2,5-Dicyanofuran(DCF)is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile,which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate(HDI).In this ...2,5-Dicyanofuran(DCF)is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile,which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate(HDI).In this study,one-pot,green and safe synthesis of DCF from 2,5-diformylfuran(DFF)and hydroxylamine ionic liquid salts was proposed.Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source.Ionic liquid exhibited three-fold function of cosolvent,catalysis and phase separation.The conversion of DFF and yield of DCF reached 100%under the following optimum reaction conditions:temperature of 120℃ for 70 min,volume ratio of paraxylene:[HSO_(3)-b-Py]HSO4 of 2:1,and molar ratio of DFF:(NH_(2)OH)_(2)[HSO_(3)-b-Py]HSO4 of 1:1.5.The reaction mechanism for the synthesis of DCF was proposed,and the kinetic model was established.The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime(DFFD)was 1.06 and 0.16,and the reaction activation energy was 64.07 kJ·mol^(-1) and 59.37 kJ·mol^(-1) respectively.After the reaction,the ionic liquid was easy to separate,recover and recycle.展开更多
Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a hi...Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.展开更多
Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Thei...Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.展开更多
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. S...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.展开更多
Promoted catalytic reaction between methanol and CO2 for dimethyl carbonate (DMC) synthesis is conducted over K2CO3/CH3I catalyst in the presence of ionic liquid under microwave irradiation. The effect of ionic liqu...Promoted catalytic reaction between methanol and CO2 for dimethyl carbonate (DMC) synthesis is conducted over K2CO3/CH3I catalyst in the presence of ionic liquid under microwave irradiation. The effect of ionic liquids incorporated with microwave irradiation on the yield of DMC is investigated. DMC was found to form at lower temperature in a relative short time, which indicated an enhanced catalytic process by ionic liquid. Among the ionic liquids used, 1-butyl-3-methylimidazolium chloride is the most effective promoter. Density functional theory calculations indicate that CO2 bond lengths and angles changed due to the molecular interaction of ionic liquid and CO2, resulting in the activation of CO2 molecules and consequently the acceleration of reaction rate.展开更多
The synthesis of cinnamoyi thiourea derivatives from cinnamoyl isothiocyanate (CIT) with substituted aniline (RC6H4NH2) was investigated in the mostly used ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborat...The synthesis of cinnamoyi thiourea derivatives from cinnamoyl isothiocyanate (CIT) with substituted aniline (RC6H4NH2) was investigated in the mostly used ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [Bmim][BF4]. Significant enhancements in reactivity, yield and reaction rate were achieved. The products could be recovered by simple filtration. [Bmlm] [BF4] could be recycled simply by removing water under vacuum and reused at least 9 times without significant decrease in activity.展开更多
Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl- 3-methylimidazolium tetrafluoroborate (abbreviated as [crnmim] [BF4]) as catalyst was su...Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl- 3-methylimidazolium tetrafluoroborate (abbreviated as [crnmim] [BF4]) as catalyst was successfully performed. The yields of the target compounds were 80-92%, the purities were 96-98%. The catalyst could be recovered and reused for at least six times without significant loss in activity.展开更多
Multiester-appended imidazolium ionic liquids were synthesized in a quatemization reaction between the imidazole derivatives carrying single or double esters and ethyl chloroacetate or bromoethane. Multicarboxylic-app...Multiester-appended imidazolium ionic liquids were synthesized in a quatemization reaction between the imidazole derivatives carrying single or double esters and ethyl chloroacetate or bromoethane. Multicarboxylic-appended imidazolium ionic liquids were achieved from the hydrolysis of the corresponding ionic liquids. The influences of multifunctional groups on the transition temperatures and viscosity of these new ionic liquids were investigated.展开更多
Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is ...Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is found that smooth and bluegreen PTh films can be obtained at a potential of ca. +1.75 V ( vs. Ag/AgCl ) or a current of ca. 1.5 mA cm-2 in the ionic liquid.展开更多
Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. ...Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of l-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.展开更多
Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). ...Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). Eco-friendly solvent free procedure, short reaction time, high yield of products and reusability of catalysts are important features of the synthesis. A comparative study on the efficiency of the two catalysts is reported. This work further demonstrates the alternate use of urea, instead of often used ammonium acetate, as source of nitrogen.展开更多
Promoted and mediated by an ionic liquid-[bmim][BF4], fused pyrans or arylbis(4-hydroxy-6-methyl-2-oxo-2H-pyran-3- yl)methanes were efficiently and selectively prepared from the reaction of aldehyde and 4-hydroxy-6-...Promoted and mediated by an ionic liquid-[bmim][BF4], fused pyrans or arylbis(4-hydroxy-6-methyl-2-oxo-2H-pyran-3- yl)methanes were efficiently and selectively prepared from the reaction of aldehyde and 4-hydroxy-6-methyl-2-oxo-pyran with or without acetic anhydride. By using these novel procedures, pyrimidine nucleoside-fused pyran and arylbis(pyranon-3-yl)methane hybrids with potential biological activities were constructed.展开更多
Synthesis of 3-naphthylcyclohexene by the Heck reactions of bromonaphthalene and naphthyl triflates with cyclohexene catalyzed by palladiun and nickel complex (promoted by ultrasonic and microwave in ionic liquid of ...Synthesis of 3-naphthylcyclohexene by the Heck reactions of bromonaphthalene and naphthyl triflates with cyclohexene catalyzed by palladiun and nickel complex (promoted by ultrasonic and microwave in ionic liquid of [bmim][BF4I) were performed with high yield and good regioselectivity. This method has advantages of environmentally benign, generality, simplicity and potential for recycling of ionic liquid and catalyat.展开更多
Quinoline derivatives were efficiently prepared through acid-catalyzed Friedlander reaction in ionic liquid ([bmim][BF4]). It is shown that the proposed method is operationally simple and environmentally benign in tha...Quinoline derivatives were efficiently prepared through acid-catalyzed Friedlander reaction in ionic liquid ([bmim][BF4]). It is shown that the proposed method is operationally simple and environmentally benign in that the reaction media and the catalyst can be recovered and be reused effectively for at least four times.展开更多
A bifunctional heterogeneous catalyst was designed and synthesized,denoted DMEDA/IL–NH2-MIL-101.The structure and physical-chemical characterization of DMEDA/IL–NH2-MIL-101 and its precursors were characterized by S...A bifunctional heterogeneous catalyst was designed and synthesized,denoted DMEDA/IL–NH2-MIL-101.The structure and physical-chemical characterization of DMEDA/IL–NH2-MIL-101 and its precursors were characterized by SEM,N2 adsorption-desorption,XPS,FT-IR,PXRD,elemental analysis,and TGA techniques.The date showed that the two catalytic components of N,N-dimethylethylenediamine(DMEDA)and 1-butyl-3-methylimidazolium bromide(BmimBr)were chemically immobilized in NH2-MIL-101 nanocages.The amine of DMEDA was grafted onto carrier NH2-MIL-101 by N–Cr coordinate covalent bonds and the ionic liquid of BmimBr(IL(Br-))was anchored in the NH2-MIL-101 nanocages by'ship-in-a-bottle'method,in which the amidogen of NH2-MIL-101 condensed with N,N-carbonyldiimidazole(CDI)firstly,and then alkylated with 1-bromo butane.This novel heterogeneous catalyst with two different active sites can efficiently catalyze the synthesis of N-aryl oxazolidin-2-ones from carbon dioxide(CO2),epoxides,and anilines in one-pot under mild solvent-free conditions.It not only showed good stability and recoverability after five cycles but also exhibited shape selectivity for the substrate due to the synergic catalysis of amine,ionic liquid,and NH2-MIL-101.This novel bifunctional material is a promising solid catalyst for the green synthesis of N-aryl oxazolidin-2-ones.展开更多
The condensation reactions of aromatic aldehydes, 5,5-dimethyl-1,3-cyclohexanedione and ammonium acetate efficiently promoted by several ionic liquids under solvent-free condition to afford corresponding 3, 3, 6, 6-te...The condensation reactions of aromatic aldehydes, 5,5-dimethyl-1,3-cyclohexanedione and ammonium acetate efficiently promoted by several ionic liquids under solvent-free condition to afford corresponding 3, 3, 6, 6-tetramethyl-1, 8-dioxo-9-aryl-1, 2, 3, 4, 5, 6, 7, 8, 9, 10-decahydroacridines in good yields.展开更多
