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%.     

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%.     

Doebner condensation in ionic liquids [Bmim]BF_4 and [Bpy]BF_4 to synthesize α,β-unsaturated carboxylic acid

Ionic liquids[Bmim]BF_4 and[Bpy]BF_4 were employed as environmentally benign media in Doebner condensation to synthesizeαβ-unsaturated carboxylic acid.The good results showed that[Bmim]BF_4 and[Bpy]BF_4 were efficient media for Doebner condensation,which could be recycled easily.The highest yields could reach 93%and 90%in[Bmim]BF_4 and[Bpy]BF_4,respectively.     

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.     

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%.     

Structural analysis of [Bmim]2CuCl4 ionic liquids in the presence of water and ethanol by XAFS technique

The structure of [Bmim]2Cu Cl4 ionic liquids(Bmim: 1-butyl-3-methylimidazolium) with different ratios of H2 O and C2H5 OH was investigated using X-ray absorption fine structure(XAFS) technique. In this study, XAFS was employed to directly probe the conformational variations of copper ions in [Bmim]2Cu Cl4 with the addition of either water or ethanol. XAFS analysis confirmed that the structure of ionic liquids gradually transformed from tetrahedral to octahedral configuration with the increase in ratio of H2 O. Our results also showed that water molecules coordinated with the copper ions of [Bmim]2Cu Cl4, leading to the conformational change in ionic liquids. However, the XAFS spectra of [Bmim]2Cu Cl4/C2H5 OH indicated no coordination of anhydrous ethanol with the copper ions of [Bmim]2Cu Cl4. The structure of [Bmim]2Cu Cl4 ionic liquids is maintained as the tetrahedral configuration in presence of ethanol. Therefore, anhydrous ethanol causes little variation in the structure of ionic liquids and it is a good solvent for the dilution of ionic liquids.     

Cationic ring-opening polymerization of 3,3-bis（chloromethyl）oxacyclobutane in ionic liquids

Cationic ring-opening polymerization of 3,3-bis(chloromethyl)oxacyclobutane catalyzed by BF_3·OEt_2 was carried out in ionic liquids [bmim]BF_4 and [bmim]PF_6.The influences of BCMO concentration and molar ratio of BCMO/BF_3·OEt_2 on the molecular weights and yield of PBCMO were investigated.The polymerization in ionic liquids proceed to high conversions,although molecular weights are limited,similar to polymerization in organic solvent such as CH_2Cl_2.Follow a viewpoint of green chemistry, we feel ionic liquid [bmim]BF_4 is superior to [bmim]PF_6.Extracting [bmim]PF_6 from the product using organic solvent as extractant limits its advantage as a green reaction media.     

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.     

加热与超声辐照条件下4-(丁二酰亚胺基)-1-丁烷磺酸Brnsted酸催化剂催化吡喃并[4,3-b]吡喃衍生物合成(英文)

4-(Succinimido)-1-butane sulfonic acid was shown to be an efficient and reusable Brnsted acid catalyst for the synthesis of pyrano[4,3-b]pyran derivatives using thermal and ultrasonic conditions. The catalyst was prepared by mixing succinimide and 1,4-butanesultone, which is simpler and safer than the preparation of succinimide sulfonic acid. This method has the advantages of high yield, clean reaction, simple methodology, and short reaction time. The catalyst can be recycled without loss of activity.     

BrФnsted Acidic Ionic Liquids as Efficient Catalysts and Mediums for the Synthesis of Half-esters: Structure-catalytic Selectivity Relationship

BrФnsted acidic ionic liquids based on imidazolium cation were employed as efficient catalysts and mediums for the ring opening of phthalic anhydride to synthesize half-esters. Good yields, short reaction time and mild reaction condition were achieved. Lower acidity of ionic liquid resulted in higher catalytic selectivity in the synthesis of half-esters. The minimum-energy geometries of sulfonic acid-functionalized ionic liquids based on imidazolium cation revealed that their acidities and catalytic selectivity in the synthesis of half-esters were related to their structures.     

Brønsted酸性离子液体中电化学合成树枝状聚苯胺

BrФnsted acid ionic liquids were successfully applied to the electrochemical synthesis of polyaniline films on platinum electrode surfaces by using cyclic voltammetry. The scanning electron micrographs showed distinct changes in morphological structures. The films exhibited quite dense packing and good ordering of polymer dendrite as compared with those prepared using conventional hydrochloric acid, indicating that Bronsting acid ionic liquids might be promising alternatives to dual medium-dopants in the synthesis of conducting polymers.     

DABCO-based ionic liquids:Green and efficient catalysts with a dual catalytic role for aza-Michael addition

Four recoverable and reusable ionic liquids based on 1,4-diazobicyclo[2.2.2]octane(DABCO) have been synthesized to catalyze the aza-Michael addition of secondary amines to a,b-unsaturated compounds.Among the catalysts tested,[DABCO-PDO][OAc] was found to be most suitable for the reaction of a wide range of cyclic substrates without any solvent at room temperature,and afford the products in good to excellent yields within an appropriate amount of time.The proposed mechanism for the dual activation of the catalyst was supported by experimental results as well as the DFT calculation.In addition,the ionic liquids used can be regenerated and recycled several times without any loss of activity.     

