从氨基酸合成手性离子液体
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摘要
室温离子液体因其独特的物理化学性质,被认为是替代常用挥发性有机溶剂的绿色溶剂。近年来,离子液体的研究开始向功能化的方向发展,即对离子液体进行性能改进以达到特定的需求。将手性引入至离子液体中是离子液体功能化的一个重要方法,手性离子液体因其在手性识别、不对称合成和手性催化方面的应用而受到广泛关注。但是到目前为止,手性离子液体的合成大多数都是在阳离子上引入手性基团,在阴离子上引入手性基团的并不多见。
本文从天然氨基酸出发,通过酯化、磺酰化反应合成出三种全氟丁基磺酰氟修饰的手性阴离子:N-全氟丁基磺酰化丙基酸甲酯[I-Ala]、N-全氟丁基磺酰化亮基酸甲酯[I-Leu]和N-全氟丁基磺酰化缬基酸甲酯[I-Val],同时以N-甲基咪唑为原料合成出1-甲基-3-乙基咪唑盐[emim]OH,将手性阴离子与[emim]OH进行酸碱中和反应,合成出一系列以N-全氟丁基磺酰化氨基酸甲酯为阴离子,[emim]+为阳离子的新型手性离子液体[emim][I-Ala]和[emim][I-Val]。本文还对反应条件进行了研究,建立了一条合成此类新型手性离子液体的新方法。同时也对该手性离子液体的光学纯度测定进行了一些探索。
实验结果表明,在低温,不加任何缚酸剂和溶剂的情况下,氨基酸甲酯与全氟丁基磺酰氟的磺酰化反应能顺利进行,且因为反应体系只有两种化合物,在此条件下的后处理方法简单,使得产物的分离更加便利。由此合成得到的手性离子液体在室温下均为液体,为以后用于手性合成打下了基础。
Because of their unique physical and chemical properties, room temperature ionic liquids(RTILs) are now expected to be an alternative to conventional volatility solvents for organic reactions.Recently, design and synthesis of RTILs with controllable physical and chemical properties or even specific functions has been developed for specifically requirements. Combine chiral with ionic liquids is an important way of the function of ionic liquids. People focused on the synthesis of chiral ionic liquids(CILs) for their particularly potential applications to chiral discrimination, including asymmetric synthesis and chiral catalysis. But up to now,most of CILs are derived from chiral cations, only part of them derived from chiral anions.
In this paper, a series of chiral ionic liquids([emim][I-Ala],[emim][I-Val]) composed of 1-ethyl-3-methylimidazolium cation([emim]) and chiral anions derived from natural amino acids modified with perfluorobutylsulfonyl groups were synthesized through the acid-base reaction.Three chiral anions: N-perfluoroethyl- sufonyl alanine ethyl ester([I-Ala]) and N-perfluoroethylsufonyl valine ethyl ester([I-Val]) and N-perfluoroethylsufonyl leucine ethyl ester([I-Leu]) were synthesized from amino acids through esterification and sulfonylation. A new method was builded to synthesize these CILs through improving the condition of reactions. The optical activity of CILs were also detected.
The results of experiment showed amino acid methyl esters could react easily with perfluorobutylsulfonyl fluoride without any solvents and catalyzer in low temperature. Product could be separated easily from reaction system using a simple method as there were only two reagent in the reaction system. All of the CILs synthesized in this paper could be used in chiral synthesis as they had low melting point and optical activity.
本文从天然氨基酸出发,通过酯化、磺酰化反应合成出三种全氟丁基磺酰氟修饰的手性阴离子:N-全氟丁基磺酰化丙基酸甲酯[I-Ala]、N-全氟丁基磺酰化亮基酸甲酯[I-Leu]和N-全氟丁基磺酰化缬基酸甲酯[I-Val],同时以N-甲基咪唑为原料合成出1-甲基-3-乙基咪唑盐[emim]OH,将手性阴离子与[emim]OH进行酸碱中和反应,合成出一系列以N-全氟丁基磺酰化氨基酸甲酯为阴离子,[emim]+为阳离子的新型手性离子液体[emim][I-Ala]和[emim][I-Val]。本文还对反应条件进行了研究,建立了一条合成此类新型手性离子液体的新方法。同时也对该手性离子液体的光学纯度测定进行了一些探索。
实验结果表明,在低温,不加任何缚酸剂和溶剂的情况下,氨基酸甲酯与全氟丁基磺酰氟的磺酰化反应能顺利进行,且因为反应体系只有两种化合物,在此条件下的后处理方法简单,使得产物的分离更加便利。由此合成得到的手性离子液体在室温下均为液体,为以后用于手性合成打下了基础。
Because of their unique physical and chemical properties, room temperature ionic liquids(RTILs) are now expected to be an alternative to conventional volatility solvents for organic reactions.Recently, design and synthesis of RTILs with controllable physical and chemical properties or even specific functions has been developed for specifically requirements. Combine chiral with ionic liquids is an important way of the function of ionic liquids. People focused on the synthesis of chiral ionic liquids(CILs) for their particularly potential applications to chiral discrimination, including asymmetric synthesis and chiral catalysis. But up to now,most of CILs are derived from chiral cations, only part of them derived from chiral anions.
