【摘要】：在金屬介導(dǎo)的偶聯(lián)反應(yīng)中,官能團(tuán)化的氯代芳烴比相應(yīng)的溴代芳烴和碘代芳烴在實(shí)際應(yīng)用上更加廣泛,然而氯代芳烴作為底物時(shí),反應(yīng)卻更加困難。研究發(fā)現(xiàn)釕催化N-活化芳烴鄰位C-H鍵可以得到單芳基化和雙芳基化偶聯(lián)產(chǎn)物,氯代、溴代和碘代芳烴都可以發(fā)生反應(yīng),但反應(yīng)活性不同。C-C鍵的形成是有機(jī)合成化學(xué)中最基本轉(zhuǎn)化之一,雖然通過(guò)釕催化N-活化芳烴鄰位C-H鍵和鹵代芳烴偶聯(lián)構(gòu)建C-C鍵已有報(bào)道,但目前使用的親電試劑主要是活性較高的溴代芳烴,碘代芳烴,而使用活性較低的氯代芳烴,同時(shí)應(yīng)用大基團(tuán)富電子的配體控制的選擇性活化特定位置C-H鍵進(jìn)行偶聯(lián)的研究鮮見(jiàn)報(bào)道。本文研究了膦配體-釕催化含氮導(dǎo)向基團(tuán)芳基化合物鄰位C-H鍵和氯代芳烴或雜環(huán)氯代烴的偶聯(lián)反應(yīng)并拓展了氯代芳烴作為反應(yīng)底物范圍。本文重點(diǎn)對(duì)反應(yīng)配體的種類進(jìn)行了探究,發(fā)現(xiàn)大基團(tuán)的含膦化合物作為配體時(shí),得到了很好的產(chǎn)率,且配體的選擇性很好。通過(guò)大量的實(shí)驗(yàn)優(yōu)化,獲得了優(yōu)化反應(yīng)條件:以商業(yè)化的二聚體釕化合物[RuC12(p-cymene)2]作為催化劑(催化劑用量1 mol%),以N-甲基吡咯烷酮作為溶劑,新型大基團(tuán)富電子含膦化合物作為配體(配體用量為2 mol%),碳酸鉀作為堿,氯代芳烴作為底物進(jìn)行偶聯(lián)反應(yīng)。對(duì)反應(yīng)底物進(jìn)行拓展研究,選擇活性不高的氯代芳烴或者雜環(huán)氯代烴作為底物,得到了一系列新的化合物,產(chǎn)物收率可以達(dá)到80%左右。又對(duì)導(dǎo)向基團(tuán)進(jìn)行了考察,并得到了一系列新的化合物,產(chǎn)物收率可以達(dá)到中等水平,同時(shí)又進(jìn)行了連續(xù)化反應(yīng)的研究,可以得到連續(xù)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.
【學(xué)位授予單位】：合肥工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.25

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