- Photoswitchable phthalocyanine-assembled nanoparticles for controlled "double-lock" photodynamic therapy
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In the current study, a new nanoparticle platform, NanoAzoPcS, is created by co-assembly of phthalocyanine and azobenzene amphiphiles, which can be used to gain precise control of PDT simply by regulating the stoichiometric ratio of the components and usi
- Cheng, Hong-Bo,Li, Xingshu,Kwon, Nahyun,Fang, Yanyan,Baek, Gain,Yoon, Juyoung
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- Metal β-diketonate complexes as highly efficient catalysts for chemical fixation of CO2 into cyclic carbonates under mild conditions
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The potential of metal β-diketonate complexes for the catalysis of the chemical fixation of CO2 into cyclic carbonates at 1 atm CO2 and near room temperature was demonstrated. Their potential for the capture and simultaneous conversi
- Wang, Hongmei,Zhang, Zulei,Wang, Hailong,Guo, Liping,Li, Lei
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- Development of an analytical method based on temperature controlled solid-liquid extraction using an ionic liquid as solid solvent
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At the present paper, an analytical method based on temperature controlled solid-liquid extraction (TC-SLE) utilizing a synthesized ionic liquid, (N-butylpyridinium hexafluorophosphate, [BPy]PF6), as solid solvent and phenanthroline (PT) as an extractant was developed to determine micro levels of Fe2+ in tea by PT spectrophotometry. TC-SLE was carried out in two continuous steps: Fe2+ can be completely extracted by PT-[BPy]PF6 or back-extracted at 80 °C and the two phases were separated automatically by cooling to room temperature. Fe2+ after back-extraction, needs 2 mol/L HNO3 as stripping agent and the whole process was determined by PT spectrophotometry at room temperature. The extracted species was neutral Fe(PT)mCl2 (m = 1) according to slope analysis in the Fe2+-[BPy]PF6-PT TC-SLE system. The calibration curve was Y = 0.20856X - 0.000775 (correlation coefficient = 0.99991). The linear calibration range was 0.10-4.50 μg/mL and the limit of detection for Fe2+ is 7.0 × 10-2 μg/mL. In this method, the contents of Fe2+ in Tieguanyin tea were determined with RSDs (n = 5) 3.05% and recoveries in range of 90.6%-108.6%.
- Pan, Zhongwei,Wang, Zhengquan,Zhu, Linna,Zhu, Zhiming,Cai, Jinying,Shen, Xiaoman,Fan, Tingli,Zhang, Yingnan,Chen, Zhixiu,McPhee, Derek J.
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- Imidacloprid photo-degradation on Ag/AgBr modified TiO2: critical impacts and quantitative study on mechanism
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To improve the visible-light catalytic performance of TiO2 for practical application, Ag/AgBr?modified TiO2 was fabricated in ionic liquid–water medium via a facile hydrothermal reduction method. Imidacloprid (IMI) was employed as the target pollutant to evaluate the critical impacts on the catalytic activity of as-prepared Ag/AgBr/TiO2, where the factors relating to the catalyst (composition, dosage, recycle and reuse) and solution chemistry (pH and concentration, simulated wastewater samples and floodwater of rice paddy field) were studied. The results suggested that benefitting from visible-light sensitive Ag/AgBr and high specific surface area TiO2, Ag/AgBr/TiO2 exhibits superior visible-light photocatalytic activity and stability to Ag/AgBr and TiO2. The quenching tests with various scavengers indicate that ·O2 ? and h+, and ·O2 ? and ·OH may be the key roles in IMI photo-degradation on Ag/AgBr and on Ag/AgBr/TiO2, respectively. Thus, the photocatalytic performance of Ag/AgBr/TiO2 differs from that of Ag/AgBr. Furthermore, the contribution of such active species is clarified for quantitative mechanisms study. The photo-degradation conducted in the simulated wastewater and the floodwater of rice paddy field proves favorable anti-interference capacity of Ag/AgBr/TiO2. The tests conducted on real wastewater sample verified that Ag/AgBr/TiO2 can mineralize IMI promptly and almost completely.
- Sun, Jialin,Dai, Jingtao,Liu, Rui,Yang, Xiaowei,Chen, Jian
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- Effects of ionic liquids for lipase-catalyzed chiral 1,1′-binaphthyl- 2- yl(phenyl)methanone O-acetyl oxime synthesis
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The resolution of 1,1'-binaphthyl-2-yl(phenyl)methanone O-acetyl oxime catalyzed by lipase in three different ionic liquids, 1-butyl-3- methylimidazolium hexafluoride-phosphate, [bmim][PF6], 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF4] and N-butyl-pyridium hexafluorophosphate, [BuPy][PF6] and organic solvents was studied. The lipase shows low activity in ionic liquids and organic solvent with ionic liquids as the additive, while the lipase coated with ionic liquids gives the best enantioselectivity as high as 95 %.
- Zhou, Yongchang,Takahashia, Motohiro,Aoyagi, Naoto,Li, Chunlei,Kijimaa, Tatsuro,Izumia, Taeko
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- Oxidative desulfurization of fuel oil by pyridinium-based ionic liquids
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In this work, an N-butyl-pyridinium-based ionic liquid [BPy]BF4 was prepared. The effect of extraction desulfurization on model oil with thiophene and dibenzothiophene (DBT) was investigated. Ionic liquids and hydrogen peroxide (30%) were tested in extraction-oxidation desulfurization of model oil. The results show that the ionic liquid [BPy]BF4 has a better desulfurization effect. The best technological conditions are: V(IL)/V(Oil)/V(H2O2) = 1:1:0.4, temperature 55 °C, the time 30 min. The ratio of desulfurization to thiophene and DBT reached 78.5% and 84.3% respectively, which is much higher than extraction desulfurization with simple ionic liquids. Under these conditions, the effect of desulfurization on gasoline was also investigated. The used ionic liquids can be recycled up to four times after regeneration.
