- Decision support towards agile eco-design of microreaction processes by accompanying (simplified) life cycle assessment
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Continuously running syntheses in microstructured reactors offers novel ways to intensify conventional chemical processes. An outstanding advantage of microreaction technology is the high surface-to-volume-ratio which enables intensive mixing phenomena as well as high mass and heat transfer rates. Thus, microstructured reactors may be a suitable means to improve multiphase reactions by increasing the interfacial area and the intensification of internal mixing. This improvement in reaction performances may lead to reduced environmental burdens of the process under consideration. The method of simplified life cycle assessment (SLCA) is a suitable tool to evaluate the environmental burdens caused by chemical processes. It has been applied already in research and development to identify the key parameters for a deliberate green process design of two biphasic reactions, the esterification of phenol and benzoyl chloride resulting in phenyl benzoate and the synthesis of one of the corresponding phase transfer catalysts, [BMIM]Cl. Further, SLCA is complemented by a simple cost estimation to investigate the main cost drivers relevant for possible industrial application of the syntheses investigated.
- Huebschmann, Sabine,Kralisch, Dana,Loewe, Holger,Breuch, Denis,Petersen, Jan Hauke,Dietrich, Thomas,Scholz, Ralf
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- Oligomerisation of isobutene with silica supported ionic liquid catalysts
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Bronsted acidic ionic liquids, supported on silica gel, have been used effectively in oligomerisation of isobutene. The supported catalysts could be used several times without loss of activity or change in selectivity. The ratio of the products could be influenced by the proper choice of the ionic liquid component of the catalyst and the reaction temperature.
- Feher, Csaba,Krivan, Eszter,Hancsok, Jen,Skoda-Foeldes, Rita
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- Catalytic hydrolysis of cellulose into furans in MnCl2-ionic liquid system
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Production of 5-hydroxymethylfurfural (HMF) and furfural from microcrystalline cellulose (MCC) was studied in 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate (IL-1) with catalytic amount of MnCl2 under atmospheric pressure within 300 min at 150 °C, in which 88.62% of conversion was obtained. With the presence of a catalytic amount of MnCl2, HMF and furfural yields were up to 37% and 18%, respectively, and generated small amount of levulinic acid (LA) and the total reducing sugars (TRS). Dimer of furans compounds as the important by-products were analyzed through HPLC-MS; some small molecular substances, methane, ethane, CO, CO2 and H2, as gas products were detected using mass spectrometry analysis. Comparing with the previous reports, our catalytic system is simple, and it provides an effective route for the conversion of microcrystalline cellulose into biofuels and important platform chemicals.
- Tao, Furong,Song, Huanling,Yang, Jian,Chou, Lingjun
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- Use of SO3H-functionalized halogenfree ionic liquid ([MIM(CH2)4SO3H] [HSO4]) as efficient promoter for the synthesis of structurally diverse spiroheterocycles
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Structurally diverse spiroheterocycles with fused systems incorporating medicinally privileged systems have been synthesized by an efficient and convenient synthetic method involving four component domino reaction of 2-aminobenzothiazoles with isatin and cyclic β-diketones using SO 3H-functionlized halogenfree ionic liquid ([MIM(CH2) 4SO3H][HSO4]) in aqueous medium.
- Kumar, Mahendra,Sharma, Kailash,Arya, Anand Kumar
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- Direct hydroxylation of p-xylene to 2,5-xylenol with hydroxylamine in ionic liquids/molybdenum catalytic system
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Direct hydroxylation of p-xylene to 2,5-xylenol with hydroxylamine was carried out in an ionic liquids/molybdenum catalytic system. High 2,5-xylenol selectivity (80-98 %) can be achieved with good p-xylene conversion (5.9-9.9 %) in this catalytic system. The recycling experiments suggested the ionic liquids/molybdenum catalytic system was stable enough to be recycled for the hydroxylation reaction.
- Zhang,Gao,Jin,Xue,Zhao,Wang,Wang
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- Revealing the Charge Transport Mechanism in Polymerized Ionic Liquids: Insight from High Pressure Conductivity Studies
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Polymerized ionic liquids (polyILs), composed mostly of organic ions covalently bonded to the polymer backbone and free counterions, are considered as ideal electrolytes for various electrochemical devices, including fuel cells, supercapacitors, and batteries. Despite large structural diversity of these systems, all of them reveal a universal but poorly understood feature: a charge transport faster than the segmental dynamics. To address this issue, we studied three novel polymer electrolyte membranes for fuel cells as well as four single-ion conductors, including highly conductive siloxane-based polyIL. Our ambient and high pressure studies revealed fundamental differences in the conducting properties of the examined systems. We demonstrate that the proposed methodology is a powerful tool to identify the charge transport mechanism in polyILs in general and thereby contribute to unraveling the microscopic nature of the decoupling phenomenon in these materials.
- Wojnarowska, Zaneta,Feng, Hongbo,Diaz, Mariana,Ortiz, Alfredo,Ortiz, Inmaculada,Knapik-Kowalczuk, Justyna,Vilas, Miguel,Verdía, Pedro,Tojo, Emilia,Saito, Tomonori,Stacy, Eric W.,Kang, Nam-Goo,Mays, Jimmy W.,Kruk, Danuta,Wlodarczyk, Patryk,Sokolov, Alexei P.,Bocharova, Vera,Paluch, Marian
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- Anionic SO3H-functionalized ionic liquid: An efficient and recyclable catalyst for the Pechmann reaction of phenols with ethyl acetoacetate
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This paper has reported an anionic SO3H-functionalized ionic liquid N-methylimidazolium sulfomethylsulfonate ([Hmim][HO3SCH2SO3]) for the synthesis of coumarins by Pechmann reaction. The [Hmim][HO3SCH2SO3] is easier to prepare by one-step neutralization reaction of N-methylimidazole with methanedisulfonic acid and show high catalytic performance for Pechmann reaction. Besides, the catalyst can simply be separated from the reaction mixture and recycled ten times without noticeable loss of activity.