Switchable ionic compounds have wide applications in chemical processes.A switchable ionic compound based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU),CH_3OH and CO_2 was synthesized and characterized.DBU/CH_3OH/CO_2 ...Switchable ionic compounds have wide applications in chemical processes.A switchable ionic compound based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU),CH_3OH and CO_2 was synthesized and characterized.DBU/CH_3OH/CO_2 ionic compound was prepared in the presence of excess methanol,and then the excess methanol was removed by reduced pressure distillation in CO_2 atmosphere.The product yield(100%) reached the theoretical maximum for the first time.Its structure was identified by NMR,FT-IR,and XRD.The crystal product shows 8strong peaks in XRD at 2θ values of 16.0547°,16.4308°,16.7651°,18.8714°,19.2140°,21.9471°,22.0780°,and25.5661°.Its decomposition onset temperature(53 ℃) was affirmed by TGA,which is lower than its melting point.And its ionic switch point was measured by conductivity.展开更多
To obtain new functional aromatic polymer materiul. 3,3'-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthen...To obtain new functional aromatic polymer materiul. 3,3'-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid ([bmim]CI/FeCl3) at mild reaction condition. Pure 3,3'-biacenaphthene was obtained hy recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, SHNMR arid FTIR analysis. The influence of various reaction conditions on the yield of 3,3'-biacenaphthene were studied by GC analysis. The result shows that the optimun synthesis conditions of the coupling reaction are, as following: the molar ratio of FeCl3 to [BmimlCl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4. the reaction temperamre being 20 ℃ the reaction time being 4h and the solvent of the reaction system being PhNO2 Under those conditions, the yield of the 3.3'-biacenaphthene will be 48.71% and selectivity, of that will be 78.56 %. Farther more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.展开更多
Electrogenerated N-heterocyclic carbene (NHC), obtained by cathodic reduction of Bmim-BF4, behaves as organocatalyst and base in the Staudinger synthesis from an acyl chloride and a deactivated imine in ionic liquid t...Electrogenerated N-heterocyclic carbene (NHC), obtained by cathodic reduction of Bmim-BF4, behaves as organocatalyst and base in the Staudinger synthesis from an acyl chloride and a deactivated imine in ionic liquid to yield ?-lactams. The effect of many parameters (temperature, amount of electricity, substituents, presence of an external base) has been evaluated and a tentative mechanism for the Staudinger synthesis in a very polar medium like the ionic liquid reported. The yields of isolated ?-lactams are good, starting from non-electrophilic imines, and predominantly trans lactams are obtained with a good diastereomeric ratio.展开更多
基金support from the National Natural Science Foundation of China(Nos.U20A20152,21236001 and 21878069).
文摘2,5-Dicyanofuran(DCF)is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile,which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate(HDI).In this study,one-pot,green and safe synthesis of DCF from 2,5-diformylfuran(DFF)and hydroxylamine ionic liquid salts was proposed.Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source.Ionic liquid exhibited three-fold function of cosolvent,catalysis and phase separation.The conversion of DFF and yield of DCF reached 100%under the following optimum reaction conditions:temperature of 120℃ for 70 min,volume ratio of paraxylene:[HSO_(3)-b-Py]HSO4 of 2:1,and molar ratio of DFF:(NH_(2)OH)_(2)[HSO_(3)-b-Py]HSO4 of 1:1.5.The reaction mechanism for the synthesis of DCF was proposed,and the kinetic model was established.The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime(DFFD)was 1.06 and 0.16,and the reaction activation energy was 64.07 kJ·mol^(-1) and 59.37 kJ·mol^(-1) respectively.After the reaction,the ionic liquid was easy to separate,recover and recycle.
基金support from the National Natural Science Foundation of China(No.21808048 and U1704251)Training Plan for University's Young Backbone Teachers of Henan Province(2021GGJS121)+5 种基金Program for Science&Technology Innovation Talents in Universities of Henan Province(23HASTIT014)Postgraduate Education Reform and Quality Improvement Project of Henan Province(YJS2022KC22)Project funded by China Postdoctoral Science Foundation(No.2018M632782)Project funded by Postdoctoral Research Grant in Henan Province(No.001802030)Key Project of Science and Technology Program of Henan Province(No.222102230109,212102310330 and 182102210050)the Science Research Start-up Fund of Henan Institute of Science and Technology(No.2015031).
文摘Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.
基金the‘973’Program of the Chinese Ministry of Science and Technology(G-2000048002).
文摘Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.
文摘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.
