【作者】 巩凯；

【导师】 刘祖亮；

【作者基本信息】 南京理工大学 ， 应用化学， 2009， 博士

【摘要】 离子液体是一类具有溶解和催化复合功能、兼有有机物和无机物特性的新型极性溶剂材料。由于一些独特的物理化学性质,如常温液态、高稳定性、选择溶解性、低挥发性和适度酸碱性等而广泛地应用于有机合成研究,并逐步向实际的生产应用拓展。离子液体的另一特性：较强的针对性和较宽的可设计性为这类物质的合成和应用研究提供了广阔的空间,提供了越来越多的选择。针对不同的反应,设计和制备相应结构和性能的离子液体已成为当前化学领域的热点。本文顺应这一发展趋势,着重在离子液体的设计与制备及其在有机合成中的应用方面进行研究,以寻求一系列具有广泛应用价值、结构新颖、性能优异的新型功能化离子液体。首先,制备碱性功能化离子液体氢氧化1-丁基-3-甲基咪唑盐（[bmim]OH）。研究离子液体[bmim]OH催化芳香醛和丙二腈／氰基乙酸乙酯／罗丹宁的Knoevenagel缩合反应和催化芳香醛、环己酮和芳香胺的Mannich反应。实验表明,该方法具有过程简单、反应速度快、副反应少、产率高等优点。研究了离子液体[bmim]OH催化芳香醛、丙二腈和α-萘酚或β-萘酚三组分“一锅法”合成2-氨基-2-色烯衍生物和催化芳香醛、丙二腈和1,3-环己二酮类化合物的缩合反应合成4H-苯并[b]吡喃衍生物。同时,探索了以绿色溶剂——水为助溶剂,实验表明该合成方法具有工艺简单、反应条件温和、反应时间短、产率高、[bmim]OH/H2O的催化体系可以循环使用等优点。其次,制备了咪唑型酸性功能化离子液体1-甲基-3-丙磺酸基咪唑硫酸氢盐（[MIMPS]HSO4）.1-甲基-3-丙磺酸基咪唑磷酸二氢盐（[MIMPS]H2PO4）、1-甲基-3-丙磺酸基咪唑四氟硼酸盐（[MIMPS]BF4）,并讨论了其催化芳香醛或脂肪族醛与β-萘酚的缩合反应合成相应地14-芳基或烷基-14H-芳苯并[a,j]氧杂蒽衍生物、催化芳香醛与二甲酮或1,3-环己二酮的缩合反应制备相应地9-芳基-2,3,4,5,6,7-六氢-2H-氧杂蒽-1,8-二酮衍生物。实验结果表明,[MIMPS]HSO4是一种有效、良好、绿色的催化剂。同时,将微波技术和离子液体相结合,在此反应体系下合成了9-芳基-2,3,4,5,6,7-六氢-2H-氧杂蒽-1,8-二酮衍生物,微波能较好地促进反应的进行,缩短反应时间、提高反应的产率和选择性。最后,设计、制备了基于脂肪族二元胺的新型酸性功能化离子液体N,N，N’,N’-四甲基-N,N’-二磺酸丙基乙二胺硫酸氢盐([TMEDAPS][HSO4]、N, N, N’,N’-四甲基-N,N’-二磺酸丙基丙二胺硫酸氢盐（[TMPDAPS][HSO4]）、N, N, N’,N’-四甲基-N,N’-二磺酸丙基己二胺硫酸氢盐（[TMHDAPS] [HSO4]）等,并用UV-vis光谱法（Hammett法）测定了其酸度函数H₀。与咪唑型酸性离子液体1-甲基-3-丙磺酸基咪唑硫酸氢盐[MIMPS][HSO4]相比,它们的酸度函数H₀值较小,其酸性更强。在无溶剂条件下,以[TMHDAPS][HSO4]为催化剂,催化一系列芳香醛、β-萘酚和酰胺化合物的缩合反应制备1-酰胺基烷基-2-萘酚衍生物。在离子液体用量为5 mol%,原料摩尔比n（芳香醛）：n（酰胺）：n（伊萘酚）=1：1：1.2,在100℃、无溶剂条件下,反应6-20 min,产率为88～98%。该方法具有催化剂用量少、反应时间短、产率高等优点,离子液体易于回收使用,且循环使用5次以上,其催化活性并未明显降低。更多还原

