亲电试剂和N-卤代酰亚胺的偶联反应—卤键的作用
发布时间：2019-02-18 12:23
【摘要】：邻苯二甲酰亚胺类化合物作为一种重要的合成原料和中间体,在医药、农药和有机材料等多个研究领域中都有极为重要的应用。因此,该类化合物的合成一直受到科学家的关注。本论文提出了一种利用多重卤键活化模式,实现了亲电试剂卤代烃和N-卤代酰亚胺的偶联反应,提供了合成邻苯二甲酰亚胺类化合物的新思路。该合成方法具有快速高效、无需金属参与、条件温和、底物适用范围广及原子利用率高等优点。当向反应体系中引入DBU时,作为亲电试剂的卤代烃和N-卤代酰亚胺的偶联反应得以发生,生成了胺化产物。反应的最佳条件是以二甲基亚砜作为溶剂,N-卤代酰亚胺(1.2倍量)、DBU(1.2倍量)与1当量的卤代烃在室温下反应,以较好的产率(25%-93%)获得目标产物。实验结果表明:在反应底物卤代烃中,反应活性顺序为:碘代烷烃溴代烷烃氯代烷烃;反应物N-卤代酰亚胺的反应活性:氯代酰亚胺的活性要高于溴代酰亚胺。在实验结果基础上,本论文提出了由多重卤键活化的偶联反应的反应机理。卤键的存在同时活化了N-卤代酰亚胺和卤代烃两种底物,使得该偶联反应可以高效平稳发生。我们的这种合成方法以及机理的提出丰富了卤键化学,为卤键活化在有机合成中的应用提供了新的例证。
[Abstract]:As an important synthetic raw material and intermediate, phthalimides have been widely used in many fields such as medicine, pesticide and organic materials. Therefore, the synthesis of this kind of compounds has been concerned by scientists. In this paper, a coupling reaction of electrophilic reagents halogenated hydrocarbons and N-halogenated imides is proposed by using the multiple halogenated bond activation mode, which provides a new idea for the synthesis of phthalimide compounds. The method has the advantages of fast and high efficiency, no metal participation, mild conditions, wide application range of substrates and high atomic utilization rate. When DBU was introduced into the reaction system, the coupling reaction of halogenated hydrocarbons and N-halogenimide as electrophilic reagents took place, resulting in amination products. The optimum reaction conditions were as follows: dimethyl sulfoxide was used as solvent, N-halogenated imide (1.2-fold), DBU (1.2-fold) reacted with 1 equivalent halogenated hydrocarbon at room temperature, and the target product was obtained in a better yield (25-93%). The experimental results show that the order of reaction activity of halogenated hydrocarbons is as follows: iodinated alkanes bromoalkanes chlorinated alkanes, the reactivity of N-halogenated imide is higher than that of bromoimide, and the reaction activity of N-haloimide is higher than that of bromoimide. Based on the experimental results, the mechanism of the coupling reaction activated by multiple halogen bonds was proposed. The existence of halogen bond activates both N-halogenimide and halogenated hydrocarbons, which makes the coupling reaction take place smoothly and efficiently. This method and its mechanism enrich the halogen bond chemistry and provide a new example for the application of halogen bond activation in organic synthesis.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25
[Abstract]:As an important synthetic raw material and intermediate, phthalimides have been widely used in many fields such as medicine, pesticide and organic materials. Therefore, the synthesis of this kind of compounds has been concerned by scientists. In this paper, a coupling reaction of electrophilic reagents halogenated hydrocarbons and N-halogenated imides is proposed by using the multiple halogenated bond activation mode, which provides a new idea for the synthesis of phthalimide compounds. The method has the advantages of fast and high efficiency, no metal participation, mild conditions, wide application range of substrates and high atomic utilization rate. When DBU was introduced into the reaction system, the coupling reaction of halogenated hydrocarbons and N-halogenimide as electrophilic reagents took place, resulting in amination products. The optimum reaction conditions were as follows: dimethyl sulfoxide was used as solvent, N-halogenated imide (1.2-fold), DBU (1.2-fold) reacted with 1 equivalent halogenated hydrocarbon at room temperature, and the target product was obtained in a better yield (25-93%). The experimental results show that the order of reaction activity of halogenated hydrocarbons is as follows: iodinated alkanes bromoalkanes chlorinated alkanes, the reactivity of N-halogenated imide is higher than that of bromoimide, and the reaction activity of N-haloimide is higher than that of bromoimide. Based on the experimental results, the mechanism of the coupling reaction activated by multiple halogen bonds was proposed. The existence of halogen bond activates both N-halogenimide and halogenated hydrocarbons, which makes the coupling reaction take place smoothly and efficiently. This method and its mechanism enrich the halogen bond chemistry and provide a new example for the application of halogen bond activation in organic synthesis.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25
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1 陈光旭;徐梊Z，
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