- Zhao, Dishun,Wang, Yanan,Duan, Erhong
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- Thermodynamic studies of ionic interactions in aqueous solutions of N-butyl-pyridinium bromide at 298.15 K
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Density and osmotic coefficient measurements for aqueous solutions of N-butyl-pyridinium bromide [Bpy][Br] in concentration range ~ 0.019 to ~ 0.39 mol·kg- 1 at 298.15 K are reported. The density data are used to obtain apparent molar volume (V), partial molar volume of solute and solvent V?2andV?1 respectively as well the limiting partial molar volume ?V0=V?20 of the solute [Bpy][Br] (by appropriate extrapolation). The experimental osmotic coefficient data are used to determine the activity and mean ionic activity coefficients of solute and solvent respectively. Experimental activity coefficient data are compared with those obtained from Debye-Hu?ckel and Pitzer models. The activity data have been further processed to obtain the Gibbs free energy change due to mixing (ΔGm) and excess Gibbs free energy change (ΔG E). The aggregation number (n) and critical micelle concentration (cmc) are obtained for ionic salt in solution phase by applying pseudo-phase separation model to andV data respectively. Application of McMillan-Mayer theory of solutions to the data is made. The results have been interpreted on the basis of structural characteristic of salt, ion-solvent and ion-ion interactions.
- Shaikh, Vasim R.,Terdale, Santosh S.,Gupta, Gaurav R.,Hundiwale, Dilip G.,Patil, Kesharsingh J.
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- Properties of Bromine Fused Salts Based on Quaternary Ammonium Molecules and Their Relevance for Use in a Hydrogen Bromine Redox Flow Battery
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Bromine complexing agents (BCA) in aqueous electrolytes for hydrogen bromine flow batteries are used to reduce bromine‘s vapour pressure, while an insoluble and liquid fused salt is formed. The properties (concentrations, composition, conductivity and viscosity) of this fused salt are investigated in this study systematically ex situ by using 7 BCAs at different state of charge in HBr/Br2/H2O electrolytes with a theoretical capacity of 179.6 Ah L?1. Bromine is stored in the fused salt at concentrations up to 13.6 M, reaching theoretical volumetrical capacities up to 730 Ah L?1 in fused salts. The fused salt consists of a pure, bromine- and water-free ionic liquid of organic [BCA]+ cations and polybromides, and its conductivity bases on a hopping mechanism among the polybromides. Alkyl side chain length of the BCAs and distribution of polybromides influence strongly the conductivity and viscosity of the fused salts. 1-ethylpyridin-1-iumbromide results to be favoured BCA for application.
- Fischer, Peter,Küttinger, Michael,Loichet Torres, Paulette A.,Meyer, Emeline
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supporting information
(2022/02/21)
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- Newly designed flow reactor as an original method of synthesis of ionic liquids by ion-exchange reactions
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Optimization of chemical reactions is often costly and requires a significant investment in both materials and time. The solution to this type of difficulty may be the use of continuous flow systems. With the use of the newly designed continuous flow system, the method of synthesizing ionic liquids (ILs) by ion exchange was optimized. The flow rate of the substrates and the selection of the packing of the column in which the reactions were carried out (random packing or a chemical compound in the form of a solid, which was the source of the anion exchanged) were also optimized. The purity of the obtained ionic liquids and the progress of the reaction was determined using ion chromatography. Additionally, for the ionic liquids, which were the starting compounds for the ion exchange reaction, the basic physicochemical properties were determined, thus extending the data library available for chemical compounds belonging to the group of ionic liquids.
- Pawlowska-Zygarowicz, Anna
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supporting information
(2021/11/16)
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- Convenient synthesis of long alkyl-chain triazolylglycosides using ionic liquid as dual promoter-solvent: Readily access to non-ionic triazolylglycoside surfactants for evaluation of cytotoxic activity
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A convenient method for the one-pot synthesis of long alkyl-chain triazolylglycosides using ionic liquid as dual promoter and solvent is described via a sequential one-pot two-step glycosidation-CuAAc click reaction. The reaction was carried out using commercially available substrates, including glycosyl bromides, sodium azide and various long alkyl-chain alkynes to achieve the corresponding products in moderate to high yields. Furthermore, this approach was successfully applied for the preparation of non-ionic monocatenary triazolylglycoside surfactants in excellent yields through simple deacetylation. Subsequently, these surfactants were further evaluated for their cytotoxic activity.
- Ketsomboon, Nutthanicha,Saeeng, Rungnapha,Srisook, Klaokwan,Sirion, Uthaiwan
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- Chemical Vapor Deposition of Ionic Liquids for the Fabrication of Ionogel Films and Patterns
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Film deposition and high-resolution patterning of ionic liquids (ILs) remain a challenge, despite a broad range of applications that would benefit from this type of processing. Here, we demonstrate for the first time the chemical vapor deposition (CVD) of ILs. The IL-CVD method is based on the formation of a non-volatile IL through the reaction of two vaporized precursors. Ionogel micropatterns can be easily obtained via the combination of IL-CVD and standard photolithography, and the resulting microdrop arrays can be used as microreactors. The IL-CVD approach will facilitate leveraging the properties of ILs in a range of applications and microfabricated devices.
