N-活化芳烃α-H与卤代芳烃偶联反应的研究
发布时间:2019-03-08 19:31
【摘要】:在金属介导的偶联反应中,官能团化的氯代芳烃比相应的溴代芳烃和碘代芳烃在实际应用上更加广泛,然而氯代芳烃作为底物时,反应却更加困难。研究发现钌催化N-活化芳烃邻位C-H键可以得到单芳基化和双芳基化偶联产物,氯代、溴代和碘代芳烃都可以发生反应,但反应活性不同。C-C键的形成是有机合成化学中最基本转化之一,虽然通过钌催化N-活化芳烃邻位C-H键和卤代芳烃偶联构建C-C键已有报道,但目前使用的亲电试剂主要是活性较高的溴代芳烃,碘代芳烃,而使用活性较低的氯代芳烃,同时应用大基团富电子的配体控制的选择性活化特定位置C-H键进行偶联的研究鲜见报道。本文研究了膦配体-钌催化含氮导向基团芳基化合物邻位C-H键和氯代芳烃或杂环氯代烃的偶联反应并拓展了氯代芳烃作为反应底物范围。本文重点对反应配体的种类进行了探究,发现大基团的含膦化合物作为配体时,得到了很好的产率,且配体的选择性很好。通过大量的实验优化,获得了优化反应条件:以商业化的二聚体钌化合物[RuC12(p-cymene)2]作为催化剂(催化剂用量1 mol%),以N-甲基吡咯烷酮作为溶剂,新型大基团富电子含膦化合物作为配体(配体用量为2 mol%),碳酸钾作为碱,氯代芳烃作为底物进行偶联反应。对反应底物进行拓展研究,选择活性不高的氯代芳烃或者杂环氯代烃作为底物,得到了一系列新的化合物,产物收率可以达到80%左右。又对导向基团进行了考察,并得到了一系列新的化合物,产物收率可以达到中等水平,同时又进行了连续化反应的研究,可以得到连续芳基化化合物。
[Abstract]:In metal-mediated coupling reaction, functionalized chlorinated aromatic hydrocarbons are more widely used than the corresponding brominated aromatic hydrocarbons and iodinated aromatics. However, chloro aromatic hydrocarbons are more difficult to react when they are used as substrates. It was found that ruthenium catalyzed N-activation of N-arene ortho-C ~ (2 +) H bond can give monoarylation and bis (aryl) coupling products, and chloro, brominated and iodinated aromatic hydrocarbons can all react with each other. The formation of C-C bond is one of the most basic transformations in organic synthesis chemistry, although it has been reported that C-C bond is formed by ruthenium-catalyzed N-activated aromatic ortho-C bond and halogenated aromatic hydrocarbon coupling, and C-C bond formation is one of the most basic transformations in organic synthesis chemistry. But the electrophilic reagents used at present are mainly brominated aromatic hydrocarbons with higher activity, iodinated aromatics, and chloro aromatic hydrocarbons with lower activity. At the same time, the application of electron-rich ligand-controlled selective activation of C _ (?) H bond to coupling has been rarely reported. In this paper, phosphine ligand-ruthenium catalyzes the coupling reaction between N-containing aryl compounds o-C, H bond and chlorinated aromatic hydrocarbons or heterocyclic chlorinated hydrocarbons, and extends the range of chloro-aromatic hydrocarbons as reaction substrates. In this paper, the species of reactive ligands were investigated. It was found that the large groups of phosphine compounds were used as ligands in good yields and the selectivity of ligands was very good. The optimum reaction conditions were obtained by a large number of experiments. The commercial ruthenium dimer [RuC12 (p-cymene) 2] was used as catalyst (catalyst dosage was 1 mol%) and N-methyl pyrrolidone was used as solvent. A novel electron-rich phosphine-containing compound was used as ligand (ligand dosage was 2 mol%), potassium carbonate was used as base, and aromatic chloride was used as substrate for coupling reaction. A series of new compounds were obtained by selecting low active chlorinated aromatic hydrocarbons or heterocyclic chlorinated hydrocarbons as substrates. The yield of the products was about 80%. A series of new compounds were obtained and the yield of the products reached the medium level. At the same time, the continuous arylation reaction was carried out and the continuous arylation compounds were obtained.
【学位授予单位】:合肥工业大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:O621.25
[Abstract]:In metal-mediated coupling reaction, functionalized chlorinated aromatic hydrocarbons are more widely used than the corresponding brominated aromatic hydrocarbons and iodinated aromatics. However, chloro aromatic hydrocarbons are more difficult to react when they are used as substrates. It was found that ruthenium catalyzed N-activation of N-arene ortho-C ~ (2 +) H bond can give monoarylation and bis (aryl) coupling products, and chloro, brominated and iodinated aromatic hydrocarbons can all react with each other. The formation of C-C bond is one of the most basic transformations in organic synthesis chemistry, although it has been reported that C-C bond is formed by ruthenium-catalyzed N-activated aromatic ortho-C bond and halogenated aromatic hydrocarbon coupling, and C-C bond formation is one of the most basic transformations in organic synthesis chemistry. But the electrophilic reagents used at present are mainly brominated aromatic hydrocarbons with higher activity, iodinated aromatics, and chloro aromatic hydrocarbons with lower activity. At the same time, the application of electron-rich ligand-controlled selective activation of C _ (?) H bond to coupling has been rarely reported. In this paper, phosphine ligand-ruthenium catalyzes the coupling reaction between N-containing aryl compounds o-C, H bond and chlorinated aromatic hydrocarbons or heterocyclic chlorinated hydrocarbons, and extends the range of chloro-aromatic hydrocarbons as reaction substrates. In this paper, the species of reactive ligands were investigated. It was found that the large groups of phosphine compounds were used as ligands in good yields and the selectivity of ligands was very good. The optimum reaction conditions were obtained by a large number of experiments. The commercial ruthenium dimer [RuC12 (p-cymene) 2] was used as catalyst (catalyst dosage was 1 mol%) and N-methyl pyrrolidone was used as solvent. A novel electron-rich phosphine-containing compound was used as ligand (ligand dosage was 2 mol%), potassium carbonate was used as base, and aromatic chloride was used as substrate for coupling reaction. A series of new compounds were obtained by selecting low active chlorinated aromatic hydrocarbons or heterocyclic chlorinated hydrocarbons as substrates. The yield of the products was about 80%. A series of new compounds were obtained and the yield of the products reached the medium level. At the same time, the continuous arylation reaction was carried out and the continuous arylation compounds were obtained.
【学位授予单位】:合肥工业大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:O621.25
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