- Song, Dayong,Chen, Jing,Liang, Yong-Min
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- Efficient synthesis of N-substituted pyrroles catalyzed by a novel an organic-inorganic hybrid solid acid catalyst
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A novel organic-inorganic hybrid solid acid [MIMBS]3PW 12O40 has been successfully prepared. It showed high catalytic activity for N-substituted pyrroles through the cyclocondensation of primary amines with 1,4-dicarbonyl compounds. The solid acid catalyst is stable and can be easily recovered and reused without losing its activity in its efficiency. In addition, a plausible mechanism for the catalytic action of [MIMBS]3PW12O40 has been introduced.
- Gao, Lanchang,Bing, Liu,Zhang, Zehui,Kecheng, Huang,Xiaoyun, Hu,Deng, Kejian
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- CFacile biodiesel synthesis from esterification of free fatty acids catalyzed by SO3H-Functionalized Ionic Liquid
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The esterifications of free fatty acids with methanol were efficiently accomplished over a SO3H-functionalized ionic liquid, 1-(4-sulphonic acid)butyl-3-methylimidazolium hydrogen sulphate ([BSMim]HSO4), which are commonly considered as both one of the typical synthetic routes and the representative pretreatment process for biodiesel production. Particularly, the maximum yield of methyl oleate was obtained in 99.9 %. Methyl oleate could be isolated through simple decantation from the biphasic system, which is attributed to the immiscibility of [BSMim]HSO4 with hydrophobic ester and the good stability and operability of ionic liquid were demonstrated by the six times reuses without dramatic decrease in methyl oleate yield.
- Zhou, Shuai,Liu, Lu,Wang, Bo,Xu, Feng,Sun, Runcang
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- Insights on the catalytic behaviour of sulfonic acid-functionalized ionic liquids (ILs) in transesterification reactions - voltammetric characterization of sulfonic task-specific ILs with bisulfate anions
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This work shows for the first time the link between the amount of free sulfuric acid (as detected by cyclic voltammetry) and the activity of sulfonic-acid-functionalized ionic liquids (ILs) as acid catalysts for a transesterification reaction, and demonstrates that sulfonic acid groups, while are not directly involved in the catalysis, release the free acid during the reaction. Two imidazolic ILs with bisulfate as the counterion and their corresponding task-specific ILs (TSILs) that resulted from the addition of a sulfonic acid group inside the imidazolic-base structure were studied. The outstanding catalytic activity at room temperature of the TSILs 1-(4-sulfonic acid)-butyl-3-methylimidazolium bisulfate ([bsmim]HSO4) and 1-(4-sulfonic acid)-butyl-imidazolium bisulfate ([bsHim]HSO4) for the transesterification ofp-nitrophenyl acetate with methanol was associated to the significant amounts of free sulfuric acid in equilibria with the ionic pairs. It was concluded that these TSILs function as reservoirs for releasing the free acid, which is the actual acid catalyst. In contrast, the corresponding non-sulfonic ILs supply very little amounts of free acid and consequently present low catalytic activities at room temperature, which in fact can be improved by increasing the reaction temperature up to 100 °C.
- Martini, María B.,Fernández, José L.,Adam, Claudia G.
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- Imidazolium-based zwitterionic butane-1-sulfonates: Synthesis and properties of 4-(1-(2-Cyanoethyl)imidazolium)butane-1-sulfonate and Crystal Structures of 4-(1-Alkylimidazolium)butane-1-sulfonates (Alkyl = Methyl, Ethyl, Propyl)
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The reaction of 1-alkylimidazoles (alkyl = methyl, ethyl, propyl, 2-cyanoethyl) with 1,4-butane sultone in equimolar stoichiometry resulted in the formation of 4-(1-methylimidazolium)butane-1-sulfonate SBMIm, 4-(1-ethylimidazolium)butane-1-sulfonate SBEIm, 4-(1-propylimidazolium)butane-1- sulfonate SBPIm, and 4-(1-(2-cyanoethyl)imidazolium)butane-1-sulfonate SBCNEtIm, respectively, in high yields. Properties of these four imidazolium-based zwitterionic compounds were investigated with respect to question of their use as suitable precursors for Ionic Liquids. The structures of the compounds SBMIm, SBEIm, and SBPIm were determined by single-crystal X-ray diffraction. SBMIm and SBEIm crystallize both in the triclinic space group P 1, SBMIm: a = 8.4454(6), b = 8.4492(6), c = 8.7532(7) A, α = 66.610(2), β = 66.235(2), γ = 70.625(2)°, Z = 2, R1(F)/wR2(F2) = 0.0279/0.0832; SBEIm: a = 8.4359(2), b = 8.5900(2), c = 8.6790(2) A, α = 73.487(2), β = 71.228(1), γ = 70.979(2)°, Z = 2, R1(F)/wR2(F2) = 0.0333/0.0820; SBPIm with monoclinic symmetry, space group P21/c: Z = 4; a = 7.2979(3), b = 17.5312(8), c = 9.5682(4) A, β = 90.922(3)°, R1(F)/wR2(F2) = 0.0507/0.1198. Copyright
- Peppel, Tim,Koeckerling, Martin
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- Efficient conversion of furfuryl alcohol into alkyl levulinates catalyzed by an organic-inorganic hybrid solid acid catalyst
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A clean, facile, and environment-friendly catalytic method has been developed for the conversion of furfuryl alcohol into alkyl levulinates making use of the novel solid catalyst methylimidazolebutylsulfate phosphotungstate ([MIMBS]3PW12O40). The solid catalyst is an organic-inorganic hybrid material, which consists of an organic cation and an inorganic anion. A study for optimizing the reaction conditions such as the reaction time, the temperature and the catalyst loading has been performed. Under optimal conditions, a high n-butyl levulinate yield of up to 93 % is obtained. Furthermore, the kinetics of the reaction pathways and the mechanism for the alcoholysis of furfuryl alcohol are discussed. This method is environmentally benign and economical for the conversion of biomass-based derivatives into fine chemicals. Size zero waste: A clean, facile, and environment-friendly catalytic method has been developed for the conversion of furfuryl alcohol into alkyl levulinates, making use of the novel solid catalyst methylimidazolebutylsulfate phosphotungstate ([MIMBS]3PW 12O40). Under the optimal conditions, a high n-butyl levulinate yield of up to 93 % was obtained, with easy work-up procedures and minimal waste generation.
