铜和钯催化的C-S和C-C偶联反应研究
发布时间：2018-12-11 06:54
【摘要】：一直以来,C-C、C-S及其它碳-杂键的构建占据着重要地位在有机化学合成中,含有C-S的芳基硫醚具有药物活性和生理活性,在功能性高分子材料的方面,亦是重要组分之一。含有C-C键的三亚苯及其衍生物是重要的多环芳烃,具有特殊的光电性能,在材料方面有很大的应用。本文主要研究了由铜催化硫化物与芳硼酸合成芳基硫醚,由钯催化2-碘联苯与碘苯合成三亚苯的方法。首先选用了无水CuSO4催化芳硼酸与2-巯基苯甲酸在溶剂水条件下反应生成芳基硫醚类化合物,配体为无毒的DL-脯氨酸,反应体系符合当前绿色化学发展。在后处理分离提纯中既用到了一般柱层析的方法,又找到了简单的过滤提纯方法,该方法操作简单且不用有机溶剂,达到绿色化学要求。然后用CuSO4催化同时含有羧基和硝基的5,5'-二硫代双(2-硝基苯甲酸)与芳硼酸反应,获得19种芳基硫醚类化合物,产率偏低。接下来用自制的CuO催化5,5'-二硫代双(2-硝基苯甲酸)与芳硼酸反应,与CuSO4催化相比,提高了其相应产率。合成芳基硫醚类化合物共用到了三种实验方法,与传统方法相比,整个体系在空气环境条件下即可进行,碳源也由低毒、商品化芳硼酸取代了卤代苯。最后用我们课题组制备的钯配合物催化2-碘联苯与碘苯反应合成三亚苯,该体系与传统合成三亚苯相比,只需单金属催化,实现了双重钯催化C-H活化和C-C键的形成。与传统的多聚环化反应相比,此过程易控制,且不需特殊气体保护。
[Abstract]:For a long time, the construction of C-CnC-S and other carbon-hetero-bonds occupies an important position in organic chemistry synthesis. Aryl sulfides containing C-S have drug activity and physiological activity, and in the aspect of functional polymer materials, It is also an important component. Triphenyl containing C-C bond and its derivatives are important polycyclic aromatic hydrocarbons (PAHs) with special optoelectronic properties and are widely used in materials. The synthesis of aryl sulfide from copper catalyzed sulphide and aryl boric acid and synthesis of triphenyl from 2-iodiphenyl and iodobenzene catalyzed by palladium were studied in this paper. Firstly, aryl sulfides were synthesized from aryl boric acid and 2-mercaptobenzoic acid catalyzed by anhydrous CuSO4 in solvent water. The ligands were nontoxic DL- proline. The reaction system was in line with the development of green chemistry. The general column chromatography method and the simple filtration and purification method are used in the post-treatment separation and purification. The method is simple and does not use organic solvent to meet the requirements of green chemistry. Then 19 aryl thioether compounds were obtained by the reaction of 5'5'5 '-dithiobis (2 nitrobenzoic acid) with arylboric acid, which contained carboxyl and nitro groups, and the yield was low. Then the self-made CuO was used to catalyze the reaction of 5o 5o dithiobis (2-nitrobenzoic acid) with aryl boric acid. Compared with the catalyst of CuSO4, the corresponding yield was increased. Three experimental methods have been used to synthesize aryl sulfide compounds. Compared with the traditional methods, the whole system can be carried out under the condition of air environment, and the carbon source is also low toxic, commercial aryl boric acid has replaced halogenated benzene. Finally, the palladium complex prepared by our research group was used to catalyze the reaction of 2-iodibiphenyl with iodiobenzene to synthesize triphenyl. Compared with the traditional synthesis of triphenyl, this system only needs a single metal catalyst to realize the activation of C-H and the formation of C-C bond catalyzed by double palladium. Compared with traditional poly-cyclization reaction, this process is easy to control and does not require special gas protection.
【学位授予单位】：温州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
本文编号：2372094
[Abstract]:For a long time, the construction of C-CnC-S and other carbon-hetero-bonds occupies an important position in organic chemistry synthesis. Aryl sulfides containing C-S have drug activity and physiological activity, and in the aspect of functional polymer materials, It is also an important component. Triphenyl containing C-C bond and its derivatives are important polycyclic aromatic hydrocarbons (PAHs) with special optoelectronic properties and are widely used in materials. The synthesis of aryl sulfide from copper catalyzed sulphide and aryl boric acid and synthesis of triphenyl from 2-iodiphenyl and iodobenzene catalyzed by palladium were studied in this paper. Firstly, aryl sulfides were synthesized from aryl boric acid and 2-mercaptobenzoic acid catalyzed by anhydrous CuSO4 in solvent water. The ligands were nontoxic DL- proline. The reaction system was in line with the development of green chemistry. The general column chromatography method and the simple filtration and purification method are used in the post-treatment separation and purification. The method is simple and does not use organic solvent to meet the requirements of green chemistry. Then 19 aryl thioether compounds were obtained by the reaction of 5'5'5 '-dithiobis (2 nitrobenzoic acid) with arylboric acid, which contained carboxyl and nitro groups, and the yield was low. Then the self-made CuO was used to catalyze the reaction of 5o 5o dithiobis (2-nitrobenzoic acid) with aryl boric acid. Compared with the catalyst of CuSO4, the corresponding yield was increased. Three experimental methods have been used to synthesize aryl sulfide compounds. Compared with the traditional methods, the whole system can be carried out under the condition of air environment, and the carbon source is also low toxic, commercial aryl boric acid has replaced halogenated benzene. Finally, the palladium complex prepared by our research group was used to catalyze the reaction of 2-iodibiphenyl with iodiobenzene to synthesize triphenyl. Compared with the traditional synthesis of triphenyl, this system only needs a single metal catalyst to realize the activation of C-H and the formation of C-C bond catalyzed by double palladium. Compared with traditional poly-cyclization reaction, this process is easy to control and does not require special gas protection.
【学位授予单位】：温州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
【参考文献】
相关期刊论文 前1条
1 Jun-Ke Wang;Ying-Xiao Zong;Xi-Cun Wang;Yu-Lai Hu;Guo-Ren Yue;;Synthesis of N-benzothiazol-2-yl-amides by Pd-catalyzed C(sp~2) H functionalization[J];Chinese Chemical Letters;2015年11期
，本文编号：2372094
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