基于甘油衍生物及生物可降解离子液体的合成与应用研究
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摘要
离子液体是由有机阳离子与无机或有机阴离子组成的在较低温度下呈液体状态的离子化合物,由于其具有特殊的化学、物理性质作为环境友好溶剂和催化剂得到了广泛的研究和关注。在绿色化学的要求下,离子液体的研究当中,环境友好性和生物可再生能力日益受到重视,以生物可再生资源作为原料合成环境友好型离子液体已经成为一个研究热点。本论文旨在利用生物可再生资源甘油衍生物合成新的功能化离子液体以及合成具有生物可降解性的离子液体并研究他们的理化性质及应用价值。
本文合成了基于甘油衍生物的甲基咪唑基、吡啶基、烷基三乙基铵基和丁基咪唑基的二羟基、二酯基功能化离子液体及甲基咪唑基侧链含有乙酰酯基、乙酰胺基官能团的生物可降解离子液体共39种(其中16种为未见文献报道的离子液体,四种为手性离子液体)。通过~1H NMR,~13C NMR,FT-IR等分析手段对其结构进行了表征确认。
甘油是天然油脂制造生物柴油过程的主要副产物,具有廉价易得、可生物再生的优点。随着生物柴油产量的提高,甘油衍生物成为廉价易得的化学品,利用其制备廉价、高效能的离子液体并研究其应用价值是很有意义的。本论文利用甘油衍生物为原料,运用简便、高效的合成方法制备了二羟基、二酯基功能化的离子液体,并在制备醋酸盐离子液体过程中采用原子经济性反应;测定了离子液体的水溶性、与有机溶剂的互溶性,研究其生物毒性,并开发其应用价值。
阳离子侧链含有酯基、酰胺基结构的离子液体已有报道确认其具有良好的生物可降解性,在自然环境中可以降解成对环境无害的成分,因而利用此类离子液体作为有机反应溶剂具有良好的环境友好性,是传统高毒性有机分子溶剂的良好替代品。此类离子液体在作为溶剂参与不对称催化氢化反应中表现出较好的性能,接近现行工艺采用甲醇作为溶剂的效果。
Ionic liquids (ILs) are salts which have low melting point and composed entirely of organic cation and inorganic or organic anion. Recently they have been received widely much attentions and widely researched for Green chemistry as environmental-friendly solvents and catalyst, for their outstanding chemical and physical properties. Synthesis ionic liquid from biorenewable resource is the focus of recently researches. This thesis was working on synthesis ILs based on biorenewable resource: glycerol derivatives and synthesis some ILs known for their biodegradability, also investigate the applications of these environmentally-friendly ILs.
In this paper, dihydroxyl, diester functionalized ILs based on methylimidazolium, pyridinium, alkyltriethylammonium and butylimidazolium from glycerol derivatives and biodegradable ILs from methylimidazole contain ester or amide group were synthesized and characterized by 1H NMR, 13C NMR and FT-IR.
Glycerol is the by-product of biodiesel by transesterificaion of nature oils or fats, as the production of biodiesel increasing, glycerol is more available and much cheaper now. This paper focuses on prepare dihydroxyl and diester functionalized ILs from biorenewable glycerol derivatives in an efficient and convenient general method. Atom economic reaction was was utilized for synthesis acetate IL. We determined the ILs’water-solubility and their miscibility with organic solvents, investigated their toxicity and the development of their applicationes: Bio-polymers and carbohydrates dissolve in ILs; Dihydroxyl functionalized non-water-soluble ionic liquids on the extraction of trace boric acid from water.
ILs contained ester, amide functionalized groups have been confirmed biodegradable in the natural environment. So we could use of such ILs as environment-friendly solvents in organic reactions. It is a good alternative solvent of traditional highly toxic organic molecules compounds. Ionic liquid solvent such as participation in the catalytic asymmetric hydrogenation showed a nice performance, close to the method of using methanol as solvent.
本文合成了基于甘油衍生物的甲基咪唑基、吡啶基、烷基三乙基铵基和丁基咪唑基的二羟基、二酯基功能化离子液体及甲基咪唑基侧链含有乙酰酯基、乙酰胺基官能团的生物可降解离子液体共39种(其中16种为未见文献报道的离子液体,四种为手性离子液体)。通过~1H NMR,~13C NMR,FT-IR等分析手段对其结构进行了表征确认。
甘油是天然油脂制造生物柴油过程的主要副产物,具有廉价易得、可生物再生的优点。随着生物柴油产量的提高,甘油衍生物成为廉价易得的化学品,利用其制备廉价、高效能的离子液体并研究其应用价值是很有意义的。本论文利用甘油衍生物为原料,运用简便、高效的合成方法制备了二羟基、二酯基功能化的离子液体,并在制备醋酸盐离子液体过程中采用原子经济性反应;测定了离子液体的水溶性、与有机溶剂的互溶性,研究其生物毒性,并开发其应用价值。
阳离子侧链含有酯基、酰胺基结构的离子液体已有报道确认其具有良好的生物可降解性,在自然环境中可以降解成对环境无害的成分,因而利用此类离子液体作为有机反应溶剂具有良好的环境友好性,是传统高毒性有机分子溶剂的良好替代品。此类离子液体在作为溶剂参与不对称催化氢化反应中表现出较好的性能,接近现行工艺采用甲醇作为溶剂的效果。
Ionic liquids (ILs) are salts which have low melting point and composed entirely of organic cation and inorganic or organic anion. Recently they have been received widely much attentions and widely researched for Green chemistry as environmental-friendly solvents and catalyst, for their outstanding chemical and physical properties. Synthesis ionic liquid from biorenewable resource is the focus of recently researches. This thesis was working on synthesis ILs based on biorenewable resource: glycerol derivatives and synthesis some ILs known for their biodegradability, also investigate the applications of these environmentally-friendly ILs.