- Zhang, Zehui,Dong, Kun,Zhao, Zongbao
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- Bronsted acid ionic liquid catalyzed formation of pyruvaldehyde dimethylacetal from triose sugars
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A series of sulfonic acid functionalized ionic liquids (SO 3H-ILs) have been synthesized, characterized and investigated as catalysts for the conversion of the triose sugars, 1,3-dihydroxyacetone (DHA) and glyceraldehyde (GLA), to pyruvaldehyde dimethylacetal (PADA) in methanol. Depending on the reaction conditions and the applied SO3H-ILs a good yield of up to 52% of PADA was obtained. Under identical reaction conditions the derivative of PADA, 1,1,2,2-tetramethoxy propane (TMP), could be obtained in yields up to 49% using another SO3H-IL.
- Saravanamurugan, Shunmugavel,Riisager, Anders
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- Metal- And solvent-free synthesis of aniline- And phenol-based triarylmethanes: Via Br?nsted acidic ionic liquid catalyzed Friedel-Crafts reaction
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A beneficial, scalable and efficient methodology for the synthesis of aniline-based triarylmethanes has been established through the double Friedel-Crafts reaction of commercial aldehydes and primary, secondary or tertiary anilines using Br?nsted acidic ionic liquid as a powerful catalyst, namely [bsmim][NTf2]. This protocol was successfully performed under metal- and solvent-free conditions with a broad range of substrates, giving the corresponding aniline-based triarylmethane products in good to excellent yields (up to 99%). In addition, alternative aromatic nucleophiles such as phenols and electron-rich arenes were also studied using this useful approach to achieve a diversity of triarylmethane derivatives in high to excellent yields. This journal is
- Jaratjaroonphong, Jaray,Saeeng, Rungnapha,Senapak, Warapong,Sirion, Uthaiwan,ponpao, nipaphorn
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p. 22692 - 22709
(2021/07/21)
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- p-Toluenesulfonic acid functionalized imidazole ionic liquids encapsulated into bismuth SBA-16 as high-efficiency catalysts for Friedel-Crafts acylation reaction
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Bismuth SBA-16 catalyst was synthesized by the hydrothermal method. Four kinds ofp-toluenesulfonic acid functionalized imidazole ionic liquids were prepared by a two-step method and their molecular structures were characterized by1H NMR and MS. The post-synthesis impregnation method was used to functionalize the Bi(10)-SBA-16 silicon mesoporous material with the ionic liquids and the obtained materials were characterized by FT-IR, XRD, BET, XPS, and TG. The results show that the volume and pore size of SBA-16 were changed by loading Bi and ionic liquids, while the three-dimensional cubic pore structure of SBA-16 was not destroyed. The composite catalyst was evaluated in Friedel-Crafts acylation of anisole with acetic anhydride. The effects of reaction temperature and the ratio of anisole and acylating agent on the acylation of anisole were investigated by experimental design. The results showed that 1.2ILc@Bi(10)-SBA-16 was used as the catalyst, the conversion of anisole was 85.41% and the yield of aromatic ketone was 69.19% under the conditions of a reaction temperature of 100 °C, a catalyst dosage of 0.5 g, a time period of 4 h and a molar ratio of 1?:?1.5. After 5 recycling runs, the reduction in the overall ratio of reactant conversion and product yield did not exceed 7.5%, indicating that 1.2ILc@Bi(10)-SBA-16 has good stability and reusability.
- Gao, Guofang,Zhao, Qian,Yang, Cheng,Jiang, Tingshun
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p. 5871 - 5882
(2021/05/10)
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- Oligomeric ricinoleic acid preparation promoted by an efficient and recoverable Br?nsted acidic ionic liquid
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Raw material from biomass and green preparation processes are the two key features for the development of green products. As a bio-lubricant in metalworking fluids, estolides of ricinoleic acid are considered as the promising substitute to mineral oil wit
- Gao, Song,He, Liang-Nian,He, Xing,Li, Hong-Ru,You, Fei
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supporting information
p. 351 - 361
(2020/03/27)
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- Mechanistic studies on counter-ionic effects of camphorsulfonate-based ionic liquids on kinetics, thermodynamics and stereoselectivity of β-amino carbonyl compounds
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Catalysis is important in various applications of organic chemistry and its output product control for stereoselective compounds is outrageous. Establishment of experimental facts of stereoselective compounds from catalysis and their validation using theoretical evidences is the key to understand various mechanisms of optically active compounds. A family of new ionic liquids (ILs) with various imidazolium cations and camphorsulfonate anion as environmentally benign liquid salts have been synthesized and deployed for catalysis of β-amino carbonyl compounds. The products were formed using ILs as a homogeneous catalyst with excellent product yield and diastereoselectivity. The effect of counter ions, Hammett acidity and viscosity of ILs along with solvent and temperature are explored in terms of reaction kinetics and product yields. Density functional theory (DFT) was used to investigate thermodynamical study of mechanistic pathway of the reaction. The DFT calculations predicted that the catalysis mechanism involved both counterions of the IL. Moreover, it is evidenced that the syn-pathway required lower activation energy while anti-pathway led to thermodynamically stable product. This study explores new avenues for using ILs as potential homogeneous catalysts for the production of stereoselective species.