- Ameloot, Rob,Arnauts, Giel,Calderon Gonzalez, Maider,Cruz, Alexander John,Hauffman, Tom,Marcoen, Kristof,Obst, Martin
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supporting information
p. 25668 - 25673
(2021/10/04)
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- ZIF-8-porous ionic liquids for the extraction of 2,2,3,3-tetrafluoro-1-propanol and water mixture
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The design of stable ionic liquids (ILs) has become crucial for efficient liquid-liquid extraction (LLE) of alcohol and water. Porous ionic liquids (PILs), as a special class of ILs, have attracted attention by virtue of their unique porous structure and IL characteristics. In this research, a series of zeolitic imidazolate framework-8 based porous ionic liquids (ZIF-8-PILs) were synthesized by simply mixing a solution of zeolitic imidazolate framework-8 (ZIF-8) and rationally designed ILs. The introduction of ZIF-8 resulted in a unique liquid porous structure and molecular sieve for ZIF-8-PILs. The improved extraction properties endowed ZIF-8/[Bpy][NTf2] with more efficiency for the separation of 2,2,3,3-tetrafluoro-1-propanol (TFP) and water with 88.1% TFP extraction rate and steady reuse. The excellent extraction performance of ZIF-8-PILs is discussed in relation to their textural property and unique intermolecular interaction.
- Wang, Zenghui,Zhao, Pingping,Wu, Jimin,Gao, Jun,Zhang, Lianzheng,Xu, Dongmei
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supporting information
p. 8557 - 8562
(2021/05/26)
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- Green Synthesis of Cobalt Oxide Nanostructures: Morphology, Optical and Magnetic Characterization
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Abstract: Synthesis of Co3O4 nanostructures with morphologies of nanoparticles and nanosheets were successfully achieved by reflux method in the presence of pyridinium based ionic liquids, N-butylpyridinium bromide [BuPy]Br and N-octylpyridinium bromide [OPy]Br. The ionic liquid plays an important role as reaction media and morphology template to control Co3O4 nanostructures. Different morphologies of Co3O4 nanostructures were obtained by changing the ratio of the NaOH to Co(NO3)2·6H2O. The structure, morphology, and properties of prepared Co3O4 nanostructures were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), vibrating sample magnetometer (VSM) and UV-visible spectroscopy. SEM and X-ray powder diffraction results showed that the Co3O4 nanostructures were obtained with smaller crystallite sizes by using butyl pyridinium ionic liquid with a shorter alkyl side chain. The results of optical measurements illustrate the blue shift of the bandgap using ILs. Furthermore, the ferromagnetic behavior of Co3O4 nanostructures was confirmed in magnetic measurement by the presence of a hysteresis loop.
- Badri, R.,Darband, M.,Sanaeishoar, H.,Tahanpesar, E.
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p. 2068 - 2076
(2022/01/19)
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- Ionic Liquid-Assisted Preparation of Co3O4 Nanosheets as a New and Efficient Catalyst for Green Synthesis of Various 1,5-Benothiazepine Derivatives in Water
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Abstract: A novel and green method for the preparation of cobalt oxide nanosheets using pyridinium-based ionic liquid by simple reflux method is described in the present work. Pyridinium-based ionic liquid, N-butyl pyridinium bromide [BuPy]Br plays an important role as reaction media and morphology template to control Co3O4 nanostructures. This catalyst is characterized by XRD, FE-SEM, FT-IR, VSM and UV-Visible spectroscopy. Further, this nanocatalyst is used to catalyzes the condensation reaction of o-amino thiophenol with α,β-unsaturated ketones for preparation of 1,5-benzothiazepine derivatives in excellent yields. This efficient catalyst could be recovered and reused several times without any significant loss of activity.
- Darband,Tahanpesar,Sanaeishoar,Badri
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p. 1624 - 1634
(2022/03/23)
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- Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm
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The reaction between α-hydroxy-(or α-acetoxy) cyclopenten-aziridines (6-azabicyclo[3.1.0]hex-3-en-2-ols or acetates) and C-based nucleophiles in the presence of Pd(0)-catalysis was investigated. In all the cases studied, the reaction was totally regio- and diastereo-selective, affording a single adduct in moderate to good yields. Specifically, attack of the nucleophile at position 3 of the cyclopentene moiety, anti to the vicinal oxy group, with vinylogous ring opening of the aziridine ring, was observed. When the carbon acid is a very acidic methylene (pKa (DMSO) ≤ 7.3), the resulting adduct is a zwitterion, resulting from an intramolecular proton transfer between the amino group and the carbon acid moiety taking place after the C–C bond formation. A plausible mechanism for this transformation is put forward.
- Oliveira, Jo?o A.C.,Kiala, Gredy,Siopa, Filipa,Bernard, Aurélie,Gontard, Geoffrey,Oble, Julie,Afonso, Carlos A.M.,Poli, Giovanni
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supporting information
(2020/04/28)
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- Physicochemical and thermodynamic properties of the {1-alkyl-1-methylpiperidinium bromide [C1Cn =2,4PIP][Br], or 1-butylpyridinium bromide, [C4Py][Br], or tri(ethyl)butylammonium bromide [N2,2,2,4] [Br] + water} binary systems
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This work is a continuation of our comprehensive study of ionic liquids, ILs (including organic salts with melting temperature above 100 °C) and their aqueous solutions as a novel alternative working pair for the absorption heat pump. A series of organic salts: 1-ethyl-1-methyl-piperidinium bromide, [C1C2PIP][Br], 1-butyl-1-methyl-piperidinium bromide, [C1C4PIP][Br], 1-butylpyridinium bromide, [C4Py][Br] and tri(ethyl)butylammonium bromide, [N2,2,2,4][Br] have been synthesized. The structures of compounds have been confirmed using NMR spectra. The basic thermal characterization of pure organic salts, including temperature and enthalpy of phase transition (Ttr, ΔtrH), temperature and enthalpy of melting (Tfus ΔfusH) have been measured using a differential scanning microcalorimetry technique (DSC). The physico-chemical properties that are: density (ρ) and dynamic viscosity (η) of the tested binary systems have been determined at wide temperature and composition range. From experimental densities data, the apparent molar volumes (V?,1) were calculated. In order to obtain limiting apparent molar volumes (V?,1 0), the concentration dependence of apparent molar volumes was correlated with Redlich–Mayer type equation. Additionally, the limiting molar expansibilities (E? 0) and isobaric thermal expansion coefficients (αP) have been calculated. Temperature dependence of the dynamic viscosity has been correlated using VFT equation. The solid?liquid phase equilibria (SLE) have been determined using a dynamic method and correlated using NRTL equation. The influence of the alkyl chain length in the piperidinium cation substituent, as well as the cation structure, on investigated properties are presented and discussed.