Measurement and Correlation of the Ionic Conductivity of Ionic Liauid-Molecular Solvent Solutions

The ionic conductivity of the solutions formed from 1-n-butyl-3-methylimidazolium tetrafluoroborate （[Bmim][BF4]） or 1-n-butyl-3-methylimidazolium hexafluorophosphate （[Bmim][PF6]） and different molecular solvents （MSs） were measured at 298.15 K. The molar conductivity of the ionic liquids （ILs） increased dramatically with increasing concentration of the MSs. It was found that the molar conductivity of the IL in the solutions studied in this work could be well correlated by the molar conductivity of the neat ILs and the dielectric constant and molar volume of the MSs.     

Imidazolium ionic liquid-supported sulfonic acids: efficient and recyclable catalysts for esterification of benzoic acid

Several imidazolium ionic liquid（IL）-supported sulfonic acids with different anions,[C₃SO₃Hmim]HSO₄,[C₃SO₃Hmim]BF₄, [C₃SO₃ Hmim]PF₆,and[C₃SO₃Hmim]CF₃SO₃,were synthesized and applied as catalysts for esterification reaction of benzoic acid. The experimental results indicate that imidazolium IL-supported sulfonic acid containing anion of HSO₄^- shows the best catalytic activity.Only when less[C₃SO₃Hmim]HSO₄（0.3 equiv.） applied,was the product obtained with high yield of 97%.Furthermore, the produced esters could be separated by decantation,and the catalyst could be reused after the removal of water.     

离子液体存在下脂肪醛的环化三聚反应

Aliphatic aldehydes such as ethanal,propanal,n-butanal,isobutyraldehyde,n-valeraldehyde,isovaleraldehyde,n-hexanal and n-octanal were converted into the corresponding 2,4,6-trialkyl-1,3,5-trioxanes through cyclotrimer-ization in the presence of the ferric chloride based ionic liquids at room temperature without solvent in high selec-tivity.The effects of different ionic liquids,acidity of ionic liquids and temperature on cyclotrimerization were alsostudied.The results showed that the ferric chloride based ionic liquids(apparent molar fraction of FeCl_3(x(FeCl_3)=0.62))were a kind of efficient catalysts for the cyclotrimerization of aliphatic aldehyde which could be separatedconveniently from the reaction mixture and recycled without loss of catalytic activity.The conversion of isobu-tyraldehyde and the selectivity to 2,4,6-triisopropyl-1,3,5-trioxane were 91.1% and 99.8% respectively under opti-mum reaction condition(isobutyraldehyde 25.0 g,[Et_3NH]Cl/FeCl_3(x(FeCl_3)=0.62)1.0 g,25 ℃for 1 h).     

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.     

4-(Succinimido)-1-butane sulfonic acid as a Br?nsted acid catalyst for the synthesis of pyrano[4,3-b]pyran derivatives using thermal and ultrasonic irradiation

4-(Succinimido)-1-butane sulfonic acid was shown to be anefficient and reusable Br?nsted acid catalyst for the synthesis of pyrano[4,3-b]pyran derivatives using thermal and ultrasonic conditions. The c...     

无溶剂条件下离子液体催化香豆素衍生物的绿色合成(英文)

Brnsted acidic ionic liquids, namely 2-pyrrolidonium hydrogen sulfate, N-methyl-2-pyrrolidonium hydrogen sulfate, N-methyl-2-pyrrolidonium dihydrogen phosphate, (4-sulfobutyl)tris(4-sulfophenyl)phosphonium hydrogen sulfate, and triphenyl(propyl-3-sulfonyl)phosphonium toluenesulfonate, catalyzed efficient Pechmann condensation of phloroglucinol with β-keto ethyl/ methyl esters. 5,7-Dihydroxy-4-methylcoumarin and 5,7-dihydroxy-4-phenylcoumarin were prepared in good to excellent yields under mild, ambient, and solvent-free conditions. Pyrano[2,3-h] coumarins were then prepared by one-pot three-component reactions of 5,7-dihydroxy-4-subsituted coumarin, malononitrile, and aldehydes in the presence of catalytic amounts of Br nsted basic ionic liquids, namely 2-hydroxyethylammonium formate, 3-hydroxypropanaminium acetate, 1-butyl-3-methylimidazolium hydroxide, pyrrolidinium formate, and pyrrolidinium acetate, under thermal solvent-free conditions. The catalysts are environmentally benign and can be easily prepared, stored, and recovered without significant loss of activity.     

Dehydration of glucose into 5-hydroxymethylfurfural in SO_3H-functionalized ionic liquids

The continuous dehydration of D-glucose into 5-hydroxymethylfurfural（HMF） was carried out under mild conditions,using SO3H-functionalized acidic ionic liquids as catalysts and H2O-4-methyl-2-pentanone（MIBK） biphasic system as solvent.High glucose conversion of 97.4% with HMF yield of 75.1%was obtained at 120 8C for 360 min,also,small amounts of levulinic acid（LA） and formic acid were generated.Generally,the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction.The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs.This paper provided a new strategy for HMF production from glucose.     

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.