In this paper, a series of chiral ionic liquids([emim][I-Ala],[emim][I-Val]) composed of 1-ethyl-3-methylimidazolium cation([emim]) and chiral anions derived from natural amino acids modified with perfluorobutylsulfonyl groups were synthesized through the acid-base reaction.Three chiral anions: N-perfluoroethyl- sufonyl alanine ethyl ester([I-Ala]) and N-perfluoroethylsufonyl valine ethyl ester([I-Val]) and N-perfluoroethylsufonyl leucine ethyl ester([I-Leu]) were synthesized from amino acids through esterification and sulfonylation. A new method was builded to synthesize these CILs through improving the condition of reactions. The optical activity of CILs were also detected.
The results of experiment showed amino acid methyl esters could react easily with perfluorobutylsulfonyl fluoride without any solvents and catalyzer in low temperature. Product could be separated easily from reaction system using a simple method as there were only two reagent in the reaction system. All of the CILs synthesized in this paper could be used in chiral synthesis as they had low melting point and optical activity.
引文
[1] Jie D., Daniel W. Review Article: Chiral ionic liquids: synthesis and applic -ations. Chirality, 2005, 17(5):281~292
[2] Maurizio S., Andreas P. Enantioselective hydrogenation of imines in ionic liquid/carbon dioxide media. J. Am. Chem. Soc.2004, 126(49):16142-16147
[3] Levillain J., Abrunhosa M. Synthesis and properties of thiazoline based ionic liquids derived from the chiral pool. Chem. Commun., 2003, (23):2914~2915
[4] Thanh G., Pegot A. Solvent-free Microwave-assisted preparation of chiral ionic liquids from (-)-N-methylephedrine. Eur. J. Org. Chem.,2004, 72(5): 1112 ~ 1116
[5] Wasserscheid P., Andreas B. Synthesis and properties of ionic liquids derived from the‘chiral pool’. Chem. Commun., 2002, (3):200~201
[6] Bao W., Wang Z., Li Y. Synthesis of chiral ionic liquids from natural amino acids. J.Org.Chem., 2003, 68(2):591~593
[7] Davis J.H. Task-specific ionic liquids. Chem. Lett. 2004, 33(9):1072~1073
[8] Baudequin C., Baudoux J. ionic liquids and chirality:opportunities and challenges. Tetrahedron Asymmetry, 2003, 14(20):3081~3093
[9] Christine B., Delphine B. Chiral ionic liquids, a renewal for the chemistry of chiral solvents? Design, synthesis and applications for chiral recognition and asymmetric synthesis. Tetrahedron Asymmetry, 2005, 16(24):3921–3945
[10] Ishida Y., Miyauchi H., Saigo K. Design and synthesis of a novel imidazolium -based ionic liquid with planar chirality. Chem. Commun. 2002, (19): 2240 ~2241
[11] Levillain J., Dubant G., Abrunhosa I. Synthesis and properties of thiazoline based ionic liquids derived from the chiral pool. Chem. Commun. 2003, (23): 2914~2915
[12] Anastas P.T., Warner J.C. In green chemistry: theory and practice. Oxford University Press, New York, 1998, p30
[13] Salzer A. Ionic liquids: not so green? Chem. Eng. News, 2002, 80(17):4
[14]刘伟山,陶国宏,何玲.功能化的离子液体:手性离子液体的合成和应用. Chinese Journal of Organic Chemistry, 2006, 26 (8):1031~1038
[15] Earle J., Mccormac B., Seddon R. Diels-Alder reactions in ionic Liquids:a safe recyclable alternative to lithium perchlorate-diethyl ether mixtures. Green Chem., 1999, 1(1):23~25
[16] Pernak J., Goc I., Mirska I. Antimicrobial activities of protic ionic liquids with lactate anion. Green Chem., 2004, 6(7):323~329