- Królikowska, Marta,Zawadzki, Maciej,Kuna, Tomasz
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p. 220 - 231
(2018/12/13)
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- Carboxylate ionic liquid as well as preparation method and application thereof
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The invention provides carboxylate ionic liquid as well as a preparation method and application thereof. According to the carboxylate ionic liquid provided by the invention, an imidazole group or a pyridine group is introduced into the cationic part of the carboxylate ionic liquid and a carboxylic acid group is introduced into the anionic part of the carboxylate ionic liquid; and the ionic liquidcatalyst provided by the invention is simple and convenient in synthesis route, high in yield and easy to recover. Anion carboxylate radical in the carboxylate ionic liquid provided by the invention serves as an active site, so that synthesis of diol can be realized through high-efficiency and high-selectivity catalysis of hydration reaction of epoxy compounds under the condition of not adding other catalysts.
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Paragraph 0130-0136
(2019/10/23)
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- Flow-Assisted Synthesis of Bicyclic Aziridines via Photochemical Transformation of Pyridinium Salts
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Herein is described the development and comparison of homemade continuous-flow reactors, a fluorinated ethylene propylene tube (FEP) reactor (internal diameter of 0.4 cm) and two parallel quartz reactors containing two different internal diameters (0.4 and 0.2 cm), and their application to the photochemical transformation of 1-n-butyl- and 1-allylpyridinium bromide salts (1a and 1b, respectively) to the corresponding α-hydroxycyclopentenoaziridines (6-azabicyclo[3.1.0]hex-3-en-2-ols) 2a and 2b. Under recirculating conditions, the FEP reactor allowed the production of a greater quantity of bicyclic aziridine (3.2 g), while the quartz reactor with the same diameter furnished the best productivity results (3.7 g L-1 h-1). In addition, the FEP reactor operated efficiently under circulating conditions (1.75 L of 1a) for 4.5 days (residence time of 17.9 h), allowing the production of 2a at a rate of 2 g/day (62-93% conversion).
- Siopa, Filipa,António, Joao P. M.,Afonso, Carlos A. M.
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p. 551 - 556
(2018/04/27)
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- Rational selection of the cation of an ionic liquid to control the reaction outcome of a substitution reaction
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A range of ionic liquids was examined as solvents for a substitution reaction. They were chosen through rationally varying the ionic liquid cation in order to enhance the rate constant. Access to charge and electron-withdrawing substituents benefitted rat
- Hawker, Rebecca R.,Haines, Ronald S.,Harper, Jason B.
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supporting information
p. 2296 - 2299
(2018/03/06)
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- Bromobismuthates: Cation-induced structural diversity and Hirshfeld surface analysis of cation–anion contacts
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Reactions of [BiBr6]3? and bromide salts of various substituted pyridinium cations in excess of HBr result in a series of bromobismuthate anionic complexes of various geometry and nuclearity: [{BiBr4}n]n?, [Bi2Br9]3? and [Bi2Br10]4?. Hirshfeld surface analysis for 19 crystal structure was performed; impact of various X-Br contacts on the crystal structures is discussed.
- Adonin, Sergey A.,Gorokh, Igor D.,Novikov, Alexander S.,Samsonenko, Denis G.,Korolkov, Ilya V.,Sokolov, Maxim N.,Fedin, Vladimir P.
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p. 282 - 288
(2017/11/27)
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- Greg Phineas intermediate preparation process
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The invention discloses a preparation method of a Greg Phineas intermediate of 4-(4-amino-3-trifluoromethyl)-N-picoline-2-formamide. The intermediate is characterized in that the preparation process comprises the steps of in the presence of alkali, conducting contact reaction of 3-fluorine-4-Aminophenol and 4-chlorine-2-Pyridine amide hydrochloride to acquire the Greg Phineas intermediate of 4-(4-amino-3-trifluoromethyl)-N-picoline-2-formamide. The Greg Phineas intermediate preparation process uses ionic liquid as both the reaction medium and the catalyst, the reaction condition is mild, environmentally friendly, the yield is high, the reaction time is greatly shortened, thus the Greg Phineas intermediate is particularly suitable for enlarged industrial production with huge application potential.
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Paragraph 0019; 0020
(2017/05/25)
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- Method for synthesizing dexmedetomidine hydrochloride intermediate
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The invention discloses a method for synthesizing a dexmedetomidine hydrochloride intermediate. The synthesis method comprises the step that 1-(1-trifluoromethanesulfonate)ethyl-2,3-dimethylbenzene and imidazole are subjected to stirring reacting in ionic liquid in the presence of alkali and [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride to obtain the dexmedetomidine hydrochloride intermediate 4-[1-(2,3-dimethylbenzene)ethyl]-1H-imidazole. The method is short in reacting time and high in product production efficiency and yield and has the good selectivity on a target (S)-isomer.
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Paragraph 0025
(2017/08/28)
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- Gold-Catalyzed Direct Alkynylation of Azulenes
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A novel catalytic method for the direct C-H alkynylation of azulenes is developed. The gold catalyzed functionalization of this special carbacycle is achieved with hypervalent iodonium reagent TIPS-EBX under mild reaction conditions. With the aid of the developed procedure, several TIPS alkynylated azulene derivatives were synthesized bearing important functional groups for further functionalization.