- Hamzah, Ahmad Sazali,Jabeen, Erum,Leveque, Jean-Marc,Sardar, Sabahat,Wilfred, Cecilia Devi
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- Ultra-small and highly dispersed Pd nanoparticles inside the pores of ZIF-8: Sustainable approach to waste-minimized Mizoroki–Heck cross-coupling reaction based on reusable heterogeneous catalyst
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The rapid development of nanomaterials, particularly advanced hybrid nanoparticles, has made new opportunities for the design and fabrication of high-performance metal-based catalysts. However, generating metal nanoparticles of desired size without aggregation is an important challenge for enhancing the catalytic activity of metal nanoparticles supported in the host matrix. In this work, a hybrid nanoporous material, namely Pd nanoparticles@N-heterocyclic carbene@ZIF-8, with a high internal surface area was successfully prepared using a dispersed anionic sulfonated N-heterocyclic carbene–Pd(II) precursor inside the cavities of zeolitic imidazolate framework (ZIF-8) using an impregnation approach followed by reduction with NaBH4. The anionic sulfonated N-heterocyclic carbene was found to be a superb ligand for the stabilization of Pd nanoparticles in the pores of ZIF-8. The resulting system was applied to the Mizoroki–Heck cross-coupling reaction, in which the catalyst showed high catalytic activity under mild reaction conditions.
- Azad, Mohammad,Rostamizadeh, Shahnaz,Estiri, Hamid,Nouri, Fatemeh
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- PRODUCTION METHOD OF ESTER COMPOUND
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PROBLEM TO BE SOLVED: To produce an ester compound at a high conversion even under mild reaction conditions. SOLUTION: A production method of an ester compound includes a reaction step for reacting a carboxylic acid of 8-22 carbons and an alcohol of 8-22 carbons at a temperature of 50-100°C in an ionic liquid composed of a phosphonium cation or an imidazolium cation and a trifluoromethanesulfonic acid anion or a bis (trifluoromethanesulfonyl) imide anion to obtain an ester compound in a liquid phase different from an ionic liquid phase. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0025
(2019/10/01)
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- Zwitterionic Hydrobromic Acid Carriers for the Synthesis of 2-Bromopropionic Acid from Lactide
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A convenient and highly efficient way of synthesizing 2-bromopropionic acid (2-BrPA) from lactide is presented. The procedure uses ionic liquids obtained from the addition of HBr to ammonium-based zwitterions as the solvent and bromination agent. The buffered HBr acidity, high polarity, and charge stabilizing character of the ionic liquid (IL) enable the synthesis of 2-BrPA with excellent selectivity. The best results are obtained with an imidazolium-based IL, that is, 1-(4-butanesulfonic acid)-3-methylimidazolium bromide ([MIMBS]Br). The HBr loading and water content of the IL are crucial parameters for the bromination reaction. The formed 2-BrPA product can be selectively isolated by extraction from the IL, and the unconverted substrate remains in the [MIMBS]Br IL for the next run. Successful recycling of the IL over four cycles is demonstrated.
- Kehrer, Matthias,Mehler, Julian,Taccardi, Nicola,Nagengast, Jens,Kadar, Julian,Collias, Dimitris,Dziezok, Peter,Wasserscheid, Peter,Albert, Jakob
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p. 1063 - 1072
(2018/03/01)
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- Olefin oligomerization via new and efficient Br?nsted acidic ionic liquid catalyst systems
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Olefin oligomerization reaction catalyzed by new catalyst systems (a Br?nsted-acidic ionic liquid as the main catalyst and tricaprylylmethylammonium chloride as the co-catalyst) has been investigated. The synthesized Br?nsted acidic ionic liquids were characterized by Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV), 1H nuclear magnetic resonance (NMR), and 13C NMR to analyze their structures and acidities. The influence of different ionic liquids, ionic liquid loading, different co-catalysts, catalyst ratios (mole ratio of ionic liquid to co-catalyst), reaction time, pressure, temperature, solvent, source of reactants, and the recycling of catalyst systems was studied. Among the synthesized ionic liquids, 1-(4-sulfonic acid)butyl-3-hexylimidazolium hydrogen sulfate ([HIMBs]HSO4) exhibited the best catalytic activity under the tested reaction conditions. The conversion of isobutene and selectivity of trimers were 83.21% and 35.80%, respectively, at the optimum reaction conditions. Furthermore, the catalyst system can be easily separated and reused; a feasible reaction mechanism is proposed on the basis of the distribution of experimental products.
- Wang, Guoqin,Song, Heyuan,Li, Ruiyun,Li, Zhen,Chen, Jing
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p. 1110 - 1120
(2018/05/28)
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- Preparation method of terpenyl plasticizer
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The invention provides a preparation method of a terpenyl plasticizer. The preparation method comprises the following steps: by taking 4-(4-methyl-3-pentenyl)-4-cyclohexene-1,2-anhydride and isooctanol as raw materials, adding a catalyst and a water-carrying agent, and performing an esterification reaction for a certain period of time at a certain temperature; after the reaction, reclaiming the water-carrying agent cyclohexane and isooctanol through reduced pressure distillation; and separating out the catalyst to obtain the terpenyl plasticizer. The molar ratio of 4-(4-methyl-3-pentenyl)-4-cyclohexene-1,2-anhydride to isooctanol is (1:3.0)-(1:4.0). The prepared terpenyl plasticizer has the advantages of excellent performance and environmental friendliness.
