离子液体的合成及其作为催化剂在有机反应中的应用研究
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摘要
近年来随着绿色化学的兴起和发展，离子液体(Ionic Liquids)的绿色性能及其作为溶剂、催化剂时高效反应介质的特性引起了人们广泛的重视。离子液体也成为绿色化学领域中最有特色的方向和热点之一。离子液体是纯粹由离子组成的液体，其本身几乎无蒸汽压，具有很高的热力学和化学稳定性，无可燃性、无着火点，离子电导率高，可以循环使用等特性，同时对无机和有机物有良好的溶解性、稳定性，常作为绿色溶剂和催化剂应用于有机合成中。
本论文主要从以下几方面进行研究：
1、分别合成和使用催化量的室温离子液体[HMIm]BF_4，[HMIm]ClO_4，[HMIm]PhSO_3，[HMIm]CF_3CO_2，[BMIm]BF_4，[BMIm]PF_6，[Bpy]HSO_4，[iso-Bqu]HSO_4作为催化剂，在温和条件下、较短时间内顺利促使一系列查尔酮与邻苯二胺发生反应，并以较高产率生成苯并二氮杂草类化合物(80～95％)。实验结果表明1-丁基吡啶硫酸氢根([Bpy]HSO_4)离子液体是新型、高效、廉价、易得、清洁的合成苯并二氮杂草衍生物的优良Brφnsted酸催化剂。该反应条件温和，操作和后处理简单易行，催化剂至少可以循环使用4次活性基本不变，可以替代用于该反应的其它催化剂，具有推广价值。
2、采用质子化离子液体[HMIm]BF_4，[HMIm]CF_3SO_3，[HMIm]PhSO_3，[HMIm]CF_3CO_2和H_2NSO_3H为催化剂，在室温条件下研究醛(酮)与原甲酸三乙酯缩合生成缩醛和缩酮的反应。通过对比实验和改变实验条件发现[HMIm]BF_4离子液体最适合完成该反应过程，产物缩醛／缩酮的产率达到84～96％。该反
Room temperature ionic liquids (RTILs) have increasingly attracted attention as the green, high-tech reaction media of the future. ILs entirely composed of cations and anions are being used as green solvents with unique properties such as wide liquid range, good solvating ability, tunable polarity, high thermal stability, nonvolatility and so forth. As a result of their green credentials and potential to enhance rates and selectivity, ionic liquids are finding increasing applications in organic synthesis. In this paper we will describe the study on the organic reactions by using ILs as catalyst.
A novel and simple ionic liquid methodology for the synthesis of 1,5-benzodiazepines is described. 1-Butylpyridinium hydrogen sulphate ([BPy]HSO_4) acidic room temperature ionic liquids as a novel and efficient catalysts was synthesized and used to the preparation of a series of 1,5-benzodiazepine derivatives by the reaction of o-phenylenediamine with chalcones under mild condition. This method is easy, efficient, environmental friendly, economical, toxic catalyst free and good yields for the formation of 1,5-benzodiazepines.
A series of acidic ionic liquids such as [HMIm]BF_4, [HMIm]CF_3SO_3,
本论文主要从以下几方面进行研究：
1、分别合成和使用催化量的室温离子液体[HMIm]BF_4，[HMIm]ClO_4，[HMIm]PhSO_3，[HMIm]CF_3CO_2，[BMIm]BF_4，[BMIm]PF_6，[Bpy]HSO_4，[iso-Bqu]HSO_4作为催化剂，在温和条件下、较短时间内顺利促使一系列查尔酮与邻苯二胺发生反应，并以较高产率生成苯并二氮杂草类化合物(80～95％)。实验结果表明1-丁基吡啶硫酸氢根([Bpy]HSO_4)离子液体是新型、高效、廉价、易得、清洁的合成苯并二氮杂草衍生物的优良Brφnsted酸催化剂。该反应条件温和，操作和后处理简单易行，催化剂至少可以循环使用4次活性基本不变，可以替代用于该反应的其它催化剂，具有推广价值。
2、采用质子化离子液体[HMIm]BF_4，[HMIm]CF_3SO_3，[HMIm]PhSO_3，[HMIm]CF_3CO_2和H_2NSO_3H为催化剂，在室温条件下研究醛(酮)与原甲酸三乙酯缩合生成缩醛和缩酮的反应。通过对比实验和改变实验条件发现[HMIm]BF_4离子液体最适合完成该反应过程，产物缩醛／缩酮的产率达到84～96％。该反
Room temperature ionic liquids (RTILs) have increasingly attracted attention as the green, high-tech reaction media of the future. ILs entirely composed of cations and anions are being used as green solvents with unique properties such as wide liquid range, good solvating ability, tunable polarity, high thermal stability, nonvolatility and so forth. As a result of their green credentials and potential to enhance rates and selectivity, ionic liquids are finding increasing applications in organic synthesis. In this paper we will describe the study on the organic reactions by using ILs as catalyst.
A novel and simple ionic liquid methodology for the synthesis of 1,5-benzodiazepines is described. 1-Butylpyridinium hydrogen sulphate ([BPy]HSO_4) acidic room temperature ionic liquids as a novel and efficient catalysts was synthesized and used to the preparation of a series of 1,5-benzodiazepine derivatives by the reaction of o-phenylenediamine with chalcones under mild condition. This method is easy, efficient, environmental friendly, economical, toxic catalyst free and good yields for the formation of 1,5-benzodiazepines.