- Székely, Anna,Péter, áron,Aradi, Klára,Tolnai, Gergely L.,Novák, Zoltán
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supporting information
p. 954 - 957
(2017/02/26)
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- Cleavage of ethers in an ionic liquid. Enhancement, selectivity and potential application
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The cleavage of a series of ethers was examined in an ionic liquid containing hydrogen bromide. Reactions that did not proceed in either water or DMSO were found to proceed readily in this system, with notable selectivity between the cleavage of the different ether types examined herein. Increasing the proportion of water in the reaction mixture dramatically decreased the rate constant of ether cleavage; this could, in part, be attributed to a decrease in the solvent stabilisation of the transition state. Through analysis of the electronic requirements of the reaction (using substrates containing substituents with different Hammett parameters) and observation of rate enhancements for an ortho substituted system, the importance of the extent of protonation of the ether prior to nucleophilic attack was demonstrated.
- Hart, William E. S.,Aldous, Leigh,Harper, Jason B.
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supporting information
p. 5556 - 5563
(2017/07/12)
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- Application of primary halogenated hydrocarbons for the synthesis of 3-Aryl and 3-Alkyl indolizines
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Indolizine is an important heterocyclic compound with several interesting properties that make it suitable for numerous applications in many fields, such as biology, medicine and materials. However, the synthesis of 3-Alkyl indolizines from bulky primary halogenated alkanes has not yet been reported. Herein, a transition-metal-free synthetic route to 3-Aryl and 3-Alkyl indolizines from electron-deficient alkenes, pyridines and primary halogenated hydrocarbons has been reported for the first time using a tandem reaction. The key step of this method is the oxidative dehydrogenative aromatization of a tetrahydroindolizine intermediate with 2,2,6,6-Tetramethylpiperidine-N-oxyl (TEMPO) as the oxidant. The advantages of this protocol are its use of easily available and low-cost starting materials, the transition-metal-free conditions and its ready scalability.
- Liu, Yan,Hu, Huayou,Zhou, Junyu,Wang, Wenhui,He, Youliang,Wang, Chao
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p. 5016 - 5024
(2017/07/10)
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- Micelle formation as a factor influencing the mode(s) of metal ion partitioning into: N -alkylpyridinium-based ionic liquids (ILs): Implications for the design of IL-based extraction systems
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Prior studies of metal ion partitioning between an acidic aqueous phase and an ionic liquid in the presence of a macrocyclic polyether have demonstrated that the overall partitioning is a composite of three distinct pathways: neutral complex/ion-pair extraction, exchange of a cationic metal-crown ether (CE) complex for the cationic constituent of the IL, and exchange of the metal ion for a hydronium ion in a CE-H3O+ complex formed during acid preconditioning of the IL. The obvious undesirability of the ion-exchange pathways, which can lead to substantial loss of the IL cation to the aqueous phase, has led to efforts to identify means by which these processes can be suppressed or eliminated. Prior work with N,N′-dialkylimidazolium and quaternary ammonium bis [(trifluoromethyl)sulfonyl]imides has shown that increasing the hydrophobicity of the IL cation can be an effective means of diminishing the contribution of ion-exchange. Work with the corresponding N-alkylpyridinium ILs, however, indicates that in certain instances, an increase in the hydrophobicity of the IL cation is accompanied by a marked increase in its propensity to self-associate, leading to the formation of micelles in the aqueous phase. The net effect is to diminish or even negate the expected beneficial effect of IL cation hydrophobicity in reducing the contribution of ion exchange to the overall metal ion partitioning process, adversely impacting the "greenness" of extraction processes employing these ILs.
- Wankowski, James L.,Kaul, Michael J.,Dietz, Mark L.
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supporting information
p. 5674 - 5682
(2017/12/06)
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- Tenofovir disoproxil preparation method
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The invention discloses a tenofovir disoproxil preparation method. The tenofovir disoproxil preparation method includes enabling tenofovir to react with halogenated chloromethyl isopropyl carbonate in ionic liquid in the presence of acid-capturers so as to obtain tenofovir disoproxil. The tenofovir disoproxil preparation method has the advantages that a great quantity of irritant N-methyl pyrrolidone and phase transfer catalysts are avoided, cost and post-treatment workload are both reduced, reaction time is shortened effectively and high yield is achieved.
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Paragraph 0020-0022
(2017/08/29)
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- Ionic liquids as solvents for rhodium and platinum catalysts used in hydrosilylation reaction
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A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.
- Zielinski, Witold,Kukawka, Rafal,Maciejewski, Hieronim,Smiglak, Marcin
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- A pyridine ionic liquid catalyzed glycerin liquid phase dehydration method of preparation of acrolein
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The present invention relates to the field of organic chemistry, particularly to a method for preparing acrolein through catalysis of glycerol liquid phase dehydration by using a pyridine ion liquid. According to the method, a pyridine ion liquid is adopted, a semi-batch reaction is adopted, and glycerol liquid phase dehydration is performed at a reaction temperature of 250-350 DEG C and a molar ratio of the ion liquid to the glycerol of 0.5:100-1.2:100 to prepare the acrolein, wherein a glycerol conversion rate is 100%, and an acrolein yield is 32.0-67.9%. According to the present invention, the biomass glycerol is adopted to prepare the high added value acrolein, raw material cost is low, raw material sources are wide, acidity of the catalyst can be adjusted, catalytic activity is high, and the process has characteristics of fast reaction, high selectivity, simple product system separation, safe and environmental protection process, and industrial production.
