【作者】 李贺；

【导师】 刘晨江；

【作者基本信息】 新疆大学 ， 化学， 2015， 硕士

【摘要】 随着绿色化学与原子经济性概念的出现,通过过渡金属催化活化不活泼的C-H键进而构建新的C-C键已经成为一个热门研究领域。而通过碳氢键氧化偶联方式构建C-C键具有很大的优越性,因为在这个过程中可以避免使用贵金属催化剂,交叉脱氢偶联反应(CDC)就是典型的代表之一。现在,无金属催化的CDC反应成为新的研究热点,而关于杂环离子液体单独用于催化或促进CDC反应的研究尚未见报道,因此我们开展了相应的研究工作。首先,基于我们课题组在离子液体合成及应用方面的研究,我们合成了一系列含溴负离子的简单结构的离子液体,并对其结构进行了表征。然后,我们以5-芳氧基-4-吡唑甲醛作为反应底物,对离子液体促进的分子内CDC反应合成吡唑并色酮类化合物的条件进行了优化,进而得出以1,3-二丁基苯并三氮唑溴盐离子液体为最佳促进剂,用量为0.5 equiv;叔丁基过氧化氢为最佳氧化剂,用量为0.2 m L;水为最佳溶剂,用量为0.1 mL;并在120 oC下反应24 h为最佳反应条件。接着,我们对反应的普适性进行了研究,无论是吸电子基团还是给电子基团,反应都会得到中等到良好的产率。当进行克级规模反应时,反应产率与模型反应产率相当。我们也考察了离子液体的循环使用性,发现离子液体可以循环再利用五次且反应活性没有明显下降。最后,我们进行了反应的控制实验,从而得出反应是以自由基机理进行的。3,4-二氢嘧啶-2(1H)-(硫)酮类化合物具有非常重要的药理活性,在抗病毒、抗肿瘤、抗菌和消炎等领域有广阔的应用,因此其绿色合成的方法引起了人们广泛的关注。本文在以乙醇为溶剂回流1.5 h的条件下,以阳离子为咪唑、阴离子为对甲苯磺酸根的离子液体作为催化剂,对Biginelli反应进行了研究,从而合成了3,4-二氢嘧啶-2(1H)-(硫)酮类化合物。含有吲哚环的Pyrroloindoline以及Furoindoline骨架广泛存在于天然产物中,具有非常重要的生理活性和药用价值。铜催化的分子间吲哚炔丙基去芳构化反应构建了这类化合物,本文合成了构建该类化合的前体化合物—色醇和炔丙酯化合物。更多还原

【Abstract】 With the emergence of the concepts of “green chemistry” and “atom economy”, forming a new C-C bond via transition-metal-catalyzed the activation of inactive C-H bond has been a hot research field. The C-C bond formation through C-H bond oxidative cross-coupling approach has great advantages, for it avoids the using of expensive metal catalysts in this process. Cross-dehydrogenative coupling(CDC) reaction is one of the typical representatives. Nowadays, metal-free catalyzed CDC reaction has been the new hotspot. However, study of using classical ionic liquids which contained heterocyclic structure as promoters or catalysts in the CDC reaction has not been reported. Based on this, we launched our research work.Firstly, based on our research in the synthesis and application of ionic liquids, a series of simple structure of the ionic liquid containing bromine negative ions were synthesized, and their structures had been characterized.Then, 5-(aryloxy)-1H-pyrazole-4-carbaldehydes were regarded as substrates, IL-promoted intramolecular CDC reaction chromeno[2,3-c]pyrazol-4(1H)-one formation conditions were optimized. We concluded that 1,3-dibutyl-1H-benzo[d]-[1,2,3]triazol-3-ium bromide was the optimum promoter which consumption was 0.5 equiv; tert-butyl hydroperoxide(TBHP) was the best oxidant which consumption was 0.2 mL; H2 O was the excellent solvent which consumption was 0.1 mL; and the reaction mixture was stirred at 90 oC for 24 h was the optimum condition. Then, the scope of the reaction was investigated. Substrates bearing either electron-withdrawing groups or electron-donating groups all led to the annulation products in moderate to good yields. Gram-scale oxidative coupling reaction was investigated, and the yield of product was considerable with mode reaction. The circulation use of the ionic liquid was also inspected which could be utilized repeatedly five times without any loss of activity. Finally, controlled experiments were carried out. We concluded that this reaction may be a radical reaction.3,4-Dihydropyrimidin-2(1H)-(thio)ones compounds which have important pharmacological activity have wide application in the field of anti-microbial, anti-virus, anti-tumor, anti-bactericidal and inflammatory, so its green method of synthesis has aroused widespread concern. The Biginelli Reaction which catalyst is ionic liquid with imidazolium cation and p-toluenesulfonic acid anion, solvent is ethanol is be studied under reflux condition for 1.5 h in this paper. 3,4-Dihydropyrimidin-2(1H)-(thio)ones compounds are be synthesized.The skeleton of Pyrroloindoline and Furoindoline with indole ring are widely present in natural products. They have very important physiological activity and medicinal value. Copper-catalyzed intermolecular asymmetric propargylic dearomatization of indoles build these compounds. This paper synthesize precursor compound of these compounds-tryptophol and propargyl ester.更多还原