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Paragraph 0031-0033; 0038-0040; 0045-0047
(2018/06/15)
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- Chiral ionic liquids supported on natural sporopollenin microcapsules
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Supported chiral ionic liquids (SILs) were prepared choosing the starting material for the ionic liquid part from the enantiopure stock of the chiral pool (monoterpenoids and an amino acid) and the sporopollenin as an environmentally friendly support. Sporopollenins are microcapsules with naturally well-defined sizes and shapes that can be obtained from pollen grains after removal of the internal cytoplasm and the second shell layer. As thermally stable organic biocompatible structures, sporopollenins have attracted increasing interest in recent years for several applications. Herein, bio-based ILs were anchored onto the surface of sporopollenins obtained from the pollen of Populus deltoides, selected as a model pollen grain. These new structures, which present an external positively charged shell, were characterized by physico-chemical techniques (ATR-FTIR, TGA, SEM, EDX, and solid-state 13C NMR). A metathesis reaction was also performed on selected bio-based IL modified sporopollenins, demonstrating the possibility to switch the surface properties by exploiting well-known IL chemistry.
- Palazzo, Ivan,Mezzetta, Andrea,Guazzelli, Lorenzo,Sartini, Stefania,Pomelli, Christian Silvio,Parker, Wallace O.,Chiappe, Cinzia
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p. 21174 - 21183
(2018/06/26)
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- Method of selectively catalytically oxidizing biomass-based furan compound
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The invention discloses a method of selectively catalytically oxidizing a biomass-based furan compound. The method comprises the following step of: by taking a heteropolyacid functional ionic liquid as a catalyst and an alcohol solution as a reaction medium, obtaining dicarboxylic acid or dicarboxylate in the conditions that the reaction temperature is 100-150 DEG C, the reaction time is 1-3h and the oxygen pressure is 0.5-1.0MPa, wherein over 62.35% of difumarate selectivity is obtained. The single chemical yield and selectivity for oxidizing preparation of a biomass-based furan derivative are far higher than those of the prior art. The method has the remarkable advantage that an ionic liquid catalyst can be recovered and recycled by simply adjusting the temperature. The method disclosed by the invention is mild in reaction condition, green and safe in process and simple to operate, and can realize intermittent and continuous production.
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Paragraph 0026; 0027; 0028
(2017/07/19)
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- A two-phase system for the clean and high yield synthesis of furylmethane derivatives over -SO3H functionalized ionic liquids
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A new and effective unique two-phase reaction system is investigated for the high yield production of tri(furyl)methane from furfural and furan. This strategy includes the use of an acidic aqueous phase (water + -SO3H functionalized IL) and furan phase, which significantly suppresses polymer formation, thereby increasing the yield of tri(furyl)methane. Furan serves as a reactant as well as an extraction solvent for the recovery of the condensation products. For comparison, different -SO3H functionalized ionic liquids are prepared and their performances evaluated for the condensation of furan and furfural. The ionic liquids with alkyl chain linkers are found to be more effective and acidic than those with imidazolium linked N-sulfonic acids. In addition, an increase in carbon chain length between imidazole/tri-ethylamine/pyridine and -SO3H, increases the catalytic activity of the respective ionic liquids. Among the several prepared ionic liquids, the strongly acidic imidazolium based butylsulfonic acid 6 shows the best activity with a maximum condensation product yield of 84%. This strategy offers a significantly high yield of the condensation products of furan and furfural compared to the traditional mineral acid route. The activity and stability of the -SO3H functionalized 6 is confirmed from seven successful recycles, in which there is no reduction in its activity. Finally, this new strategy is successfully extended for the condensation of furan derivatives (e.g. furan and 2-methylfuran) with several different aldehydes, ketones and alcohols.
- Shinde,Rode
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p. 4804 - 4810
(2017/10/19)
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- Comprising zwitterionic and/or acid-functionalized ion liquid palladium catalyst system
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The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3COCHCOCH3), Pd (CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications.
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Paragraph 0172-0175
(2017/01/26)
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- Green synthesis of dipyrromethanes in aqueous media catalyzed by SO3H-functionalized ionic liquid
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A mild, efficient and metal-free method was described for the green synthesis of dipyrromethanes from aldehydes and unsubstituted pyrrole catalyzed by SO3H-functionalized ionic liquids (SO3H-ILs) in aqueous media at room temperature. Notably, SO3H-ILs, 1-butylsulfonic-3-methylimidazolium hydrogen sulfate ([bsmim][HSO4]) was the most efficient catalyst for moderate to good yields of the corresponding desired products.
- Senapak,Saeeng,Jaratjaroonphong,Kasemsuk,Sirion
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p. 1302 - 1310
(2016/02/03)
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- 1-(1-Alkylsulfonic)-3-methylimidazolium chloride as a reusable Br?nsted acid catalyst for the regioselective azidolysis of epoxides under solvent-free conditions
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In this study, 1-(1-alkylsulfonic)-3-methylimidazolium chloride as a new, green, and reusable Br?nsted acid catalyst was prepared. In this protocol, we used for the regioselective ring-opening reactions of various epoxiodes with sodium azide to afford the
- Rezayati, Sobhan,Nezhad, Eshagh Rezaee,Hajinasiri, Rahimeh
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p. 974 - 978
(2016/06/13)
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- Catalytic hydrolysis of cellulose into furans
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Chromium chloride in 4-(3-methylimidazolium-1-yl)butane-1-sulfonic acid hydrogen sulfate (IL-1) was found to effectively catalyze the hydrolysis of microcrystalline cellulose (MCC) at 150°C for 300 min to achieve 87.8% conversion to a slate of products. With a catalytic amount of CrCl3, the yields of 5-hydroxymethyl furfural (HMF) and furfural were up to 32.4 and 15.2%, respectively, small molecules levulinic acid (LA, 10.8%) and the total reducing sugars (TRS, 10.7%) were also generated. Through LC-MSD analysis and mass spectra, dimer of furan compounds as the main by-products were speculated, and the components of gas products were methane, ethane, CO, CO2, and H2. We suggested that IL-1 and CrCl3 exhibited a coordination interaction; the formation of the intermediate via the hydride shift played a key role in the formation of HMF. The catalyst was recycled and exhibited constant activity for five successive trials.