基金supported by the Natinal Science Foundation (NSFC 21006130)the Key Research Programs of Chongqing Science and Technology Commission Foundation (CSTC,2009AB4012)
文摘Promoted catalytic reaction between methanol and CO2 for dimethyl carbonate (DMC) synthesis is conducted over K2CO3/CH3I catalyst in the presence of ionic liquid under microwave irradiation. The effect of ionic liquids incorporated with microwave irradiation on the yield of DMC is investigated. DMC was found to form at lower temperature in a relative short time, which indicated an enhanced catalytic process by ionic liquid. Among the ionic liquids used, 1-butyl-3-methylimidazolium chloride is the most effective promoter. Density functional theory calculations indicate that CO2 bond lengths and angles changed due to the molecular interaction of ionic liquid and CO2, resulting in the activation of CO2 molecules and consequently the acceleration of reaction rate.
文摘The synthesis of cinnamoyi thiourea derivatives from cinnamoyl isothiocyanate (CIT) with substituted aniline (RC6H4NH2) was investigated in the mostly used ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [Bmim][BF4]. Significant enhancements in reactivity, yield and reaction rate were achieved. The products could be recovered by simple filtration. [Bmlm] [BF4] could be recycled simply by removing water under vacuum and reused at least 9 times without significant decrease in activity.
基金the Key Project of Shanghai Educational Committee(No.06ZZ82)
文摘Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl- 3-methylimidazolium tetrafluoroborate (abbreviated as [crnmim] [BF4]) as catalyst was successfully performed. The yields of the target compounds were 80-92%, the purities were 96-98%. The catalyst could be recovered and reused for at least six times without significant loss in activity.
基金The National Natural Science Foundation of China(Grant No.20206010)Guangdong Province Natural Science Foundation(Grant No.031419,203C33503)are gratefully acknowledged for financial support for this project.
文摘Multiester-appended imidazolium ionic liquids were synthesized in a quatemization reaction between the imidazole derivatives carrying single or double esters and ethyl chloroacetate or bromoethane. Multicarboxylic-appended imidazolium ionic liquids were achieved from the hydrolysis of the corresponding ionic liquids. The influences of multifunctional groups on the transition temperatures and viscosity of these new ionic liquids were investigated.
基金support from the National Natural Science Foundation of China(20004010)
文摘Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is found that smooth and bluegreen PTh films can be obtained at a potential of ca. +1.75 V ( vs. Ag/AgCl ) or a current of ca. 1.5 mA cm-2 in the ionic liquid.
基金the grant from the National Natural Science Foundation of China (Key Program 20533010).
文摘Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of l-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.
文摘Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). Eco-friendly solvent free procedure, short reaction time, high yield of products and reusability of catalysts are important features of the synthesis. A comparative study on the efficiency of the two catalysts is reported. This work further demonstrates the alternate use of urea, instead of often used ammonium acetate, as source of nitrogen.
基金the National Natural Science Foundation of China(No.20772025)the Program for Science & Technology Innovation Talents in Universities of Henan Province(No.2008HASTIT006)the Natural Science Foundation of Department of Education of Henan Province(No.2008A150013).
文摘Promoted and mediated by an ionic liquid-[bmim][BF4], fused pyrans or arylbis(4-hydroxy-6-methyl-2-oxo-2H-pyran-3- yl)methanes were efficiently and selectively prepared from the reaction of aldehyde and 4-hydroxy-6-methyl-2-oxo-pyran with or without acetic anhydride. By using these novel procedures, pyrimidine nucleoside-fused pyran and arylbis(pyranon-3-yl)methane hybrids with potential biological activities were constructed.
文摘Synthesis of 3-naphthylcyclohexene by the Heck reactions of bromonaphthalene and naphthyl triflates with cyclohexene catalyzed by palladiun and nickel complex (promoted by ultrasonic and microwave in ionic liquid of [bmim][BF4I) were performed with high yield and good regioselectivity. This method has advantages of environmentally benign, generality, simplicity and potential for recycling of ionic liquid and catalyat.
文摘Quinoline derivatives were efficiently prepared through acid-catalyzed Friedlander reaction in ionic liquid ([bmim][BF4]). It is shown that the proposed method is operationally simple and environmentally benign in that the reaction media and the catalyst can be recovered and be reused effectively for at least four times.
基金Support of this work by the National Natural Science Foundation of China(21573016)is gratefully acknowledged.
