Pyridinium ionic liquids（ILs, 1-ethyl acetate pyridinium hexfluorophosphate [EAPy][PF6] and 1-ethyl acetate-3-methyl pyridinium hexfluorophosphate [EAMPy][PF6]）, were synthesized by a two-step process involving intr...Pyridinium ionic liquids（ILs, 1-ethyl acetate pyridinium hexfluorophosphate [EAPy][PF6] and 1-ethyl acetate-3-methyl pyridinium hexfluorophosphate [EAMPy][PF6]）, were synthesized by a two-step process involving introduction of one ethyl acetate group and anion metathesis. Colorless single crystals of the two ILs were initially obtained using the solvent-evaporation method in mixed solvents. Single-crystal X-ray diffraction was used to deter- mine the crystal structures. [EAPy][PF6] crystallizes in the monoclinic space group C2/c with a-2.2748（16） nm, b=0.6204（4） nm, c=1.8552（12） nm and Z-8, whereas [EAMPy][PF6] crystallizes in the orthorhombic space group P212121 with a=0.7126（17） nm, b=1.2792（3） nm, c=1.5327（3） nm and Z-4. The structure of [EAPy][PF6] contains double zigzag chains formed by alternately pairing large organic cations with the octahedral anions of [P1F6]- or [P2F6] . The [P1F6] and [P2F6]- anions occupy respectively two distinct crystallographic sites in crystal packing models. The structure of [EAMPy][PF6] includes ladder-type chains constructed through pairing pyridinium cations with inorganic anions of [PF6]-. The [PF6]- anion in [EAMPy][PF6] shows a distorted octahedron structure and is sandwiched by ethyl acetate groups in crystallographic stacking. This study reveals the influence of chemical modification involving the methyl group（CH3） onto crystallographic structure of pyridinium ILs. Thermal analysis indicates that the difficult crystallization of the two 1Ls is related to the low void filling of ion pairs in crystal structure, leading to relatively low melting point and evident supercooling during the cooling process. Additionally, the experimental results indicate that the two ILs have electrochemical activity. The ethyl acetate group also allows downward shifting of electrochemical windows to less negative positions and the ionic conductivities of the two ILs follow an Arrhenius-type behavior.展开更多
The Knoevenagel condensation of carbonyl substrates with active methylene compounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in mo...The Knoevenagel condensation of carbonyl substrates with active methylene compounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in moderate yields.展开更多
A simple, green, and efficient method for the N-tert-butoxycarbonylation of amines by pyridinium 2,2,2- trifluoroacetate （[Py][OTf]） as an efficient and reusable catalyst is reported. In general, electron donating g...A simple, green, and efficient method for the N-tert-butoxycarbonylation of amines by pyridinium 2,2,2- trifluoroacetate （[Py][OTf]） as an efficient and reusable catalyst is reported. In general, electron donating groups on aryl group give rise to the higher yields than electron withdrawing groups. Clean reaction, short reaction times, high yields, reusability of catalyst, and easy preparation of it are some advantages of this work.展开更多