【Abstract】 Ionic liquids, considered as novel solvents/catalysts compounded functionalized materials, have been widely used in organic reactions because of their unique chemical and physical properties of low melting points, high thermally stability, controlled miscibility, nonvalatility, moderate acidity or alkalescence and so on. Another feature of high pertinence and a wide range of designability of ionic liquids provide a broad space for its sythesis and application. For different reactions, design and preparation of corresponding structure and properties of ionic liquids have become a hot area of current chemistry. To conform to this trend of development, we focused on the design, preparation and application in organic synthesis of ionic liquids, aiming at searching for a series of new functionalized ionic liquids with a value of broad applications, novel structures and high-performances in our dissertation.Firstly, a basic task-specific ionic liquid, 1-butyl-3-methylimidazolium hydroxide [bmim]OH, has been synthesized. It has been introducted as a catalyst for the Knoevenagel condensation reactions of aromatic aldehydes with malononitrile or ethyl cyanoacetat or rhodanine, and the Mannich-type reactions of aromatic aldehydes, cyclohexanone, and aromatic amines. The present protocol offers several advantages, including simple work-up procedure, short reaction time and high yields.Furthermore, ionic liquid [bmim]OH catalyzed three-component condensation reaction of aromatic aldehydes, malononitrile andα-orβ-naphthol proceeded rapidly in water at reflux to afford corresponding 2-amino-2-chromenes in high yields, catalyzed three-component condensation reaction of aromatic aldehydes, malononitrile and active methylene carbonyl compounds for the synthesis of 4H-benzo[b]pyrans at room temperature in aqueous media. In addition, water was chosen as a green solvent. The attractive features of this protocol are simple procedure, mild conditions, short reaction time, excellent yields, mild conditions and the easy workup procedure.Secondly, some acidic ionic liquids that bear imidaolium cation, such as [MIMPS]HSO4, [MIMPS]H2PO4 and [MIMPS]BF4, have been synthesized. And then, the ionic liquid [MIMPS]HSO4 was empolyed as catalyst for the synthesis of 14-alkyl-or aryl-14H-dibenzo[a,j]xanthenes via the one-pot condensation ofβ-naphthol with aliphatic or aromatic aldehydes and the synthesis of 1,8-dioxo-octahydroxanthenes by a one-pot condensation of aromatic aldehydes and active methylene carbonyl compounds. It was indicated that [MIMPS]HSO4 is an efficient, novel and green catalyst. Simultaneously, the synthesis of 1,8-dioxo-octahydroxanthenes in the same reaction conditions was carried out under microwave irradiation. It is an efficient method to reduce reaction time, increase yields and improve selectivity.Lastly, some novel SO3H-functional Br(?)nsted-acidic ionic liquids that bear an alkene sulfonic acid group in acyclic diamine cations have been synthesized via two-step atom economic reactions. The Br(?)nsted acidities of these ionic liquids were evaluated from the determination of the Hammett acidity functions, using UV-visible spectroscopy. Compared with 1-methyl-3-propane sulfonic-imidazolium hydrosulfate [MIMPS][HSO4], the Hammett acidity functions of these ionic liquids are smaller, in other words, the Br(?)nsted acidities of these ionic liquids are stronger. An efficient and direct proceduce has been developed for the preparation of amidoalkyl naphthols by a one-pot condensation of aryl aldehydes,β-naphthol and amides, in the presence of [TMHDAPS][HSO4] as catalyst under solvent-free conditons. Under the optimum conditions as n(aromatic aldehydes):n(β-naphthol):n(amides)=1:1:1.2, and in the presence of 5 mol%, the yields of amidoalkyl naphthols was obtained with 88～98% at 100℃for 6-20 min under solvent-free conditions. This novel synthesis method offers several advantages such as excellent yields, short reaction times and simple procedure. The catalyst could be recycled and reused at least five times without noticeably decrease in catalytic activity.更多还原