文摘A bifunctional heterogeneous catalyst was designed and synthesized,denoted DMEDA/IL–NH2-MIL-101.The structure and physical-chemical characterization of DMEDA/IL–NH2-MIL-101 and its precursors were characterized by SEM,N2 adsorption-desorption,XPS,FT-IR,PXRD,elemental analysis,and TGA techniques.The date showed that the two catalytic components of N,N-dimethylethylenediamine(DMEDA)and 1-butyl-3-methylimidazolium bromide(BmimBr)were chemically immobilized in NH2-MIL-101 nanocages.The amine of DMEDA was grafted onto carrier NH2-MIL-101 by N–Cr coordinate covalent bonds and the ionic liquid of BmimBr(IL(Br-))was anchored in the NH2-MIL-101 nanocages by'ship-in-a-bottle'method,in which the amidogen of NH2-MIL-101 condensed with N,N-carbonyldiimidazole(CDI)firstly,and then alkylated with 1-bromo butane.This novel heterogeneous catalyst with two different active sites can efficiently catalyze the synthesis of N-aryl oxazolidin-2-ones from carbon dioxide(CO2),epoxides,and anilines in one-pot under mild solvent-free conditions.It not only showed good stability and recoverability after five cycles but also exhibited shape selectivity for the substrate due to the synergic catalysis of amine,ionic liquid,and NH2-MIL-101.This novel bifunctional material is a promising solid catalyst for the green synthesis of N-aryl oxazolidin-2-ones.
基金Sponsored by the National Nature Science Foundation of China (20272018) the Scientific ResearchFoundation for the Returned Overseas Chinese Scholars+1 种基金 State Education Ministry of China and the Nature ScienceFoundation of Guangdong Province (974021 021166)
基金the Guangdong Natural Science Foundation (No. 04010458).
文摘The condensation reactions of aromatic aldehydes, 5,5-dimethyl-1,3-cyclohexanedione and ammonium acetate efficiently promoted by several ionic liquids under solvent-free condition to afford corresponding 3, 3, 6, 6-tetramethyl-1, 8-dioxo-9-aryl-1, 2, 3, 4, 5, 6, 7, 8, 9, 10-decahydroacridines in good yields.
基金Supported by the Doctoral Fund of Ministry of Education of China(20130181130006)the Key Program of National Natural Science Foundation of China(21336008)the National Natural Science Foundation of China(21476150)
文摘Switchable ionic compounds have wide applications in chemical processes.A switchable ionic compound based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU),CH_3OH and CO_2 was synthesized and characterized.DBU/CH_3OH/CO_2 ionic compound was prepared in the presence of excess methanol,and then the excess methanol was removed by reduced pressure distillation in CO_2 atmosphere.The product yield(100%) reached the theoretical maximum for the first time.Its structure was identified by NMR,FT-IR,and XRD.The crystal product shows 8strong peaks in XRD at 2θ values of 16.0547°,16.4308°,16.7651°,18.8714°,19.2140°,21.9471°,22.0780°,and25.5661°.Its decomposition onset temperature(53 ℃) was affirmed by TGA,which is lower than its melting point.And its ionic switch point was measured by conductivity.
基金National Natural Science Foundation of China (No. 20207003)
文摘To obtain new functional aromatic polymer materiul. 3,3'-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid ([bmim]CI/FeCl3) at mild reaction condition. Pure 3,3'-biacenaphthene was obtained hy recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, SHNMR arid FTIR analysis. The influence of various reaction conditions on the yield of 3,3'-biacenaphthene were studied by GC analysis. The result shows that the optimun synthesis conditions of the coupling reaction are, as following: the molar ratio of FeCl3 to [BmimlCl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4. the reaction temperamre being 20 ℃ the reaction time being 4h and the solvent of the reaction system being PhNO2 Under those conditions, the yield of the 3.3'-biacenaphthene will be 48.71% and selectivity, of that will be 78.56 %. Farther more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.
文摘Electrogenerated N-heterocyclic carbene (NHC), obtained by cathodic reduction of Bmim-BF4, behaves as organocatalyst and base in the Staudinger synthesis from an acyl chloride and a deactivated imine in ionic liquid to yield ?-lactams. The effect of many parameters (temperature, amount of electricity, substituents, presence of an external base) has been evaluated and a tentative mechanism for the Staudinger synthesis in a very polar medium like the ionic liquid reported. The yields of isolated ?-lactams are good, starting from non-electrophilic imines, and predominantly trans lactams are obtained with a good diastereomeric ratio.