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Paragraph 0015; 0016
(2017/01/09)
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- Selective hydrogenation of phenol to cyclohexanone in water over PD@N-doped carbon derived from ionic-liquid precursors
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In this report, a kind of mesoporous N-doped carbon (CN-x) derived from N-containing ionic-liquid (IL) precursors were synthesized, and Pd@CN-x prepared by a simple ultrasound-assisted method showed higher catalytic activity for the selective hydrogenation of phenol and its derivatives under mild reaction conditions in water than commercial Pd@C and other common Pd heterogeneous catalysts. The catalytic activities of Pd@CN-x derived from different ILs were different, and further study into the influencing factors, including physical properties, N species of CN-x, and Pd status of Pd@CN-x, were performed. Being picky: N-Doped carbon (CN-x) derived from N-containing ionic-liquid precursors are used as Pd nanoparticle supports for the selective hydrogenation of phenol to cyclohexanone with high activity and selectivity under mild reaction conditions. The activities of the Pd@CN-x catalysts derived from a variety of ionic liquids are different, and studies on the physical properties, Pd status, and N species of the catalysts are performed.
- Xu, Xuan,Li, Haoran,Wang, Yong
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p. 3328 - 3332
(2015/04/16)
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- Octanol/water partition coefficients of pyridinium-based ionic liquids
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Nine pyridinium-based ionic liquids were synthesised, which include 1-butylpyridinium bromide ([BPYR] [Br]), 1-hexylpyridinium bromide ([HPYR][Br]), 1-octylpyridinium bromide ([OPYR][Br]), 1-hexylpyridinium bis(trifluoromethylsulfonyl)imide ([HPYR] [NTf2]), 1-octylpyridinium bis(trifluoromethylsulfonyl)imide ([OPYR][NTf2]), 1-hexylpyridinium trifluoromethanesulfonate ([HPYR] [TFO]), 1-octylpyridinium trifluoromethanesulfonate ([OPYR][TFO]), 1-hexylpyridinium tetrafluoroborate ([HPYR] [BF4]), 1-octylpyridinium I tetrafluoroborate ([OPYR][BF4]). The octanol/water partition coefficients (KOWs) of these pyridinium-based ionic liquids were determined by shake-flask method. It is found that the pyridinium-based ionic liquids measured in this work are extremely hydrophilic except for [OPYR] [NTf2]. It is also found that KOWs of [NTf2] ionic liquids were dependent on the concentration and high ionic liquids concentration in water leads to big KOW.
- Zhang, Teng,Wang, Yaquan
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p. 2819 - 2822
(2015/12/11)
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- FIVE-MEMBERED CYCLIC ANION USE THEREOF AS AN ELECTROLYTE
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A pentacyclic anion salt is provided for use thereof in electrolyte compositions. The compound has an inorganic, organic or organometallic cation M of valency m (1≦m≦3) and m anions corresponding to the formula (I) in which Rf is a —CFZ′Z″ group in which Z′ is F or a perflouroalkyl group having from 1 to 3 carbon atoms, and Z″ is an H, F or Cl group, an optionally fluorinated or perfluorinated alkoxy group having from 1 to 5 carbon atoms, an optionally fluorinated or perfluorinated oxaalkoxy group having 1 to 5 carbon atoms or an optionally fluorinated or perfluorinated alkyl group having from 1 to 5 carbon atoms; Z″ being other than F when Z′ is F. An electrolyte composition comprises said salt in solution in a liquid solvent or a polymer solvent.
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Paragraph 0092
(2015/11/28)
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- Structural diversity in hybrid vanadium(iv) oxyfluorides based on a common building block
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There are only limited reports on vanadium(iv) oxyfluorides (VOFs) with extended crystal structures. Here we expand and enrich the list of existing VOFs with a series of 14 new materials "VOF-n (n = 1-14)" prepared using ionothermal and solvothermal synthesis methods. All of these materials arise from the condensation of a dimeric structural motif. These VOFs can be classified into three groups depending on their key structural features; layer structures: VOF-1 "[HN2C7H6][V 2O2F5]", VOF-2 "[HN2C 4H4][V2O2F5]", VOF-3 "[HN2C3H4][V2O 2F5]" and VOF-4 "V2(N 2C4H4)O2F4", ladder like structures: VOF-5 "[NH4(HN2C3H 4)][V2O2F6]", VOF-6 "[K(HN2C3H4)][V2O 2F6]", VOF-7 "[HNH2CH 2CH3][VOF3]", VOF-8 "[HN 2C7H6][VOF3]", VOF-9 "[H2N2C4H6][V2O 2F6]", VOF-10 "β-RbVOF3", VOF-11"α-KVOF3", VOF-12 "β-KVOF 3", VOF-13 "[H2(NH2) 2(CH2)2][V2O2F 6]", and a chain structure: VOF-14 "[H2N 2C6H12][V2O2F 7]". The crystal structures of VOF-n are presented, and their synthetic and structural relationships are discussed.
- Aidoudi, Farida H.,Black, Cameron,Arachchige, Kasun S. Athukorala,Slawin, Alexandra M. Z.,Morris, Russell E.,Lightfoot, Philip
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supporting information
p. 568 - 575
(2014/01/06)
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- One-pot synthesis of 2,4,5-trisubstituted imidazoles using [BPy]H 2PO4, an efficient and recyclable catalyst
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[BPy]H2PO4 was easily prepared and used as an efficient and recyclable catalyst for the one-pot synthesis of 2,4,5-trisubstituted imidazoles under solvent-free conditions in good to excellent yields. Solvent-free conditions, simple experimental and workup procedures, and the use of a nontoxic, recyclable catalyst of an environmentally benign nature are remarkable features of the procedure.
