1-Butyl-3-methylimidazolium Hydrogen Sulfate [bmim]HSO4: An Efficient Reusable Acidic Ionic Liquid for the Formylation of Alcohols

1-Butyl-3-methylimidazolium hydrogen sulfate [bmim]HSO4 as an acidic ionic liquid was prepared and used as a catalyst for the formylation of alcohols with ethyl formate at room temperature with good to excellent yields. A good selectivity was observed for the formylation of primary alcohols in the presence of tertiary alcohols.     

BrФnsted Acidic Ionic Liquids: Novel Efficient,Cost-effective and Reusable Solvent-catalysts for Ritter Reaction

Several Brnsted acidic ionic liquids(ILs) were synthesized and used as dual solvent-catalysts for the Ritter reaction of benzonitrile with tert-butanol. In particular, IL11([NSPTEA][OTF]) showed excellent catalytic activity for the Ritter reaction. In the presence of IL11, various nitriles and tertiary alcohols as well as secondary alcohols were converted smoothly to the corresponding amides in good to excellent yields. In addition, this cost-effective ionic liquid [NSPTEA][OTF] was easily separated from the reaction mixture by extraction with a small amount of water, and was recycled five times without any significant loss in activity.     

Polystyrene-supported chloroaluminate ionic liquid as a new heterogeneous Lewis acid catalyst for Knoevenagel condensation

Non-hygroscopic polystyrene-supported chloroaluminate ionic liquid was prepared from the reaction of Memfield resin with 1- methylimidazole followed by reaction with aluminum chloride.This Lewis acidic ionic liquid is environmentally friendly heterogeneous catalyst for the Knoevenagel condensation of aromatic and aliphatic aldehydes with ethyl cyanoacetate.The catalyst is stable(as a bench top catalyst) and reusable.     

Room Temperature Ionic Liquid： a Powerful Additive of Mn（Salen） Catalyzed Oxidation of sec-Alcohols

A simple, mild, efficient Mn(salen)-catalyzed oxidation system of secondary alcohols, in which the ionic liquid [bmim]PF6 acts as a powerful additive, has been described. The reaction proceeded with higher efficiency. The catalyst was more easier to recycle in ionic liquid [bmim]PF6 with a well-proportioned CH2Cl2 than in the single CH2Cl2 or ionic liquid.     

Preparation and Characterization of a Novel Benzimidazolium Bronsted Acid Ionic Liquid and Its Application in the Synthesis of Arylic Esters

A novel Brφnsted acid task specific ionic liquid 1-ethylbenzimidazolium tetrafluoroborate （[Hebim]BF4） with functional benzimidazolium cation was synthesized and characterized by ^1H NMR, IR, MS spectra and elemental analysis. This novel ionic liquid was successfully used as dual solvent-catalyst for the synthesis of arylic esters. Higher yields were obtained in the presence of [Hebim]BF4 in comparison with other imidazolium ionic liquids because of the good solubility of the aromatic alcohols and aromatic carboxylic acids in [Hebim]BF4. The product could be separated conveniently from the reaction system, and the ionic liquid could be easily reused after removal of water under vacuum. After 10 times reuse, the selectivity of the ester was still 100%.     

Ambient Ionic Liquids Used in the Reduction of Aldehydes and Ketones

The sodium borohydride reduction of aldehydes and ketones to corresponding alcohols has been accomplished via the use of ionic liquids. The alcohols are easily obtained with excellent yields and the ionic liquid BMImBF4 could be reused.     

Immobilization of HX：[Hmim]X as Halogenating Agent, Recyclable Catalyst and Medium for Conversion of Alcohols to Alkyl Halides

HX is immobilized by reaction of halogen acid with methylimidazole, and the formed ionic liquid [Hmim]X was used as halogenating agent, catalyst as well as medium for conversion of alcohols to alkyl halides. Excellent yields were obtained. The halides produced could be easily separated from the reaction mixture via simple decantation, and the ionic liquid [Hmim]X could be regenerated conveniently by adding equivalent of halogen acids followed by removal of water.     

新型吡咯烷键合反相高效液相色谱固定相的制备与研究（英文）

正A new ionic liquid-based high-performance liquid chromatography stationary phase is reported.A derivative of N-methyl pyrrolidinium tetrafluoroborate was covalently immobilized on the surface of silica particles to prepare silica-based N-methyl pyrrolidinium tetrafluoroborate(SilprMP BF4)stationary phase.The obtained ionic liquid-modified silica was evaluated and confirmed by elemental analysis,infrared spectroscopy,and thermogravimetric analysis.A column was packed with the modified particles.The retention behavior of aromatic compounds,alkyl benzenes,and acidic and basic compounds on the SilprMP BF4 stationary phase was studied under reversed-phase liquid chromatography conditions.The effect of the eluent pH on the separation of the acidic and basic compounds was also studied.The new stationary phase involves multiple retention mechanisms,such as electrostatic,hydrophobic,ion-dipole,and anion-exchange interactions,which might lead to multipurpose separation media.     