A series of acidic ionic liquids such as [HMIm]BF_4, [HMIm]CF_3SO_3,
引文
[1] 绿色化学导论武汉：武汉大学出版社 徐汉生编著 2002．
[2] 绿色化学原理和应用北京：中国石化出版社 胡常伟、李贤均著 2002．
[3] 绿色溶剂—离子液体的合成与应用．李汝雄 化学工业出版社 2004．
[4] Suman Sahoo, Trissa Joseph, S.B. Halligudi. Mannich reaction in Bronsted acidic ionic liquid: A facile synthesis of β-amino carbonyl compounds J. Mol. Catal. A: Chem., 2006, 244: 179-182.
[5] Vasundhara Singh, Sukhbir Kaur, Varinder Sapehiyia et al. Microwave accelerated preparation of [bmim][HSO4] ionic liquid: an acid catalyst for improved synthesis of coumarins. Catal. Commun., 2005, 6: 57-60.
[6] Peter Wasserscheid, Martin Sesing, Wolfgang Korth. Hydrogensulfate and tetrakis(hydrogensulfato)borate ionic liquids: synthesis and catalytic application in highly Brnsted-acidic systems for Friedel-Crafts alkylation Green Chem., 2002, 4: 134-138.
[7] Gu, Da-Gong; Ji, Shun-Jun; Jiang, Zhao-Qin et al. An Efficient Synthesis of Bis(indolyl)methanes Catalyzed by Recycled Acidic Ionic Liquids. Synlett, 2005, 6: 959-962.
[8] Shu Guo, Zhengyin Du, Shiguo Zhang et al. Clean Beckmann rearrangement of cyclohexanone oxime in caprolactam based Brnsted acidic ionic liquids. Green Chem., 2006, 8： 296-300.
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[2] 绿色化学原理和应用北京：中国石化出版社 胡常伟、李贤均著 2002．
[3] 绿色溶剂—离子液体的合成与应用．李汝雄 化学工业出版社 2004．
[4] Suman Sahoo, Trissa Joseph, S.B. Halligudi. Mannich reaction in Bronsted acidic ionic liquid: A facile synthesis of β-amino carbonyl compounds J. Mol. Catal. A: Chem., 2006, 244: 179-182.
[5] Vasundhara Singh, Sukhbir Kaur, Varinder Sapehiyia et al. Microwave accelerated preparation of [bmim][HSO4] ionic liquid: an acid catalyst for improved synthesis of coumarins. Catal. Commun., 2005, 6: 57-60.
[6] Peter Wasserscheid, Martin Sesing, Wolfgang Korth. Hydrogensulfate and tetrakis(hydrogensulfato)borate ionic liquids: synthesis and catalytic application in highly Brnsted-acidic systems for Friedel-Crafts alkylation Green Chem., 2002, 4: 134-138.
[7] Gu, Da-Gong; Ji, Shun-Jun; Jiang, Zhao-Qin et al. An Efficient Synthesis of Bis(indolyl)methanes Catalyzed by Recycled Acidic Ionic Liquids. Synlett, 2005, 6: 959-962.
[8] Shu Guo, Zhengyin Du, Shiguo Zhang et al. Clean Beckmann rearrangement of cyclohexanone oxime in caprolactam based Brnsted acidic ionic liquids. Green Chem., 2006, 8： 296-300.
[9] a) Schutz H., Benzodiazepines, Springer Verlag, Heidelberg, 1982; b) J. K. Landquist, in: Comprehensive Hetero-cyclic Chemistry, (Eds.: A. R. Katritzky; C. W. Rees), Pergamon, Oxford, 1984, 1, 116.
[10] a) Randall L. O., Kamal B., in: Benzodiazepines, (Eds.: Garattini S., Mussini E., Randall L. O.), Raven Press, New York, 1973, p. 27, and references cited therein; b) Baun J. R. D., Pallos F. M., Baker D. R., US Patent 3,978,227, 1976; Chem. Abstr. 1977, 86, 5498d.
[11] Haris R. C., Straley J. M., US Patent 1,537,757, 1968; Chem. Abstr. 1970, 73, 100054w.
[12] (a)Aversa, M. C.; Ferlazzo, A.; Giannetto, P.; et al. A convenient synthesis of novel[1,2,4]triazolo[4,3-a] [1,5]benzodiazepine derivatives. Synthesis 1986, 230. (b) Chimirri, A.; Grasso,S.; Ottana, R.; Romeo; Zappala, G. M. Synthesis and stereochemistry of novel [1,2,4] oxadiazolo [4,5-a] [1,5]benzodiazepine derivatives. J. Heterocycl. Chem. 1990, 27, 371.
[13] Herbert, J. A. L.; Suschitzky, H. J. Chem. Soc., Perkin Trans. 1, 1974, 2657-2661.
[14] Morales, H. R.; Bulbarela, A.; Contreras, R. New synthesis of dihydro- and tetrahydro-1,5-benzodiazepines by reductive condensation of o-phenylenediamine and ketones in the presence of sodium borohydride. Heterocycles. 1986, 24, 135-139.
[15] Jung, D.I.; Choi, T.W.; Kim, Y.Y.; et al. Synthesis of 1,5-benzodiazepine derivatives. Synth. Commun., 1999, 29, 1941-1951.
[16] Yadav, J.S.; Reddy, B.V.S.; Eshwaraian, B.; Anuradha, K. Amberlyst-15: a novel and recyclable reagent for the synthesis of 1,5-benzodiazepines in ionic liquids. Green Chem., 2002, 4, 592-594.
[17] Curini, M.; Epifano, F.; Marcotullio, M.C.; et al. Ytterbium triflate promoted synthesis of 1,5-benzodiazepine derivatives. Tetrahedron Lett., 2001, 42, 3193-3195.
[18] Balakrishna, M.S.; Kaboundin, B. A simple and new method for the synthesis of 1,5-benzodiazepine derivatives on a solid surface. Tetrahedron Lett., 2001, 42, 1127-1129.
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