2-异腈基联苯自由基环化反应合成菲啶衍生物

发布时间：2018-01-13 06:02

本文关键词：2-异腈基联苯自由基环化反应合成菲啶衍生物　出处：《大连理工大学》2016年硕士论文　论文类型：学位论文

【摘要】：菲啶在有机化学以及药物化学领域是一类非常重要的结构单元。菲啶类化合物具有非常好的生物活性,被广泛用于抗肿瘤、抗病毒、杀菌、治疗白血病药物的研发。同时,因其具有优良的光电性能,在功能材料领域也有重要用途。因此,菲啶衍生物的合成很受研究者关注。然而,传统的合成菲啶的方法存在一些不足,比如条件苛刻,反应步骤较长,原料不易得,产率较低等。本文通过2-异腈基联苯类化合物的自由基环化反应合成菲啶衍生物,实现了无过渡金属参与的6-芳／烷基硫取代的菲啶衍生物以及6-三氯甲基取代的菲啶衍生物的合成,具体工作如下：1)以邻溴苯胺类与苯硼酸类化合物为原料,根据参考文献,经过Suzuki偶联、甲酰化、酰胺脱水后合成了多种异腈化合物。2)异腈是与CO分子结构相似的非常活泼的有机化合物,是一类良好的自由基受体。本课题组发现了一种TBPB促进的2-异腈联苯与硫酚／醇反应构建菲啶环的方法,提出了反应的机理并且给出了依据,该方法能够适应多种取代基比如乙酰基、酯基、氰基、叔丁基、卤素等,并能获得中等收率的产品,是合成6-芳基硫取代的菲啶的实用方法。3)三氯甲基易于衍生化,可以转化为相应的甲基、二氯甲基、三氟甲基、羧基、酯基以及恶唑类等。2-异腈基联苯与便宜的四氯化碳,在BPO的引发下,可以发生自由基加成和分子内环化反应,成功地合成6-三氯甲基取代的菲啶衍生物。经过三氯甲基的转化,可以很方便的制备6-甲基、羧基、三氟甲基、苯并咪唑等取代的菲啶衍生物。
[Abstract]:Phenanthroline is a very important structural unit in the field of organic chemistry and pharmaceutical chemistry. Phenanthroline compounds have very good biological activity and are widely used in anti-tumor, anti-virus and bactericidal. Research and development of leukemic drugs. At the same time, because of its excellent photoelectric properties, it also has important applications in the field of functional materials. Therefore, the synthesis of phenanthroline derivatives has attracted much attention. The traditional method of synthesizing phenanthroline has some shortcomings, such as harsh conditions, long reaction steps, and the raw materials are not easy to obtain. In this paper, the derivatives of phenanthroline were synthesized by radical cyclization of 2-isonitrile biphenyls. The synthesis of 6-aryl / alkyl sulfur substituted phenanthroline derivatives and 6-trichloromethyl substituted phenanthroline derivatives without transition metal participation was achieved. The specific work is as follows: (1) from o-bromoaniline and phenylboric acid compounds as raw materials, according to the reference, through Suzuki coupling, formylation. A variety of isonitrile compounds. 2) isonitrile is a very active organic compound similar to CO molecular structure after dehydration. TBPB promoted the reaction of 2-isonitrile biphenyls with thiophenol / alcohol to construct phenanthroline ring. The mechanism of the reaction was proposed and the basis was given. The method can be used for many substituents such as acetyl, ester, cyanide, tert-#china_person0#, halogen, etc. It is a practical method of synthesizing 6-aryl thiosubstituted phenanthroline. 3) trichloromethyl is easy to be derivatized and can be converted to corresponding methyl dichloromethyl trifluoromethyl carboxyl. Free radical addition and intramolecular cyclization can take place with cheap carbon tetrachloride, such as ester group, oxazole and so on. The 6-trichloromethyl substituted phenanthroline derivatives were successfully synthesized, and 6-methyl, carboxyl, trifluoromethyl, benzimidazole and other substituted phenanthroline derivatives could be easily prepared by the conversion of trichloromethyl.
【学位授予单位】：大连理工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

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