【作者】 刘超；

【导师】 文丽荣；

【作者基本信息】 青岛科技大学 ， 应用化学， 2010， 硕士

【摘要】 β-邻氯芳基杂环烯酮缩胺有着极高的反应活性,是有机化学中碳-碳键和碳-氮键形成的一种优秀合成子。而新型的合成方法多组分反应(MCR)和串联反应不仅能快速大量地合成具有结构多样性和复杂性的化合物和化合库,而且具有环保,操作简便等优势,已经成为有机合成中强有力的手段。本论文基于β-邻氯芳基杂环烯酮缩胺独特结构和突出的反应性能,采用新型的有机合成方法,构筑和发展新型1, 8-二氮杂萘类杂环体系的合成方法。从多样性导向合成来看,该方法灵活,富有变换,具有高化学选择性,能显著提高键形成的效率。论文研究了以β-邻氯芳基杂环烯酮缩胺,芳醛和乙酰乙酸乙酯在三乙胺和K2CO3催化下进行多组分串联反应,构建新型1, 8-二氮杂萘类化合物骨架。研究了溶剂,催化剂,原料摩尔比等条件对反应的影响,确定了最佳反应条件为:0.4当量Et3N做催化剂,β-邻氯芳基杂环烯酮缩胺,芳醛和乙酰乙酸乙酯的摩尔比为1:1.2:1.2,乙腈为溶剂回流反应。反应完成后,不分离中间体,在DMF溶剂中使用K2CO3为催化剂进行串联反应,高产率的得到目标产物。反应条件温和,操作简便,产品易于纯化。这种方法合成苯并二氮杂萘类化合物迄今未见文献报道,是一种环境友好的方法。合成中间体(4c)1个,目标化合物(5a-o)15个。论文探讨了β-邻氯芳基杂环烯酮缩,芳醛和麦氏酸进行多组分串联反应,生成了一类新型的1, 8-二氮杂萘类化合物。合成中间体(7c)1个,目标化合物(8a-l)12个。在反应中,有7个不同活性位点参与反应,经历了一系列Knoevenagel缩合、氮杂烯反应、环化和分子内亲核取代反应,生成了两个新环、三个新键,充分体现了“原子经济性”。所合成的化合物均经IR、1H NMR、13C NMR和高分辨质谱分析表征。其中对化合物5c进行了X-单晶衍射分析,确定了其精确的空间结构。并提出了可能的反应机理。更多还原

【Abstract】 β- (2-Chloroaryl)-heterocyclic ketene aminals are good synthons in the form of C-C bond and C-N bond because of its high reactivity. They play a significant role in organic synthesis and much attention has been given to them. New strategy of organic synthesis-multicomponent reaction and tandem reaction-can synthesize libraries of compounds with structural complexity and diversity rapidly, by virtue of their convergence, productivity, ease of execution, and generally high yields of products, have become the most enabling synthetic tools in organic synthesis. This thesis focus on building new framework of [1, 8]naphthyridine from high functionalβ- (2-Chloroaryl)-heterocyclic ketene aminals. This method is flexible, which includs the advantages of high chemo- and regioselectivity and high bond-forming efficiency.In this thesis, Tetrahydroimidazo[3,2,1-ij]bezeno[1,8]naphthyridine derivatives unreported in the literatures have been synthesised withβ- (2-chloroaryl)- heterocyclic ketene aminals by the multicomponent and tandem reactions in the presence of Et3N and K2CO3 as catalyst. The reaction conditions including solvent, catalyst and molar ratio were also investigated. The optimal condition was Et3N as catalyst, molar ratio ofβ- (2-chloroaryl) - heterocyclic ketene aminals, ethyl acetoacetate and aldehyde with1: 1.2: 1.2 and acetonitrile as solvent. The intermediate was not separated, and then proceeded intramolecular cyclization reactions in the presence of K2CO3 in DMF to obtain the target compounds in high yields. These reactions were very mild, convenient and effective. One intermediate (4c) and 15 target compounds (5a-o) were synthesized.Then,β- (2-Chloroaryl)-heterocyclic ketene aminals react with aldehyde and Meldrum’s acid to get a new skeleton of 1, 8- naphthyridine. One intermediate (7c) and 12 target compounds (8a-l) were synthesized.In this reaction, seven different active sites were involved; three new bonds and two new rings were constructed with all reactants which efficiently utilized via a sequence of Knoevenagel condensation, aza-ene reaction, cyclization and intramolecular nucleophilic substitution reactions. It fully reflects the“atom economy”in this reactionThe structures of all the target compounds were confirmed by IR, 1 H NMR, 13 C NMR, and HRMS, and the plausible mechanism was also presented. The unambiguous molecular structure of 5c was determined by X-ray diffraction analysis.更多还原