- Shi, Chengmei,Tao, Furong,Cui, Yuezhi
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p. 2508 - 2516
(2016/11/18)
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- Synthesis of polyoxymethylene dimethyl ethers from methylal and trioxane catalyzed by Br?nsted acid ionic liquids with different alkyl groups
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Br?nsted acid ionic liquids with different alkyl group carbon chain lengths and an alkane sulfonic acid group were synthesized through bromoalkane, imidazole and 1,4-butane sultone as raw materials. The structures and properties of the ionic liquids were experimentally characterized. Catalytic reaction of methylal (DMM) with trioxane (TOX) for preparation of polyoxymethylene dimethyl ethers (PODMEn, CH3O(CH2O)nCH3, where n > 1) was investigated in various Br?nsted acid ionic liquids with different carbon chain length of alkyl groups. The carbon chain length of alkyl groups and activity correlation for the ionic liquids was studied. It was found that the structures of ionic liquids were consistent with the designed structure and their purities were high. They possessed high thermal stability and wide liquid range. The hydrophobicity of ionic liquids became stronger with the increase of carbon chain length. With increasing the carbon chain length of ionic liquids, the selectivity of PODME3-8 is increased at first and then decreased. Among all the ionic liquids, [C6ImBS][HSO4] shows the best catalytic performance and the selectivity of PODME3-8 is 57.85%.
- Wu, Qin,Li, Weijiao,Wang, Min,Hao, Yu,Chu, Tonghua,Shang, Jiqing,Li, Hansheng,Zhao, Yun,Jiao, Qingze
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p. 57968 - 57974
(2015/07/20)
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- Highly efficient synthesis of 1,3-dioxanes via prins reaction in bronsted-acidic imidazolium ionic liquid
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The high-yielding synthesis of a wide variety of 1,3-dioxanes via the Prins reaction under mild conditions has been demonstrated using Bronsted- acidic imidazolium ionic liquid [bmim(SO3H)][OTf] or bmimOTf. The use of ionic liquid makes this synthesis simple, convenient, cost-effective, and environmentally friendly. Furthermore, bmimOTf was conveniently separated from the products and can be easily recycled for the Prins reaction with excellent yields. This method works well with a variety of aliphatic aldehydes including formaldehyde, acetaldehyde, propionaldehyde, and cyclohexanecarboxaldehyde. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Kalkhambkar, Rajesh G.,Jeong, Yeon T.
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supporting information
p. 762 - 771
(2014/03/21)
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- Pd-catalyzed ethylene methoxycarbonylation with Bronsted acid ionic liquids as promoter and phase-separable reaction media
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Bronsted acid ionic liquids (BAILs) were prepared and applied as combined acid promoters and reaction media in Pd-phosphine catalyzed methoxycarbonylation of ethylene to produce methyl propionate. The BAILs served as alternatives to common mineral acids required for the reaction, e.g. methanesulfonic acid or sulfuric acid, resulting in high catalytic activity and selectivity towards methyl propionate. In addition, the BAILs yielded a biphasic system with the product and provided stability to palladium intermediates avoiding the undesirable formation of palladium black after reaction. These special features enabled facile methyl propionate separation and recovery of the ionic liquid catalyst system, thus allowing its re-use up to 15 times without apparent loss of catalytic activity or selectivity.
- Garcia-Suarez, Eduardo J.,Khokarale, Santosh G.,Van Buu, Olivier N.,Fehrmann, Rasmus,Riisager, Anders
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p. 161 - 166
(2014/01/06)
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- Synthesis and thermophysical properties of imidazolium-based bronsted acidic ionic liquids
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A range of imidazolium-based Bronsted acidic ionic liquids (ILs) have been synthesized by varying the side chain length of the alkyl and alkyl sulfonic group incorporated to the C1 and C3 positions in the imidazolium ring respectively with a fixed HSO4- anion. The synthesized ILs were characterized using NMR for structure confirmation and CHNS for elemental analysis. The thermal properties such as thermal decomposition temperature were determined using thermogravimetric analysis, and several key physical properties such as viscosity and density were measured within a temperature range of 20 C to 80 C using an Anton Paar viscometer and densitometer. The density measurement results and established equations were used to calculate the molecular volumes, standard entropies, crystal lattice energies, and thermal expansion coefficients of the synthesized ILs.
- Muhammad, Nawshad,Man, Zakaria,Elsheikh, Yasir A.,Bustam, M. Azmi,Mutalib, M.I. Abdul
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p. 579 - 584
(2014/04/03)
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- Broensted acidic ionic liquids as efficient and recyclable catalysts for the carbonylation of formaldehyde
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Methyl glycolate (MG), as a precursor to ethylene glycol (EG), was synthesized by an efficient and eco-friendly procedure of one-pot, two-step, sequential reaction, including carbonylation and esterification from HCHO with Broensted acidic ionic liquids (BAILs) as catalysts. MG was obtained in high yield under mild conditions. In addition, the catalyst could be recycled eight times after separating the unreacted materials and products from the reaction system by distillation under vacuum and no significant decrease in catalytic activity was observed.
