【作者】 方东；

【导师】 刘祖亮；

【作者基本信息】 南京理工大学 ， 应用化学， 2008， 博士

【摘要】 离子液体具有很多独特的理化性能:熔点很低;蒸汽压几乎察觉不到;热稳定性高;对部分无机盐具有很强的溶解能力;电化学窗口较宽;其稳定的液态范围可达300～400℃;易于循环使用。近年来在精细有机合成等方面应用广泛。1—烷基—3—甲基咪唑四氟硼酸盐（[AMIM][BF₄]）和1—烷基—3—甲基咪唑六氟磷酸盐（[AMIM][PF₆]）,N—烷基吡啶四氟硼酸盐（[APy][BF₄]1）和N—烷基吡啶六氟磷酸盐（[APy][PF₆]）等几类离子液体是研究最多也是最具代表性的室温离子液体。本文提出并设计了无溶剂一步法合成[AMIM][BF₄]、[AMIM][PF₆]、[APy][BF₄]和[APy][PF₆]等经典离子液体的新的清洁合成路线。一步法合成工艺的反应温度为70～100℃,反应时间为3.0～4.0h,分离产率可达86～98%,符合绿色化学的要求。Brφnsted酸性功能化离子液体（TSILs）结合了固体酸与无机酸的优点,具有取代目前工业用酸催化材科的潜力。功能化离子液体可用于烷基化反应,Fischer酯化反应,醚化反应及重排反应。本文设计并合成了含咪唑阳离子、吡啶阳离子以及含开链结构的季铵阳离子的Brφnsted酸功能化离子液体,得到了几乎定量的产率。用¹HNMR、¹³CNMR、FT-IR以及MS等对所合成的TSILs的结构进行表征。取代二苯醚类化合物是重要的精细化工中间体。该类化合物的合成路线为典型的亲核取代反应,如Ullmann醚化反应和Williamson反应。我们用一步法合成的离子液体作为绿色溶剂,替代DMF、DMSO等强极性溶剂用于取代二苯醚的合成,同时考察了离子液体的循环使用性能。为了考察新型功能化离子液体的催化性能,本文利用所设计合成的1—甲基—3—丙磺酸基咪唑盐的一系列功能化室温离子液体,以及N,N,N—三烷基—N—磺酸丙基—硫酸氢铵、磷酸氢铵盐的一系列功能化室温TSILs作为溶剂/催化剂双功能体系,考察了TSILs对部分脂肪族、芳香族羧酸与醇的Fischer酯化反应的催化性能。在室温或100℃左右反应1.5～3.0h,酯化产率达88%～95%。反应结束后,产物与催化体系形成液—液两相,通过简单的倾析便可实现产物与催化体系的分离。催化体系可以重复使用而催化活性基本不变。探索了本学位论文设计、合成的新型开链结构的季铵阳离子的Brφnsted酸功能化离子液体,作为相转移/Brφnsted酸双功能催化剂,在水溶液中催化醛、酮、胺三组分Mannich反应,合成了16个β—氨基酮（Mannich碱）类化合物。反应于室温下进行,催化剂可以循环使用,是一项具有广泛应用前景的清洁生产技术。本文选择季铵盐结构的阳离子,与不含卤素的无机酸根阴离子,组成功能化离子液体,作为Biginelli反应的催化剂,能够在无溶剂条件下或在水相中实现芳香醛、二羰基化合物、尿素（硫脲）一锅法三组分Biginelli反应。考察了在不同溶剂中、不同反应条件下的催化活性,并将其与咪唑型离子液体以及其它常用的一些催化剂进行比较。用优化后的工艺条件,合成了一系列的3,4—二氢嘧啶—2—酮（硫酮）（DHPMs）类化合物。离子液体经过六次循环使用,其催化性能无明显变化。目前工业上仍采用已沿袭了一百多年的由硫酸、硝酸组成的混酸进行硝化的传统工艺。本文以1—甲基—3—丙磺酸基咪唑硫酸氢盐（[MIMPS][HSO₄]）以及开链季铵盐型N,N,N—三烷基—N—磺酸丙基—硫酸氢铵盐（[TMPSA][HSO₄]、[TEPSA][HSO₄]、[TBPSA][HSO₄]）等功能化室温离子液体作为催化剂,在室温～80℃下对一取代的芳香族化合物进行绿色硝化反应,可达到良好的效果。反应后处理简单,催化剂能够循环使用。更多还原