采用开环聚合法合成聚环氧氯丙烷中间体,再分别与N-甲基咪唑和吡啶反应合成了聚醚咪唑型离子液体(PIIL)与聚醚吡啶型离子液体(PPIL),并用红外与核磁进行结构表征。然后将合成的2种聚醚离子液体分别与酚醛树脂预聚物共混,制备了改性酚醛...采用开环聚合法合成聚环氧氯丙烷中间体,再分别与N-甲基咪唑和吡啶反应合成了聚醚咪唑型离子液体(PIIL)与聚醚吡啶型离子液体(PPIL),并用红外与核磁进行结构表征。然后将合成的2种聚醚离子液体分别与酚醛树脂预聚物共混,制备了改性酚醛树脂。研究了2种聚醚离子液体及其用量对改性酚醛树脂的拉伸剪切强度、冲击强度及游离醛释放量的影响。结果表明:聚醚型离子液体的添加明显改善了酚醛树脂的胶合性能和冲击强度,并降低了游离醛含量。聚醚咪唑离子液体改性酚醛树脂的性能优于聚醚吡啶型离子液体,其拉伸剪切强度从最初的1.15 MPa提高到6.94 MPa,冲击强度从最初的2.10 k J/m2提高到9.51 k J/m2,游离醛含量从最初的1.76%降低到0.14%。展开更多
离子液体型电解质在储能材料、电化学沉积等方面具有重要的研究意义。从酯基异构化的角度出发,设计合成了互为异构体的含酯基吡啶类离子液体,丁酸甲酯基吡啶六氟磷酸盐[n-C_4MePy][PF_6](记IL1)和异丙酸乙酯基吡啶六氟磷酸盐[i-C_3EAPy]...离子液体型电解质在储能材料、电化学沉积等方面具有重要的研究意义。从酯基异构化的角度出发,设计合成了互为异构体的含酯基吡啶类离子液体,丁酸甲酯基吡啶六氟磷酸盐[n-C_4MePy][PF_6](记IL1)和异丙酸乙酯基吡啶六氟磷酸盐[i-C_3EAPy][PF_6](记IL2)。对离子液体(记IL)-有机溶剂体系的电导性能进行研究,在0.0005~0.01 mol·L^(-1)浓度范围内,酯基异构化对二元体系的电导率影响相对较大。与IL2-有机溶剂体系相比,IL1-CH_3OH的电导率约为IL2-CH_3OH的2倍,而IL1-CH_3CN和IL1-(CH_3)_2NOH的电导率相对较小。同时在相同条件下,其不同溶剂体系的电导率为κ_(甲醇)>κ_(乙腈)>κ_(N,N二甲基甲酰胺),这可能与溶剂的介电常数大小有关。进一步研究表明,离子液体异构体(IL)-有机溶剂体系的导电行为均符合阿伦尼乌斯行为,在N,N-二甲基甲酰胺溶剂体系中,离子液体的酯基异构使得体系的电导活化能变化较为显著。与IL1-(CH_3)_2NOH相比,IL2-(CH_3)_2NOH的电导活化能减小了8.454 k J·mol^(-1),这可能是由于IL2与溶剂分子上的基团相互吸引力增强,导致了其体系活化能减小。最后对离子液体异构体的热稳定性分析表明,与IL1的分解温度487.48℃相比,酯基异构化使IL2的热分解温度降低了301.77℃。展开更多
基金Supported by the Natural Science Foundation of Shaanxi Province, China（No.2013JQ6010） and the Special Research Plan of Shaanxi Provincial Department of Education for Young Talents, China（No. 12JK0457）.
文摘Pyridinium ionic liquids（ILs, 1-ethyl acetate pyridinium hexfluorophosphate [EAPy][PF6] and 1-ethyl acetate-3-methyl pyridinium hexfluorophosphate [EAMPy][PF6]）, were synthesized by a two-step process involving introduction of one ethyl acetate group and anion metathesis. Colorless single crystals of the two ILs were initially obtained using the solvent-evaporation method in mixed solvents. Single-crystal X-ray diffraction was used to deter- mine the crystal structures. [EAPy][PF6] crystallizes in the monoclinic space group C2/c with a-2.2748（16） nm, b=0.6204（4） nm, c=1.8552（12） nm and Z-8, whereas [EAMPy][PF6] crystallizes in the orthorhombic space group P212121 with a=0.7126（17） nm, b=1.2792（3） nm, c=1.5327（3） nm and Z-4. The structure of [EAPy][PF6] contains double zigzag chains formed by alternately pairing large organic cations with the octahedral anions of [P1F6]- or [P2F6] . The [P1F6] and [P2F6]- anions occupy respectively two distinct crystallographic sites in crystal packing models. The structure of [EAMPy][PF6] includes ladder-type chains constructed through pairing pyridinium cations with inorganic anions of [PF6]-. The [PF6]- anion in [EAMPy][PF6] shows a distorted octahedron structure and is sandwiched by ethyl acetate groups in crystallographic stacking. This study reveals the influence of chemical modification involving the methyl group（CH3） onto crystallographic structure of pyridinium ILs. Thermal analysis indicates that the difficult crystallization of the two 1Ls is related to the low void filling of ion pairs in crystal structure, leading to relatively low melting point and evident supercooling during the cooling process. Additionally, the experimental results indicate that the two ILs have electrochemical activity. The ethyl acetate group also allows downward shifting of electrochemical windows to less negative positions and the ionic conductivities of the two ILs follow an Arrhenius-type behavior.