An efficient method to synthesize TNAD by the nitration of 1,4,5,8- tetraazabicyclo-[4,4,0]-decane with N20s and acidic ionic liquids

An experimental study was carried out on the direct nitration of 1,4,5,8-tetraaza-bicyclo-[4,4,0]-decane to synthesize 1,4,5,8-tetranitro-1,4,5,8-tetraazabicyclo-[4,4,0]-decane(TNAD) with N2O5 catalyzed by acidic ionic liquids. Various ionic liquids, such as [HMim]X, [(CH2)4SO3HMim]X and [Capl]X(X = pTSO, NO3, HSO4), and various parameters such as equivalents of ionic liquid, molar ratio of N2O5 to the starting material, reaction time and temperature, and solvent were investigated. Ionic liquid [(CH2)4SO3HMim]HSO4 showed better catalytic activity. In the presence of 3% molar ratio of [(CH2)4SO3HMim]HSO4 ionic liquid to the staring material, the yield of 1,4,5,8-tetranitro-1,4,5,8-tetraazabicyclo-[4,4,0]-decane was improved by 6.2% compared to the system without ionic liquid.     

Synthesis of Tetrahydrofuran and Tetrahydropyran Derivatives Catalyzed by Tungstophosphoric Acid in Ionic Liquid

Synthesis of tetrahydrofuran and tetrahydropyran derivatives catalyzed by tungstophosphoric acid （H3PW12040） were conveniently performed with high yield from the corresponding unsaturated alcohols in ionic liquid. Sufuric acid （H2SO4）, trifluoromathanesulfonic acid （TfOH） and p-toluenesulfonic acid （TsOH） were also explored for preparing these products in ionic liquid. The catalysts and ionic liquid can be easily recovered and reused.     

Oxidation of alcohols to aldehydes and ketones using selenium ionic liquid

A new type of ionic liquid supported selenium reagents were synthesized and found to be an excellent catalyst in the oxidation of alcohols to aldehydes and ketones in the presence of 30%H₂O₂.The predictable solubility of ionic liquids allows an easy separation of the oxidation products from the reaction mixture.Furthermore,the oxidation reaction can be carried out using an ionic liquid as the solvent,and the ionic liquid-supported selenium reagents can be recycled and used for four times with a little decrease in catalytic performance.     

The alcoholysis of acetonitrile prompted by BrФrnsted acidic ionic liquid [HSO3-pmim]HSO4

BrФnsted acidic ionic liquids based on imidazolium cation were employed as a series of environmentally benign catalysts and mediums in the alcoholysis of acetonitrile to synthesize ester. The results showed that BrФnsted acidic ionic liquid [HSO3- pmim]HSO4 was an efficient catalyst and medium for the alcoholysis of acetonitrile which could be recycled easily without obvious decline in catalytic activity, the highest yield could reach 85%.     

The alcoholysis of acetonitrile prompted by Brфnsted acidic ionic liquid [HSO_3-pmim]HSO_4

Br(?)nsted acidic ionic liquids based on imidazolium cation were employed as a series of environmentally benign catalysts and mediums in the alcoholysis of acetonitrile to synthesize ester.The results showed that Br(?)nsted acidic ionic liquid [HSO_3- pmim]HSO_4 was an efficient catalyst and medium for the alcoholysis of acetonitrile which could be recycled easily without obvious decline in catalytic activity,the highest yield could reach 85%.     

The effect of hydrogen bond acceptor properties of ionic liquids on their cellulose solubility

It is nowadays well-known that ionic liquids can dissolve cellulose. However, little systematic data has been published that shed light onto the influence of the ionic liquid structure on the dissolution of cellulose. We have conducted 1H NMR spectroscopy of ethanol in a large number of ionic liquids, and found an excellent correlation of the data obtained with the hydrogen acceptor properties (β-values). With this tool in hand, it is possible to distinguish between cellulose-dissolving and non-dissolving ionic liquids. A modulating effect of both, the anion of the non-dissolving ionic liquid and its cation was found in solubility studies with binary ionic liquid mixtures. The study was extended to other non-dissolving liquids, namely water and dimethylsulfoxide, and the effect of the cation was also investigated.     

A dicationic ionic liquid-modified phosphotungstate hybrid catalyst for the heterogeneous oxidation of alcohols with H2O2

An ionic hybrid catalyst 1,1’-(butane-1,4-diyl)-bis(3-methylimidazolium) phosphotungstate(abbreviated [Dmim] 1.5 PW) has been prepared by anion-exchange of the divalent ionic liquid(IL) 1,1’-(butane-1,4-diyl)-bis(3-methylimidazolium) di(bromide) with the Keggin phosphotungstic acid H 3 PW 12 O 40,and characterized by IR,1 H NMR,13 C NMR,ESI-MS,TG,SEM,XRD,BET surface area measurements,elemental analysis,and melting point.The hybrid material was evaluated as a catalyst for the oxidation of alcohols with aqueous hydrogen peroxide under various conditions.The catalytic performance of [Dmim] 1.5 PW was also compared with related catalysts bearing other cations or anions.The new hybrid [Dmim] 1.5 PW proved to be an efficient liquid-solid heterogeneous catalyst for H2O2-based oxidation of alcohols,with the advantages of high conversion and selectivity,easy recovery,and quite good reusability.     