- Zhang, Yuliang,Zhou, Zhongqiang
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p. 189 - 196
(2013/04/10)
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- Thermochemistry of the pyridinium- and pyrrolidinium-based ionic liquids
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We applied DSC for the determination of enthalpies of synthesis reactions of pyridinium- and pyrrolidinium-based ionic liquids (ILs) from pyridine (or N-methyl-pyrrolidine) and n-alkyl bromides (with n = 4, 5, 6, 7, and 8). The combination of reaction enthalpy measurements by DSC with modern high-level first-principles calculations opens valuable indirect thermochemical options to obtain values of enthalpies of the formation and vaporization enthalpies of ILs.
- Verevkin, Sergey P.,Ralys, Ricardas V.,Emel'Yanenko, Vladimir N.,Zaitsau, Dzmitry H.,Schick, Christoph
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p. 353 - 358
(2013/06/04)
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- Does alkyl chain length really matter? Structure-property relationships in thermochemistry of ionic liquids
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DSC was used for determination of reaction enthalpies of synthesis of ionic liquids [Cnmim][Cl]. A combination of DSC with quantum chemical calculations presents an indirect way to study thermodynamics of ionic liquids. The indirect procedure for vaporization enthalpy was validated with the direct experimental measurements by using thermogravimetry. First-principles calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the CBS-QB3 and G3 (MP2) theory. Experimental DSC data for homologous series of alkyl substituted imidazolium, pyridinium, and pyrrolidinium based ionic liquids with anions [Cl] and [Br] were collected from the literature. We have shown that enthalpies of formation, enthalpies of vaporization, and lattice potential energies are linearly dependant on the alkyl chain length. The thermochemical properties of ILs generally obey the group additivity rules and the values of the additivity parameters for enthalpies of formation and vaporization seem to be very close to those for molecular compounds.
- Verevkin, Sergey P.,Zaitsau, Dzmitry H.,Emel'Yanenko, Vladimir N.,Ralys, Ricardas V.,Yermalayeu, Andrei V.,Schick, Christoph
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- Three different types of heterocycle of nitrogen-containing alkaline ionic liquids treatment of acid oil to remove naphthenic acids
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Ionic liquids had enormous potential for industrial use as environmental friendly chemicals. A green and effective deacidification method was found based on ionic liquids. N-alkylpyridinium bromide ([APy]Br), 1-alkyl-3- methylimidazolium bromide ([AMIm]Br) and 1-alkyl-3-methylimidazolium imidazolide ([AMIm]Im) were used to remove naphthenic acids from acid oil. The performance of deacidification followed the order [APy]Br [AMIm]Br [AMIm]Im. The stronger alkalinity of ionic liquids was, the higher deacidification would be. The growth of alkyl chain length was also beneficial to get high deacidification. The deacidification mechanism was that liquid clathrate could form due to interaction between the ionic liquids and π-bond in naphthenic acids through π-π interaction. When the reagent/oil ratio of [OMIm]Im (1-octyl-3-methylimidazolium imidazolide)/oil was 0.008, the deacidification rate could be reached 100%. The preliminary results reveal that the process consumes less energy, saves time and produces less pollution to environment.
- Duan, Jiyun,Sun, Yu,Shi, Li
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p. 180 - 185
(2013/07/26)
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- Application of ionic liquids for extraction and synthesis of organosulfur compounds
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We consider the possible application of pyridinium ionic liquids to desulfurize hydrocarbon raw products and to transform the extracted toxic admixtures into promising sulfur compounds. Anodic oxidation of the extracted thiols as well as oxidation in the presence of electron mediators (N,N,N′,N′-tetramethyl-1,4-phenylenediamine, tri-p-bromophenylamine, and tri-p-tolylamine) leads to the corresponding disulfides.
- Okhlobystina,Okhlobystin,Koldaeva,Movchan,Litvin,Berberova
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p. 2062 - 2065
(2014/01/17)
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- Molten ammonium salt as a solvent for menschutkin quaternization reaction (synthesis of ionic liquids) and other heterocyclic compounds
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An efficient one pot synthesis of ionic liquids (ILs) employing molten salt as a solvent is described. The imidazolium salts and pyridinium bromide and other heterocyclic compounds were synthesized using tetrabutylammonium halides as ionized solvents when melt. The yields were good and compounds were confirmed by their mass and spectral data. The utility of the method as a green one is suggested by comparing yield and kinetic time requirements with other known well established methods.
- Gupta, Gaurav R.,Chaudhari, Ganesh R.,Tomar, Preeti A.,Waghulade, Govinda P.,Patil, Keshar Singh J.
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experimental part
p. 4675 - 4678
(2012/08/27)
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- Scalable synthesis of ionic liquids: Comparison of performances of microstructured and stirred batch reactors
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A range of alkylpyridinium bromide ionic liquids have been synthesized in a stirred reactor at multigram scale and characterized by physical methods (viscosity, conductivity, melting point, electrochemical window, and water content). One ionic liquid, octylpyridinium bromide, was chosen to be synthesized in both macro and reduced scale reactors, in order to compare its performance and to afford evidence of the advantages of a cross channel micro reactor (channel width = 1 mm) compared to a stirred reactor.
- Iken, Hicham,Guillen, Frédéric,Chaumat, Hélène,Mazières, Marie-Rose,Plaquevent, Jean-Christophe,Tzedakis, Théodore
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supporting information; experimental part
p. 3474 - 3477
(2012/08/13)
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- Parallel microwave-assisted synthesis of ionic liquids and screening for denitrogenation of straight-run diesel feed by liquid-liquid extraction
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Fifty-six ionic liquids were efficiently synthesized in parallel format under one-pot, solvent-free microwaveassisted synthesis. These compounds were evaluated as extracting agents of nitrogen-containing compounds from a real Diesel feed before being submitted to the hydrodesulfurization process to obtain ultralow sulfur Diesel. Our results showed that halogenated ionic liquids are an excellent alternative due to these ionic liquids are relatively inexpensive, presenting a high selectivity for the extraction of nitrogen-containing compounds and can be regenerated and recycled.