基金The project sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministrypartly supported by the Natural Science Foundation of Guangdong Province(Grant No 97104).
文摘The Knoevenagel condensation of carbonyl substrates with active methylene compounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in moderate yields.
基金the Research Committee of Persian Gulf University and Guilan University for financial support
文摘A simple, green, and efficient method for the N-tert-butoxycarbonylation of amines by pyridinium 2,2,2- trifluoroacetate （[Py][OTf]） as an efficient and reusable catalyst is reported. In general, electron donating groups on aryl group give rise to the higher yields than electron withdrawing groups. Clean reaction, short reaction times, high yields, reusability of catalyst, and easy preparation of it are some advantages of this work.
文摘采用开环聚合法合成聚环氧氯丙烷中间体,再分别与N-甲基咪唑和吡啶反应合成了聚醚咪唑型离子液体(PIIL)与聚醚吡啶型离子液体(PPIL),并用红外与核磁进行结构表征。然后将合成的2种聚醚离子液体分别与酚醛树脂预聚物共混,制备了改性酚醛树脂。研究了2种聚醚离子液体及其用量对改性酚醛树脂的拉伸剪切强度、冲击强度及游离醛释放量的影响。结果表明:聚醚型离子液体的添加明显改善了酚醛树脂的胶合性能和冲击强度,并降低了游离醛含量。聚醚咪唑离子液体改性酚醛树脂的性能优于聚醚吡啶型离子液体,其拉伸剪切强度从最初的1.15 MPa提高到6.94 MPa,冲击强度从最初的2.10 k J/m2提高到9.51 k J/m2,游离醛含量从最初的1.76%降低到0.14%。
文摘离子液体型电解质在储能材料、电化学沉积等方面具有重要的研究意义。从酯基异构化的角度出发,设计合成了互为异构体的含酯基吡啶类离子液体,丁酸甲酯基吡啶六氟磷酸盐[n-C_4MePy][PF_6](记IL1)和异丙酸乙酯基吡啶六氟磷酸盐[i-C_3EAPy][PF_6](记IL2)。对离子液体(记IL)-有机溶剂体系的电导性能进行研究,在0.0005~0.01 mol·L^(-1)浓度范围内,酯基异构化对二元体系的电导率影响相对较大。与IL2-有机溶剂体系相比,IL1-CH_3OH的电导率约为IL2-CH_3OH的2倍,而IL1-CH_3CN和IL1-(CH_3)_2NOH的电导率相对较小。同时在相同条件下,其不同溶剂体系的电导率为κ_(甲醇)>κ_(乙腈)>κ_(N,N二甲基甲酰胺),这可能与溶剂的介电常数大小有关。进一步研究表明,离子液体异构体(IL)-有机溶剂体系的导电行为均符合阿伦尼乌斯行为,在N,N-二甲基甲酰胺溶剂体系中,离子液体的酯基异构使得体系的电导活化能变化较为显著。与IL1-(CH_3)_2NOH相比,IL2-(CH_3)_2NOH的电导活化能减小了8.454 k J·mol^(-1),这可能是由于IL2与溶剂分子上的基团相互吸引力增强,导致了其体系活化能减小。最后对离子液体异构体的热稳定性分析表明,与IL1的分解温度487.48℃相比,酯基异构化使IL2的热分解温度降低了301.77℃。