[17] Fukumoto K., Yoshizawa M., Ohno H. Room temperature ionic liquids from 20 natural amino acids. J. Am. Chem. Soc., 2005, 127(8):2398~2399
[18] Hiroyuki Ohno. Design and synthesis of hydrophobic and chiral anions from amino acids as precursor for functional ionic liquids. Chem. Commun., 2006, (29):3081~3083
[19] Howarth J., Hanlon K., Fayne D. Moisture-stable dialkylimidazolium salts as heterogeneous and homogeneous Lewis acids in the Diels-Alder reaction. Tetrahedron Lett., 1997, 38(17):3097~3100
[20] Lee S.G., Zhang J. Catalytic asymmetric hydrogenation in a room temperature ionic liquid using chiral Rh-complex of ionic liquid grafted 1,4-bisphosphine ligand. Chem. Commun., 2003, (20):2624~2625
[21] Gadenne B., Hesemann P., Moreau J. Ionic liquids incorporating cam- phorsulfonamide units for the Ti-promoted asymmetric diethylzinc addition to benzaldehyde. Tetrahedron Lett., 2004, 45(44):8157~8159
[22] Pegot B., Vo-Thanh G., Loupy A. First application of chiral ionic liquids in asymmetric Baylis–Hillman reaction. Tetrahedron Lett.,2004, 45(34): 6425~ 6428
[23] BiedrońT., Kubisa P. Ionic liquids as reaction media for polymerization pro- cesses: Atom transfer radical polymerization (ATRP) of acrylates in ionic liq- uids. Polym. Int., 2003, 52(10):1584~1588
[24] Ma H., Wan X., Chen X. Design and synthesis of novel chiral ionic liquids and their application in free radical polymerization of methyl methacrylate. Polym.Sci., 2003, 21(3):265
[25] Ding J., Desikan V., Han X. Use of chiral ionic liquids as solvents for the photoisomerization of dibenzobicyclo[2.2.2]octatrienes. Org. Lett., 2005, 7(2): 335 ~337
[26] Ishida Y., Sasaki D., Saigo K. Design and synthesis of novel imidazolium-based ionic liquids with a pseudo crown-ether moiety: diastere- omeric interaction of a racemic ionic liquid with enantiopure europium com- plexes. Tetrahedron Lett., 2004, 45(51): 9455~9459.
[27] Biedron T., Kubisa J. Radical polymerization in a chiral ionic liquid: Atom transfer radical polymerization of acrylates. Polym. Sci. Part A: Polym.Chem., 2005, 43(15):3454~3459
[28] Ding J., Welton T., Armstrong D. Chiral Ionic Liquids as Stationary Phases in Gas Chromatography. Anal. Chem., 2004, 76(22): 6819~6822
[29] Seddon R. Ionic liquids: A taste of the future.Nat. Mater. 2003, 2(6), 363~364
[30] Rogers D., Seddon R. Chemistry Ionic liquids-solvents of the future?. Science , 2003, 302(5646): 792~793
[31] Zhao D., Wu M., Kou Y. Ionic liquids: applications in catalysis. Catal. Today. 2002, 74(2):157~189
[32] Freemantle M. Ionic liquids show promise for clean separation technology. Chem. Eng. News. 1998, 76(4):32~33
[33]程能林.溶剂手册第二版,化学工业出版社, 1994年9月
[34]国家标准局.中华人民共和国国家标准离子交换树脂预处理方法, 1985
[35]王炳琴.氨基酸酯的制备方法及应用. Amino Acids & Biotic Resources. 1995, 17(4):40~45
[36]张小琴.氨基酸快速酯化方法的研究.安庆师范学院学报, 1997, 3(4):66~67
[37]思洋,刘乐乐.氨基酸甲乙酯的合成及纯化.内蒙古医学院学报, 2005, 27(1):33~34
[38]刘国湘,张新信.氨基酸酯化方法的比较及其红外光谱研究. Amino Acids & Biotic Resources.1995, 17(3):36~38
[39] Michael A., Hofmann M. Synthesis of polyphosphazenes with sulfonimide side groups. Macromolecules, 2002, 35(17):6490~6493
[40] Malika B., Zine R. Simple and efficient synthesis of new chiral N,N'-sulfonyl bis-oxazolidin-2-ones. Heteroatom Chemistry, 2006, 17(1):61~ 65
[41]陈先进,徐卫国. N-乙基全氟辛基磺酰胺的制备和应用.浙江化工,2004, 6:1