- Song, Heyuan,Li, Zhen,Chen, Jing,Xia, Chungu
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experimental part
p. 81 - 86
(2012/04/10)
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- Catalytic conversion of cellulose to 5-hydroxymethyl furfural using acidic ionic liquids and co-catalyst
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Efficient catalytic conversion of microcrystalline cellulose (MCC) to 5-hydroxymethyl furfural (HMF), is achieved using acidic ionic liquids (ILs) as the catalysts and metal salts as co-catalysts in the solvent of 1-ethyl-3-methylimidazo-lium acetate ([emim][Ac]). A series of acidic ILs has been synthesized and tested in conversion of MCC to HMF. The effect of reaction conditions, such as reaction time, temperature, catalyst dosage, metal salts, water dosage, Cu2+ concentration and various acidic ILs are investigated in detail. The results show that CuCl2 in 1-(4-sulfonic acid) butyl-3-methylimidazolium methyl sulfate ([C4SO 3Hmim][CH3SO3]), is found to be an efficient catalyst for catalytic conversion of MCC to HMF, and 69.7% yield of HMF is obtained. A mechanism to explain the high activity of CuCl2 in [C4SO3Hmim][CH3SO3] is proposed. To the best of our knowledge, this report first proposes that the Cu2+ and [C4SO3Hmim][CH3SO3] show better catalytic performance in catalytic conversion of MCC to HMF.
- Ding, Zhen-Dong,Shi, Jin-Cai,Xiao, Jing-Jing,Gu, Wen-Xiu,Zheng, Chang-Ge,Wang, Hai-Jun
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experimental part
p. 792 - 798
(2012/10/18)
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- PALLADIUM CATALYST SYSTEM COMPRISING ZWITTERION AND/OR ACID-FUNCTIONALYZED IONIC LIQUID
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The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCl2, Pd(CH3COCHCOCH3), Pd(CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications.
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Page/Page column 8
(2011/04/18)
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- Catalytic conversion of cellulose to chemicals in ionic liquid
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A simple and effective route for the production of 5-hydroxymethyl furfural (HMF) and furfural from microcrystalline cellulose (MCC) has been developed. CoSO4 in an ionic liquid, 1-(4-sulfonic acid) butyl-3- methylimidazolium hydrogen sulfate (IL-1), was found to be an efficient catalyst for the hydrolysis of cellulose at 150 °C, which led to 84% conversion of MCC after 300 min reaction time. In the presence of a catalytic amount of CoSO4, the yields of HMF and furfural were up to 24% and 17%, respectively; a small amount of levulinic acid (LA) and reducing sugars (8% and 4%, respectively) were also generated. Dimers of furan compounds were detected as the main by-products through HPLC-MS, and with the help of mass spectrometric analysis, the components of gas products were methane, ethane, CO, CO 2, and H2. A mechanism for the CoSO4-IL-1 hydrolysis system was proposed and IL-1 was recycled for the first time, which exhibited favorable catalytic activity over five repeated runs. This catalytic system may be valuable to facilitate energy-efficient and cost-effective conversion of biomass into biofuels and platform chemicals.
- Tao, Furong,Song, Huanling,Chou, Lingjun
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experimental part
p. 58 - 63
(2011/02/25)
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- Intramolecular hydroalkoxylation in Bronsted acidic ionic liquids and its application to the synthesis of (±)-centrolobine
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The SO3H-tethered imidazolium and triazolium salts, nonvolatile and recyclable Bronsted acidic ionic liquids, efficiently mediate intramolecular hydroalkoxylations of alkenyl alcohols. They have been successfully employed in the synthesis of (±)-centrolobine.
- Jeong, Yunkyung,Kim, Do-Young,Choi, Yunsil,Ryu, Jae-Sang
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supporting information; experimental part
p. 374 - 378
(2011/02/28)
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- Heteropolyacid salts as self-separation and recyclable catalysts for transesterification of trimethylolpropane
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A series of heteropolyacid (HPA) salts as catalysts were prepared and characterized. Transesterifications of trimethylolpropane (TMP) were carried out using these catalysts. The influence of organic cations and heteropolyanions on the reaction, optimization of reaction conditions, and catalytic reusability were investigated. The results show that the heteropolyacid (HPA) salts present a self-separation performance after reaction, which can be easily recovered and quite steadily reused as demonstrated by a eight-run recycling test. Moreover, the pyridinium with PW12O403- as the anion ([PyBS]3PW12O40) showed the best catalytic performance among the heteropolyacid salts for the transesterification of trimethylolpropane with various methyl esters.