【Abstract】 Ionic liquids are simply liquids that are composed entirely of ions.They have been the subject of considerable interest as environmentally benign alternative to volatile solvents （VOCs）in organic synthesis during the last few years.These solvents possess a number of interesting properties,notably their low melting points,lack of vapor pressure,high thermally stability,ease of reuse,good capacity for solubilizing organic substrates,lack of flammability and large accessible temperature range.To date,some of the important organic reactions have been carried out and investigated in ionic liquids.The vast majority of ionic liquid chemistry based on nitrogen-containing heterocycles focuses on the use of 1-alkyl-3-methylimidazolium and N-alkylpyridinium cations. 1-Alkyl-3-methylimidazolium hexafluorophosphate（AMIMPF₆）, 1-alkyl-3-methylimidazolium tetrafluoroborate（AMIMBF₄）,N-alkylpyridinium tetrafluoroborate（APyBF₄）and N-alkylpyridinium hexafluorophosphate（APyPF₆）are typically ionic liquids.It has been found that AMIMPF₆,AMIMBF₄,APyBF₄ and APyPF₆ can be prepared with stoichiometric amounts of 1-methylimidazole or pyridine, alkylhalides and potassium,sodium or ammonium salt of hexafluorophosphate or tetrafluoroborate in one-pot solvent-free conditions under 70℃to 100℃to give excellent yields of 88%-95%with shortened time within 3.0-4.0h.The apparent kinetics of the novel procedure has also been investigated.Bronsted acidic task-specific ionic liquids（TSILs）combining the advantageous characteristics of solid acids and mineral acids,are designed to replace traditional mineral liquid acids,such as sulfuric acid and hydrochloric acid in chemical processes.However, the development and exploring of Brφnsted-acidic TSILs are currently in preliminary stage and the number of published Brφnsted-acidic TSILs is limited.Here,some novel SO₃H-functional Brφnsted-acidic TSILs that bear an alkane sulfonic acid group in an imidazolium cation,pyridinium cation,or acyclic tri-alkanyl-ammonium cation have been synthesized via two-step atom economic reactions.The chemical yields for both the zwitterion formation and acidification steps are essentially quantitative,since neither reaction produces byproducts.Their structures were analyzed by ¹HNMR,¹³CNMR,IR and MS spectroscopes.The substituted diphenyl ethers are important intermediate chemicals used in fine chemicals,pesticides and medicines.As a nucleophilic reaction,the substituted diphenyl ether can be prepared in aprotic polar solvent such as DMF,DMSO etc.,in view of economical and environmental points,studying the use of ionic liquids as the green solvents is of great significance.The preparation of some substituted diphenyl ethers in ionic liquids prepared as above has been explored.Some substituted diphenyl ethers were synthesized via Williamson or Ullmann reactions using the ionic liquids as the recyclable green solvents with high yields.Brφnsted acidic ionic liquids（TSILs）synthesized in our work have been used as dual solvent-catalysts for Fischer esterification reactions of acetic acid,metacetonic acid,and benzoic acid with ethanol,butanol,and benzyl alcohol were investigated.The reactions were completed smoothly at room temperature to 110℃for 1.5-3.0h with good yields of 88%-95%.The results indicate that catalytic activity depends on anion acidity and the solubility of the starting material in TSILs.The increasing of the anion’s acidity improves the catalytic activity of the TSILs.Furthermore,the produced esters could be separated by decantation after the reaction and the TSILs could be reused without noticeably decreasing the catalytic activity.Then the TSILs have been used as the cheap and recyclable catalysts for one-pot three-component Mannich reaction in water.Sixteenβ-amino carbonyl compounds were obtained in good yields under the mild conditions.The products could simply be separated from the catalyst/water,and the catalyst could be reused at least 7 times without noticeably decreasing the catalytic activity.Subsequently,the TSILs have been found to be effective catalysts for assembling 3,4-dihydropyrimidine-2-（1H）-ones via one-pot three-component Biginelli reaction.The satisfactory results were obtained with good yields,short reaction time and simplicity in the experimental procedure.The catalysts could be recycled and reused for several times without noticeably decreasing the catalytic activity.Electrophilic nitration of aromatics is a fundamental reaction of great industrial importance,whose products are used as organic intermediates or energetic materials.It is also among the most important unit reactions in chemical industry.Brφnsted acidic TSILs have also been used as halogen-free catalysts for regioselective mononitration of aromatic compounds.The reaction conditions including reaction temperature,reaction time,molar ratio of aromatic compounds,nitrating agents and catalyst have also been investigated. Under the optimal reaction conditions,the nitration reactions of aromatic compounds were carried out at r.t.to 80℃with reasonable to good yields;in addition,the TSILs could be recovered and reused without noticeably decreasing the catalytic activity.更多还原