吡啶衍生物的绿色合成研究

发布时间：2018-04-22 15:54

本文选题：吡啶 + 1　；参考：《华侨大学》2017年硕士论文

【摘要】：在有机合成中,亚甲基桥联的双1,3-二羰基化合物是一种非常重要的中间体或构建骨架。杂环化合物种类繁多,数量庞大在自然界中占有重要地位,而在所有含氮六元杂环中吡啶类化合物因其在医药,农药,食品添加剂等众多方面表现出来的巨大价值,吸引着众多化学家不断探索符合绿色化学规则的全新的合成方法。我们以1,3-二羰基化合物,DMSO和铵盐三组分为原料,在酸的催化下实现了无过渡金属催化氧化甲基化反应/Hantzsch吡啶合成法串联反应,这种分子间的环加成反应条件温和,原料易得,其中值得一提的是,DMSO分别作为溶剂,亚甲基化试剂和氧化剂参与到反应中,巧妙的实现了高效、经济化学策略。完全不饱和的单环1,4-氧氮杂卓类化合物由于它反芳香性的特征,很难用传统的合成方法获得,我们发现了一种极具吸引力并且操作简便的分子内/分子间捕捉原位生成的1,4-氧氮杂卓构建2-烷氧基吡啶类化合物或者与二氢呋喃并[2,3-b]吡啶类化合物的级联反应。该方法对一系列官能团包括碘,末端炔烃,和游离胺等特殊官能团显示出良好的耐受性。这种环境友好的反应是在无金属的条件下进行的,水是转化的产生的唯一副产物。
[Abstract]:In organic synthesis, methylene-bridged bis-(1 +)-3-dicarbonyl compound is a very important intermediate or framework. Heterocyclic compounds have a large number of heterocyclic compounds and play an important role in nature. Pyridine compounds in all nitrogen-containing heterocyclic compounds have shown great value in many aspects, such as medicine, pesticides, food additives and so on. It attracts many chemists to explore new synthetic methods that conform to green chemistry rules. In this paper, a series reaction of non-transition metal catalyzed oxidative methylation reaction and synthesis of Hantzsch pyridine was carried out by using the three components of 1,10-dicarbonyl compound (DMSO) and ammonium salt as raw materials. The conditions of the cycloaddition reaction between the molecules were mild and the raw materials were easy to obtain. It is worth mentioning that DMSO is used as solvent, methylene reagent and oxidant to participate in the reaction respectively, and the high efficiency and economical chemical strategy is achieved. The completely unsaturated monocyclic 1-trioxy-4-oxazepines are difficult to obtain by traditional synthetic methods because of their anti-aromatic properties. We have found an attractive and easy to operate intramolecular / intramolecular capture of 1o 4-oxazazepines to form 2-alkoxy pyridines or cascade reactions with dihydrofurano [2o 3-b] pyridines. The method shows good tolerance to a series of functional groups, including iodine, terminal alkynes, and free amines. This environmental-friendly reaction takes place without metal and water is the only byproduct of the conversion.
【学位授予单位】：华侨大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626.32

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