Novel BrФnsted Acidic Ionic Liquid Based on a Cyclic Guanidinium Cation： a Green, Efficient, and Recyclable Dual Slovent-catalyst System for Fisher Esterification

A novel Brфnsted acidic ionic liquid(IL)based on the cyclic guanidinium cation has been synthesized.This IL,as a strong Brфnsted acid catalyst or solvent,shows high catalytic activity and biphsaic behavor in the esterifications of carboxylic acids and alcohols.The produced esters as a separate phase can be conveniently decanted out from the IL and the IL is recyclable without any loss of catalytic activity.     

Supported ionic liquid phase-boosted highly active and durable electrocatalysts towards hydrogen evolution reaction in acidic electrolyte

Platinum is generally known as the most effective electrocatalyst for hydrogen evolution reaction because it can greatly lower the overpotential and accelerate the reaction kinetics,while its commercial potential always suffers from scarcity,high cost,low utilization,and poor durability particularly in acidic electrolytes.We herein demonstrate a facile method to improve the hydrogen evolution performance of Pt-based electrocatalysts by simply decorating the-state-of-the-art and commercially available Pt/C with hydrophobic protic([DBU][NTf2])or aprotic([BMIm][NTf2])ionic liquid.The current densities of[BMIm]@Pt/C and[DBU-H]@Pt/C with 10% ionic liquid at an overpotential of 40 mV are 2.81 and 4.15 times,respectively,higher than that of the pristine Pt/C.More importantly,ionic liquid-decoration significantly improves the long-term stability of Pt nanoparticles.After 8 h of chronoamperometric measurements,[DBU-H]@Pt/C and[BMIm]@Pt/C can still retain 83.7% and 78.3% of their original activity,respectively,which is much higher than that of the pristine Pt/C(24.4%).The improved performance of Pt/C decorated with ionic liquid is considered to arise from the improved proton conductivity(particularly for protic ionic liquid)and hydrophobic microenvironment created by the supported ionic liquid phase.The presence of ionic liquid layer not only de-coordinates H+from hydronium ions nearby the Pt nanoparticles,but it also protects Pt nanoparticles from dissolution in the acidic media.     

室温离子液体BMIGaCl4热力学性质研究

An ionic liquid （IL） BMIGaCh was prepared by directly mixing GaCl3 and 1-methyl-3-butylimidazolium chloride with molar ratio of 1/1 under argon atmosphere. The densities and surface tensions of this pure ionic liquid were determined in the temperature range of 268.15 to （338.15±0.1） K. A new theoretical model of ionic liquids, an interstice model, was applied to calculate the thermal expansion coefficient of IL BMIGaCh, a, and the magnitude order of its value calculated by the theory was the same as experimental one. Both Raman scattering and ab initio calculations indicate that GaCl4^- is the only species containing Ga in the ionic liquid BMIGaCl4.     

Immobilization of Pd（Ⅱ）Catalysts for Cyclopropanation in Ionic Liquid

Cyclopropanation of styrene with ethyl diazoacetate catalyzed by Pd(Ⅱ） in ionic liquid [omim][BF4] was investigated.Palladium catalysts can be effectively immobilized in ionic liquid.The catalysts PdCl2 and cyclopalladated complex 2 contained in ionic liquid could be recycled for 6 and 7 times,respectively,without losing the efficiency.     

Selectivity of guanidinium ionic liquid for capillary gas chromatography

<正>A guanidinium ionic liquid,N,N,N',N'-tetrahexyl-N",N"-dimethylguanidinium bis(trifluoromethane)sulfonylimide(THDMGNTf_2), was synthesized and used as stationary phase for capillary gas chromatography.In comparison with imidazolium ionic liquid stationary phase,the present new stationary phase exhibits quite different selectivity and behaves more like a low polar stationary phase.The guanidinium ionic liquid of THDMG-NTf_2 exhibited better separation of Grab test mixture than imidazolium ionic liquid of 1-octyl-3-butylimidazolium bis(trifluoromethane)sulfonylimide(OBIM-NTf_2).Solvation parameter model was also used to evaluate the selectivity of THDMG-NTf_2.Additionally,essential oil of Magnolia biondii Pamp was analyzed to further evaluate the selectivity of THDMG-NTf_2 for a sample of complicated components.Satisfactory separation of the essential oil was achieved on a THDMG-NTf_2 column(10 m) while using a commercial column(30 m) as reference.The present study shows that the guanidinium ionic liquid possesses novel chromatographic selectivity and has great potential for wide applications.