[42]李焰,陈志启,田娟. N-烷基全氟辛基磺酰胺合成工艺研究.湖北大学学报, 2003, 25(2):141~143
[43] Jie Z., Darryl D. Synthesis of the first difunctional N-fluoro perfluoro alkyl- sulfonylimides:CF3SO2NFSO2(CF2)nSO2NFSO2CF3. Journal of Fluorine Chemistry, 2002, 116(1):45~48
[44] Lino C., Gian P., Gambaretto D. Perfluoroalkanesulfonylimides and their lithium salts: synthesis and characterisation of intermediates and target compounds. Journal of Fluorine Chemistry, 2004, 125(2):243~252
[45] Hong R., Verma J., Shreeve M. Review of ionic liquids with fluorine contain- ing anions. Journal of Fluorine Chemistry, 2006, 127(2):159~176
[2] Maurizio S., Andreas P. Enantioselective hydrogenation of imines in ionic liquid/carbon dioxide media. J. Am. Chem. Soc.2004, 126(49):16142-16147
[3] Levillain J., Abrunhosa M. Synthesis and properties of thiazoline based ionic liquids derived from the chiral pool. Chem. Commun., 2003, (23):2914~2915
[4] Thanh G., Pegot A. Solvent-free Microwave-assisted preparation of chiral ionic liquids from (-)-N-methylephedrine. Eur. J. Org. Chem.,2004, 72(5): 1112 ~ 1116
[5] Wasserscheid P., Andreas B. Synthesis and properties of ionic liquids derived from the‘chiral pool’. Chem. Commun., 2002, (3):200~201
[6] Bao W., Wang Z., Li Y. Synthesis of chiral ionic liquids from natural amino acids. J.Org.Chem., 2003, 68(2):591~593
[7] Davis J.H. Task-specific ionic liquids. Chem. Lett. 2004, 33(9):1072~1073
[8] Baudequin C., Baudoux J. ionic liquids and chirality:opportunities and challenges. Tetrahedron Asymmetry, 2003, 14(20):3081~3093
[9] Christine B., Delphine B. Chiral ionic liquids, a renewal for the chemistry of chiral solvents? Design, synthesis and applications for chiral recognition and asymmetric synthesis. Tetrahedron Asymmetry, 2005, 16(24):3921–3945
[10] Ishida Y., Miyauchi H., Saigo K. Design and synthesis of a novel imidazolium -based ionic liquid with planar chirality. Chem. Commun. 2002, (19): 2240 ~2241
[11] Levillain J., Dubant G., Abrunhosa I. Synthesis and properties of thiazoline based ionic liquids derived from the chiral pool. Chem. Commun. 2003, (23): 2914~2915
[12] Anastas P.T., Warner J.C. In green chemistry: theory and practice. Oxford University Press, New York, 1998, p30
[13] Salzer A. Ionic liquids: not so green? Chem. Eng. News, 2002, 80(17):4
[14]刘伟山,陶国宏,何玲.功能化的离子液体:手性离子液体的合成和应用. Chinese Journal of Organic Chemistry, 2006, 26 (8):1031~1038
[15] Earle J., Mccormac B., Seddon R. Diels-Alder reactions in ionic Liquids:a safe recyclable alternative to lithium perchlorate-diethyl ether mixtures. Green Chem., 1999, 1(1):23~25
[16] Pernak J., Goc I., Mirska I. Antimicrobial activities of protic ionic liquids with lactate anion. Green Chem., 2004, 6(7):323~329
[17] Fukumoto K., Yoshizawa M., Ohno H. Room temperature ionic liquids from 20 natural amino acids. J. Am. Chem. Soc., 2005, 127(8):2398~2399
[18] Hiroyuki Ohno. Design and synthesis of hydrophobic and chiral anions from amino acids as precursor for functional ionic liquids. Chem. Commun., 2006, (29):3081~3083
[19] Howarth J., Hanlon K., Fayne D. Moisture-stable dialkylimidazolium salts as heterogeneous and homogeneous Lewis acids in the Diels-Alder reaction. Tetrahedron Lett., 1997, 38(17):3097~3100