In this paper, dihydroxyl, diester functionalized ILs based on methylimidazolium, pyridinium, alkyltriethylammonium and butylimidazolium from glycerol derivatives and biodegradable ILs from methylimidazole contain ester or amide group were synthesized and characterized by 1H NMR, 13C NMR and FT-IR.
Glycerol is the by-product of biodiesel by transesterificaion of nature oils or fats, as the production of biodiesel increasing, glycerol is more available and much cheaper now. This paper focuses on prepare dihydroxyl and diester functionalized ILs from biorenewable glycerol derivatives in an efficient and convenient general method. Atom economic reaction was was utilized for synthesis acetate IL. We determined the ILs’water-solubility and their miscibility with organic solvents, investigated their toxicity and the development of their applicationes: Bio-polymers and carbohydrates dissolve in ILs; Dihydroxyl functionalized non-water-soluble ionic liquids on the extraction of trace boric acid from water.
ILs contained ester, amide functionalized groups have been confirmed biodegradable in the natural environment. So we could use of such ILs as environment-friendly solvents in organic reactions. It is a good alternative solvent of traditional highly toxic organic molecules compounds. Ionic liquid solvent such as participation in the catalytic asymmetric hydrogenation showed a nice performance, close to the method of using methanol as solvent.
引文
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[2] Welton T. Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis[J]. Chemical Reviews, 1999, 99(8):2071-2083.
[3] Han X X and Armstrong D W. Ionic Liquids in Separations[J]. Acc. Chem. Res., 2007, 40(11):1079-1086.
[4]王风彦,邵光杰.离子液体应用研究进展[J].化学试剂, 2009, 31(1):25-30.
[5] Roger S. Catalytic reactions in ionic liquids[J]. Chem. Commun., 2001, 23:2399- 2407.
[6] Tang S L Y, Smith R L and Poliakoff M. Principles of green chemistry: PRODUCTIVELY[J]. Green Chem., 2005, 7:761-762.
[7] Anastas P and Eghbali N. Green Chemistry: Principles and Practice[J]. Chem. Soc. Rev., 2010, 39:301-312.
[8] Wilkes J S. A short history of ionic liquids—from molten salts to neoteric solvents[J]. Green Chemistry, 2002, 4:73-80.
[9]顾彦龙,彭家建,乔琨,杨宏洲,石峰,邓友全.室温离子液体及其在催化和有机合成中的应用[J].化学进展, 2003, 15(3):222-241.
[10] Sun J, Forsyth M, and MacFarlane D R. Room-Temperature Molten Salts Based on the Quaternary Ammonium Ion[J]. J. Phys. Chem. B, 1998, 102:8858-8864.
[11] Byrne R, Coleman S, Gallagher S and Diamond D. Designer molecular probes for phosphonium ionic liquids[J]. Phys. Chem. Chem. Phys., 2010, 12:1895-1904.
[12] a. Wilkes J S, Levisky J A, Wilson R A and Hussey C L. Dialkylimidazolium Chloroaluminate Melts: A New Class of Room-Temperature Ionic Liquids for Electrochemistry, Spectroscopy, and Synthesis[J]. Inorg. Chem., 1982, 21(3):1263-1264. b. Bonhote P, Dias A, Papageorgiou N, Kalyanasundaram K and Gratzel M. Hydrophobic, Highly Conductive Ambient-Temperature Molten Salts[J]. Inorg. Chem., 1996, 35(5): 1168- 1178.
[13] Gale R J and Osteryoung R A. Infrared Spectral Investigations of Room-Temperature Aluminum Chloride-1-Butylpyridinium Chloride Melts[J]. Inorg. Chem., 1980, 19(8):2240- 2242.
[14] Mateus N M M, Branco L C, Lourenco N M T and Afonso C A M. Synthesis and properties of tetra-alkyl-dimethylguanidinium salts as a potential new generation of ionic liquids[J]. Green Chemistry, 2003, 5:347-352.
[15] Fang S H, Yang L, Wei Chao, Peng C G, Tachibana K, Kamijima K. Low-viscosity and low-melting point asymmetric trialkylsulfonium base dionic liquids as potential electrolytes[J]. Electrochemistry Communications, 2007, 9:2696-2702.
[16] Wilkes J S and Zaworotko M J. Air and Water Stable I-Ethyl-3-methylimidazolium BasedIonic Liquids[J]. J. Chem. Soc., Chem. Commun., 1992:965-967.
[17] MacFarlane D R, Pringle J M, Johansson K M, Forsyth S A, Forsyth M. Lewis base ionic liquids[J]. Chem. Commun., 2006, 18:1905-1917.
[18] Plechkovaa N V and Seddon K R. Applications of ionic liquids in the chemical industry[J]. Chem. Soc. Rev., 2008, 37:123-150.
[19]包伟良,王治明.离子液体的研究现状与发展趋势[C].中国科协第143次青年科学家论坛—离子液体与绿色化学, 2007:3-9.
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