- Li, Kaixin,Chen, Li,Wang, Honglin,Lin, Weibin,Yan, Zongcheng
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experimental part
p. 233 - 237
(2011/11/06)
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- Bronsted acidic ionic liquids as efficient catalysts for clean synthesis of carbamatoalkyl naphthols
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Under mild conditions and without any additional organic solvent, synthesis of carbamatoalkyl naphthols could be carried out in the present of two halogen-free Bronsted acidic ionic liquids, 3-methyl-1-(4-sulfonic acid)butylimidazolium hydrogen sulfate and N-(4-sulfonic acid)butylpyridinium hydrogen sulfate. A widerange of aromatic aldehydes easily undergo condensation with β-naphthol and methyl or benzyl carbamate to afford the desired products of good purity in excellent yields. The present methodology offers several advantages such as a simple procedure with an easy work-up, short reaction times, and excellent yields. The catalysts could be recycled and reused for several times without substantial reduction in their catalytic activities. Copyright
- Tavakoli-Hoseini, Niloofar,Heravi, Majid M.,Bamoharram, Fatemeh F.,Davoodnia, Abolghasem
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experimental part
p. 787 - 792
(2011/12/22)
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- Acidic ionic liquid [(CH2)4SO3HMIM] [HSO4]: A green media for the simple and straightforward synthesis of 2,4,5-trisubstituted imidazoles
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2,4,5-Trisubstituted imidazoles have been synthesized in excellent yields (85-95%) in the presence of 5mol% of [(CH2)4SO3HMIM] [HSO4] as a Brnsted acidic ionic liquid. Copyright
- Heravi, Majid M.,Zakeri, Masoumeh,Karimi, Narges,Saeedi, Mina,Oskooie, Hossien A.,Tavakoli-Hosieni, Niloofar
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experimental part
p. 1998 - 2006
(2010/09/06)
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- Green, one-pot, solvent-free synthesis of 1,2,4,5-tetrasubstituted imidazoles using a bronsted acidic ionic liquid as novel and reusable catalyst
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3-Methyl-1-(4-sulfonic acid)butylimidazolium hydrogen sulfate [(CH 2)4SO3HMIM][HSO4], a Brnsted acidic ionic liquid, has been used as an efficient, green, and reusable catalyst for the synthesis of 1,2,4,5-tetrasubstituted imidazoles using benzil, an aromatic aldehyde, and a primary amine in the presence of ammonium acetate under solvent-free conditions. The catalyst could be recycled and reused several times without noticeably decreasing the catalytic activity. Taylor & Francis Group, LLC.
- Davoodnia, Abolghasem,Heravi, Majid M.,Safavi-Rad, Zahra,Tavakoli-Hoseini, Niloofar
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experimental part
p. 2588 - 2597
(2010/10/03)
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- Alkylation of isobutane with 2-butene using ionic liquids as catalyst
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Alkylation of isobutane with 2-butene was performed in a batch reactor using the ionic liquid 1-n-octyl-3-methylimidazolium bromide aluminium chloride ([OMIM]Br-AlCl3) pure, and in a mixture with compounds containing SO3H-groups. The acidity of the ionic liquid (IL) was modified by the addition of acid cation exchange resins (dry or with a small amount of water), or by the addition of a second IL ([(HO3SBu)MIM]HSO4). A high content of the desired trimethylpentanes (up to 64%) and thus a high research octane number (RON up to 96) of the alkylate was obtained. The reusability of the IL systems was studied and compared with a catalyst commercially used at present (H2SO4).
- Bui, Thi Le Thuy,Korth, Wolfgang,Aschauer, Stephan,Jess, Andreas
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experimental part
p. 1961 - 1967
(2010/06/15)
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- Improved 1-butene/isobutane alkylation with acidic ionic liquids and tunable acid/ionic liquid mixtures
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A new process for 1-butene/isobutane alkylation to yield C 8-alkylates is described using binary mixtures of certain acidic imidazolium ionic liquids (ILs) and strong acids such as sulfuric or trifluoromethanesulfonic (triflic) acid. Equivalent or better conversion (>95%), C8-alkylates selectivity (>70%) and trimethylpentane/ dimethylhexane selectivity (TMP/DMH > 7) were achieved with the IL/acid mixtures over the pure acids themselves. Six types of substituted 3-methyl-imidazolium ionic liquids were investigated, wherein acidity is imparted via either the cation with sulfonic acid groups or the anion (hydrogen sulfate) or both. Long-term studies up to 30+ recycles indicate that the catalyst stability was increased by sometimes greater than 30+% with the IL/acid mixtures over the pure acid. The ionic liquid is believed to tune the acidity, solubility, and interfacial properties, resulting in these enhanced results. In addition, this concept could also be applicable to Friedel-Crafts alkylation, acylation chemistries, or other acid-catalyzed reactions.
- Tang, Shengwei,Scurto, Aaron M.,Subramaniam, Bala
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experimental part
p. 243 - 250
(2011/05/07)
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- METHOD OF MAKING A LACTAM IN AN IONIC LIQUID
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The invention relates to a method of contacting a cyclic oxime with a Br?nsted acidic ionic liquid having a sulfur atom in the anionic portion and/or the cationic portion further comprising mechanical stirring, microwave irradiation and/or ultrasonic treatment.
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Page/Page column 9
(2009/01/20)
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- Chlorination of aromatics with trichloroisocyanuric acid (TCICA) in bronsted-acidic imidazolium ionic liquid [BMIM(SO3H)][OTf]: An economical, green protocol for the synthesis of chloroarenes
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A survey study on electrophilic chlorination of aromatics with trichloroisocyanuric acid (TCICA) in Bronsted-acidic imidazolium ionic liquid [BMIM(SO3H)][OTf] is reported. The reactions are performed under very mild conditions (at ~50°C) and give good to excellent yields, depending on the substrates. Chemoselectivity for mono- v. dichlorination can be tuned by changing the arene-to-TCICA ratio and the reaction time. The survey study and competitive experiments suggest that triprotonated/protosolvated TCICA is a selective/moderately reactive transfer-chlorination electrophile. Density functional theory was used as guide to obtain further insight into the nature of the chlorination electrophile and the transfer-chlorination step. CSIRO 2007.
- Hubbard, Abigail,Okazaki, Takao,Laali, Kenneth K.
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p. 923 - 927
(2008/03/17)
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- DEHYDRATION PROCESS
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A process for producing an olefin and/or an ether is described, which comprises heating an alcohol in the presence of an acidic ionic compound which exists in a liquid state at a temperature of below 150°C.
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Page/Page column 13
(2008/06/13)
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