[20] Lee S.G., Zhang J. Catalytic asymmetric hydrogenation in a room temperature ionic liquid using chiral Rh-complex of ionic liquid grafted 1,4-bisphosphine ligand. Chem. Commun., 2003, (20):2624~2625
[21] Gadenne B., Hesemann P., Moreau J. Ionic liquids incorporating cam- phorsulfonamide units for the Ti-promoted asymmetric diethylzinc addition to benzaldehyde. Tetrahedron Lett., 2004, 45(44):8157~8159
[22] Pegot B., Vo-Thanh G., Loupy A. First application of chiral ionic liquids in asymmetric Baylis–Hillman reaction. Tetrahedron Lett.,2004, 45(34): 6425~ 6428
[23] BiedrońT., Kubisa P. Ionic liquids as reaction media for polymerization pro- cesses: Atom transfer radical polymerization (ATRP) of acrylates in ionic liq- uids. Polym. Int., 2003, 52(10):1584~1588
[24] Ma H., Wan X., Chen X. Design and synthesis of novel chiral ionic liquids and their application in free radical polymerization of methyl methacrylate. Polym.Sci., 2003, 21(3):265
[25] Ding J., Desikan V., Han X. Use of chiral ionic liquids as solvents for the photoisomerization of dibenzobicyclo[2.2.2]octatrienes. Org. Lett., 2005, 7(2): 335 ~337
[26] Ishida Y., Sasaki D., Saigo K. Design and synthesis of novel imidazolium-based ionic liquids with a pseudo crown-ether moiety: diastere- omeric interaction of a racemic ionic liquid with enantiopure europium com- plexes. Tetrahedron Lett., 2004, 45(51): 9455~9459.
[27] Biedron T., Kubisa J. Radical polymerization in a chiral ionic liquid: Atom transfer radical polymerization of acrylates. Polym. Sci. Part A: Polym.Chem., 2005, 43(15):3454~3459
[28] Ding J., Welton T., Armstrong D. Chiral Ionic Liquids as Stationary Phases in Gas Chromatography. Anal. Chem., 2004, 76(22): 6819~6822
[29] Seddon R. Ionic liquids: A taste of the future.Nat. Mater. 2003, 2(6), 363~364
[30] Rogers D., Seddon R. Chemistry Ionic liquids-solvents of the future?. Science , 2003, 302(5646): 792~793
[31] Zhao D., Wu M., Kou Y. Ionic liquids: applications in catalysis. Catal. Today. 2002, 74(2):157~189
[32] Freemantle M. Ionic liquids show promise for clean separation technology. Chem. Eng. News. 1998, 76(4):32~33
[33]程能林.溶剂手册第二版,化学工业出版社, 1994年9月
[34]国家标准局.中华人民共和国国家标准离子交换树脂预处理方法, 1985
[35]王炳琴.氨基酸酯的制备方法及应用. Amino Acids & Biotic Resources. 1995, 17(4):40~45
[36]张小琴.氨基酸快速酯化方法的研究.安庆师范学院学报, 1997, 3(4):66~67
[37]思洋,刘乐乐.氨基酸甲乙酯的合成及纯化.内蒙古医学院学报, 2005, 27(1):33~34
[38]刘国湘,张新信.氨基酸酯化方法的比较及其红外光谱研究. Amino Acids & Biotic Resources.1995, 17(3):36~38
[39] Michael A., Hofmann M. Synthesis of polyphosphazenes with sulfonimide side groups. Macromolecules, 2002, 35(17):6490~6493
[40] Malika B., Zine R. Simple and efficient synthesis of new chiral N,N'-sulfonyl bis-oxazolidin-2-ones. Heteroatom Chemistry, 2006, 17(1):61~ 65
[41]陈先进,徐卫国. N-乙基全氟辛基磺酰胺的制备和应用.浙江化工,2004, 6:1
[42]李焰,陈志启,田娟. N-烷基全氟辛基磺酰胺合成工艺研究.湖北大学学报, 2003, 25(2):141~143
[43] Jie Z., Darryl D. Synthesis of the first difunctional N-fluoro perfluoro alkyl- sulfonylimides:CF3SO2NFSO2(CF2)nSO2NFSO2CF3. Journal of Fluorine Chemistry, 2002, 116(1):45~48
[44] Lino C., Gian P., Gambaretto D. Perfluoroalkanesulfonylimides and their lithium salts: synthesis and characterisation of intermediates and target compounds. Journal of Fluorine Chemistry, 2004, 125(2):243~252
[45] Hong R., Verma J., Shreeve M. Review of ionic liquids with fluorine contain- ing anions. Journal of Fluorine Chemistry, 2006, 127(2):159~176