本文選題：C-H活化 + C-O/S偶聯(lián)��； 參考：《內(nèi)蒙古師范大學(xué)》2017年碩士論文

【摘要】：由于C-H鍵結(jié)構(gòu)單元在自然界中的廣泛存在,構(gòu)建C-C或C-雜原子鍵的過渡金屬催化C-H鍵活化反應(yīng)研究已成為有機(jī)及生物科學(xué)領(lǐng)域研究的熱點(diǎn);并且廣泛應(yīng)用于藥物、材料、香料等領(lǐng)域。通常情況下,合成C-C或C-雜原子鍵的方法主要是先讓其原料連接一種化學(xué)鍵,然后再把這種化學(xué)鍵轉(zhuǎn)換成目標(biāo)化學(xué)鍵。所以研究直接轉(zhuǎn)變C-H鍵為C-C或C-R鍵,不僅可以提高反應(yīng)的原子經(jīng)濟(jì)性,而且可以增加多步合成反應(yīng)的總效率。該論文研究?jī)?nèi)容包括兩部分:第一部分是過渡金屬銅鹽催化醛基C-H鍵活化與醇C-O鍵合成酯;第二部分是負(fù)載型納米鈀催化2-苯基吡啶鄰位誘導(dǎo)sp2C-H鍵的活化與芳香磺酰氯C-S鍵偶聯(lián)合成砜及機(jī)理研究。得出以下結(jié)論:探索廉價(jià)金屬Cu+/Cu2+鹽催化醛醇直接氧化合成酯的反應(yīng),其中以CuCl為催化劑,過氧化叔丁醇(TBHP)為氧化劑,反應(yīng)溫度為80℃,反應(yīng)時(shí)間24 h,對(duì)甲氧基苯甲酸甲酯的產(chǎn)率可達(dá)90.0%。研究結(jié)果表明連有不同取代基的芳香醛與相同醇反應(yīng)時(shí),其反應(yīng)受電子效應(yīng)沒有顯著的影響,但不同的醇與對(duì)甲氧基苯甲醛反應(yīng)時(shí),醇的空間位阻越大,產(chǎn)率越低。以采用浸漬-還原法制備負(fù)載型納米鈀粒子Pd/γ-Al2O3為催化劑、乙基苯為溶劑、并以K2CO3為堿中和反應(yīng)過程中產(chǎn)生的HCl,催化誘導(dǎo)2-苯基吡啶鄰位C-H鍵活化與芳香磺酰氯C-S鍵偶聯(lián)合成砜的反應(yīng)。反應(yīng)溫度為125℃,反應(yīng)時(shí)間24 h,2-苯基吡啶的轉(zhuǎn)化率為83.0%,目標(biāo)產(chǎn)物產(chǎn)率達(dá)73.0%。并對(duì)該催化劑進(jìn)行了 3次回收并重復(fù)利用試驗(yàn)后,目標(biāo)產(chǎn)物產(chǎn)率降低了 44.0%。為了說(shuō)明其回收率低的原因及該體系的反應(yīng)機(jī)理,用AAS、XPS和TEM實(shí)驗(yàn)檢測(cè)方法對(duì)催化劑中鈀性質(zhì)進(jìn)行了一系列的表征,同時(shí)進(jìn)行了熱過濾以及對(duì)濾液進(jìn)行了 ICP-MS檢測(cè)。AAS及TEM測(cè)試結(jié)果表明,目標(biāo)產(chǎn)物降低44.0%的可能原因?yàn)榇呋瘎┲蠵d的流失所引起的;同時(shí)通過熱過濾實(shí)驗(yàn)也證明了催化劑中Pd含量的減少。通過XPS分析可知,該反應(yīng)中起催化循環(huán)作用的并不是Pd0/PdⅡ,所以證明負(fù)載型納米鈀催化的鄰位誘導(dǎo)2-苯基吡啶C-H鍵活化與芳香磺酰氯合成砜的磺酰化反應(yīng)為均相催化。
[Abstract]:Due to the widespread existence of C-H bond structural units in nature, the study of transition metal-catalyzed C-H bond activation of C-C or C-heteroatom bonds has become a hot topic in the field of organic and biological sciences, and has been widely used in drugs and materials. An area of spice, etc. In general, C-C or C-heteroatom bonds are synthesized by first connecting the material with a chemical bond, and then converting the chemical bond into the target chemical bond. Therefore, the direct conversion of C-H bond to C-C or C-R bond can not only improve the atomic economy of the reaction, but also increase the overall efficiency of the multi-step synthesis reaction. This paper includes two parts: the first part is transition metal copper salt catalyzed the activation of formyl C-H bond and synthesis of ester with alcohol C-O bond; In the second part, the activation of 2-phenylpyridine sp2C-H bond catalyzed by supported nano-palladium and the coupling of aromatic sulfonyl chloride C-S bond to sulfone were studied. The conclusions are as follows: the reaction of direct oxidation of aldehydes to esters catalyzed by Cu / Cu _ 2 salt was studied. The reaction temperature was 80 鈩，

本文編號(hào)：1976274