom simulation results and experimental data. Nafion–[bmim][BF4] composite membranes were then simulated using all‐atom and coarse‐grained models. Ionic liquid cluster formation inside Nafion was revealed by coarse‐grained simulations. Diffusion coefficients of both [bmim]+ cations and anions are reduced by one to two orders of magnitude depending on their concentrations in Nafion membrane. [Bmim]+ cations have faster self‐diffusion coefficient than anions, while this phenomenon is more pronounced when ionic liquids are confined in Nafion. This work provides molecular basis for understanding Nafion–ionic liquid composite membranes. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2630–2639, 2013 相似文献
19.
Fatty acid methyl ester heterogeneous self‐metathesis in hydrophobic green solvent: Mass transfer limitations,catalyst recyclability,and stability
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The role of room‐temperature ionic liquids (RTILs), [bmim][PF6] and [bmim][Tf2N], as reaction media regarding the catalytic activity and stability of methyltrioxorhenium (MTO) supported on ZnCl2‐modified mesoporous Al2O3 has been studied for self‐metathesis of a functionalized olefin, methyl oleate. The humidity influence on the catalytic activity was probed. The catalyst recycling ability and the kinetics of the metathesis reaction using these RTILs were also investigated. It was found that the MTO‐based catalyst was efficient in viscous hydrophobic RTIL solvents. However, their high viscosity was found to increase the mass transfer limitations thus somewhat impacting the reaction kinetics. Nevertheless, better catalyst stability was reached allowing its possible recycling when used in RTIL media. 相似文献
20.
Mingxia Li Zhiyong Zhou Fan Zhang Wenshuai Chai Lele Zhang Zhongqi Ren 《American Institute of Chemical Engineers》2016,62(11):4023-4034
Four benzyl‐based ionic liquids (ILs) were synthetized and used for deep desulfurization of model oil and real diesel fuel. The removal efficiencies of benzothiophene (BT) and dibenzothiophene (DBT) with [Bzmim][NTf2] and [Bzmim][SCN] as extractants are higher than that with [Bzmp][NTf2] and [Bzmp][SCN] as extractants. The desulfurization capability follows the Nernst's Law. A reactive extraction mathematical model for desulfurization was established. An oxidative‐extractive two‐step deep desulfurization method was developed. DBT was first oxidized by H2O2 with CH3COOH as catalyst and then the unoxidized DBT and uncrystallized dibenzothiophene sulfoxide (DBTO2) in model oil were extracted by [Bzmim][NTf2], and finally the removal efficiency was 98.4% after one‐stage extraction. Besides, the removal efficiency of 4,6‐DMDBT was 96.4% after oxidation and one‐stage extraction processes. Moreover, the oxidative‐extractive two‐step deep desulfurization method was also effective for desulfurization of diesel fuel. The removal efficiency of sulfur reached up to 96% after oxidation and three‐stage cross‐current extraction processes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4023–4034, 2016 相似文献