- Ceron, Miguel A.,Guzman-Lucero, Diego J.,Palomeque, Jorge F.,Martinez-Palou, Rafael
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experimental part
p. 427 - 432
(2012/07/01)
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- Ionic-liquid-mediated active-site control of MoS2 for the electrocatalytic hydrogen evolution reaction
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The layered crystal MoS2 has been proposed as an alternative to noble metals as the electrocatalyst for the hydrogen evolution reaction (HER). However, the activity of this catalyst is limited by the number of available edge sites. It was previously shown that, by using an imidazolium ionic liquid as synthesis medium, nanometre-size crystal layers of MoS2 can be prepared which exhibit a very high number of active edge sites as well as a de-layered morphology, both of which contribute to HER electrocatalytic activity. Herein, it is examined how to control these features synthetically by using a range of ionic liquids as synthesis media. Non-coordinating ILs with a planar heterocyclic cation produced MoS2 with the de-layered morphology, which was subsequently shown to be highly advantageous for HER electrocatalytic activity. The results furthermore suggest that the crystallinity, and in turn the catalytic activity, of the MoS2 layers can be improved by employing an IL with specific solvation properties. These results provide the basis for a synthetic strategy for increasing the HER electrocatalytic activity of MoS2 by tuning its crystal properties, and thus improving its potential for use in hydrogen production technologies. Copyright
- Lau, Vincent Wing-Hei,Masters, Anthony F.,Bond, Alan M.,Maschmeyer, Thomas
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experimental part
p. 8230 - 8239
(2012/08/29)
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- Synthesis of imidazolium and pyridinium-based ionic liquids and application of 1-alkyl-3-methylimidazolium salts as pre-catalysts for the benzoin condensation using solvent-free and microwave activation
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An efficient one-pot procedure for the synthesis of ionic liquids based on nitrogen-containing heterocycles, imidazolium or pyridinium under 'green chemistry' conditions has been described. Imidazolium salts and DBU have been found to catalyze efficiently the benzoin condensation giving good yields within very short reaction time using solvent-free microwave activation conditions.
- Aupoix, Audrey,Pégot, Bruce,Vo-Thanh, Giang
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experimental part
p. 1352 - 1356
(2010/04/02)
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- Density and surface tension of ionic liquids [Cnpy][NTf 2] (n = 2, 4, 5)
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Density and surface tension of the air- and water-stable hydrophobic ionic liquids N-alkylpyridinium bis(trifluoromethylsulfonyl)imide ([C npy][NTf2], n = 2, 4, 5) were measured in the temperature range T = (283.15 to 338.15) K. The melting temperatures of the samples were determined by differential scanning calorimetry (DSC). Decomposition temperatures are higher than 600 K as determined by thermogravimetric analysis (TG).
- Liu, Qing-Shan,Yang, Miao,Yan, Pei-Fang,Liu, Xiu-Mei,Tan, Zhi-Cheng,Welz-Biermann, Urs
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scheme or table
p. 4928 - 4930
(2011/09/12)
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- Biodegradable pyridinium ionic liquids: Design, synthesis and evaluation
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A range of ionic liquids (ILs) with a pyridinium cation were synthesised and their biodegradability was evaluated using the CO2 Headspace test (ISO 14593). ILs bearing an ester side chain moiety were prepared from either pyridine or nicotinic acid and showed high levels of biodegradation under aerobic conditions and can be classified as 'readily biodegradable'. In contrast, pyridinium ILs with alkyl side chains showed significantly lower levels of biodegradability in the same test. The utility of the biodegradable IL 6c as a reaction solvent for the Diels-Alder reaction was also investigated.
- Harjani, Jitendra R.,Singer, Robert D.,Garcia, M. Teresa,Scammells, Peter J.
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experimental part
p. 83 - 90
(2010/04/22)
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- Reaction of thiolesters with nitrogen ylides
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The pairing of unstabilized nitrogen ylides generated in situ with functionalized thiolesters under ambient conditions resulted in a new intramolecular carbon-carbon bond forming reaction. The scope of the reaction was illustrated with a series of substit
- Voltrova, Svatava,Srogl, Jiri
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supporting information; experimental part
p. 1677 - 1679
(2009/04/06)
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- Ionic liquids on the basis of 2,3,4,6,7,8,9,10-octahydropyrimido-[1,2-a] azepine (1,8-diazabicyclo[5.4.0]undec-7-ene)
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New ionic liquids containing alkyl and polyfluoroalkyl substituents and various anions were synthesized from 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a] azepinium ion (1,8-diazabicyclo[5.4.0]undec-7-en-8-ium). Their NMR spectra and miscibility with water and organic solvents were studied. Pleiades Publishing, Inc., 2006.
- Tolstikova,Shainyan
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p. 1068 - 1074
(2007/10/03)
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- Organic salt conditioner, organic salt-containing composition, and uses thereof
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The present invention relates to the use of, and a composition containing, at least one non-polymeric organic salt with a melting point of less than 60° C. These organic salts may be imidazolium, pyrazolium, pyridinium, pyrimidinium or tetraalkylphosphonium salts. The inventinon composition may be used for washing (cleaning) and/or conditioning keratin materials, and especially the hair.
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- Microwave-assisted synthesis of room-temperature ionic liquid precursor in closed vessel
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We report here the synthesis of various alkylpyridinium and 1-alkyl-3-methylimidazolium halides on a large scale under microwave irradiation, in a closed vessel. The reaction time was drastically reduced as compared to conventional methods, and good yields were obtained.
- Khadilkar, Bhushan M.,Rebeiro, Geeta L.
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p. 826 - 828
(2013/09/06)
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