【摘要】：一直以來,C-C、C-S及其它碳-雜鍵的構(gòu)建占據(jù)著重要地位在有機(jī)化學(xué)合成中,含有C-S的芳基硫醚具有藥物活性和生理活性,在功能性高分子材料的方面,亦是重要組分之一。含有C-C鍵的三亞苯及其衍生物是重要的多環(huán)芳烴,具有特殊的光電性能,在材料方面有很大的應(yīng)用。本文主要研究了由銅催化硫化物與芳硼酸合成芳基硫醚,由鈀催化2-碘聯(lián)苯與碘苯合成三亞苯的方法。首先選用了無水CuSO4催化芳硼酸與2-巰基苯甲酸在溶劑水條件下反應(yīng)生成芳基硫醚類化合物,配體為無毒的DL-脯氨酸,反應(yīng)體系符合當(dāng)前綠色化學(xué)發(fā)展。在后處理分離提純中既用到了一般柱層析的方法,又找到了簡(jiǎn)單的過濾提純方法,該方法操作簡(jiǎn)單且不用有機(jī)溶劑,達(dá)到綠色化學(xué)要求。然后用CuSO4催化同時(shí)含有羧基和硝基的5,5'-二硫代雙(2-硝基苯甲酸)與芳硼酸反應(yīng),獲得19種芳基硫醚類化合物,產(chǎn)率偏低。接下來用自制的CuO催化5,5'-二硫代雙(2-硝基苯甲酸)與芳硼酸反應(yīng),與CuSO4催化相比,提高了其相應(yīng)產(chǎn)率。合成芳基硫醚類化合物共用到了三種實(shí)驗(yàn)方法,與傳統(tǒng)方法相比,整個(gè)體系在空氣環(huán)境條件下即可進(jìn)行,碳源也由低毒、商品化芳硼酸取代了鹵代苯。最后用我們課題組制備的鈀配合物催化2-碘聯(lián)苯與碘苯反應(yīng)合成三亞苯,該體系與傳統(tǒng)合成三亞苯相比,只需單金屬催化,實(shí)現(xiàn)了雙重鈀催化C-H活化和C-C鍵的形成。與傳統(tǒng)的多聚環(huán)化反應(yīng)相比,此過程易控制,且不需特殊氣體保護(hù)。
[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.
【學(xué)位授予單位】：溫州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

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

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本文編號(hào)：2372094