以甲酸為CO來源的鈀催化鹵代芳烴的羰基化反應(yīng)研究
發(fā)布時間：2018-07-17 22:22
【摘要】：作為最便宜的C1源之一,CO在工業(yè)領(lǐng)域中占據(jù)了不可替代的地位,但其高毒性和無色無味性質(zhì)以及高壓設(shè)備的要求阻礙了其在學(xué)術(shù)領(lǐng)域的廣泛應(yīng)用。近年來,開發(fā)和利用新的CO替代品吸引了有機化學(xué)家的越來越多的關(guān)注,并成為羰基化化學(xué)的研究熱點。根據(jù)CO產(chǎn)生的方式,已經(jīng)報道的方法可以分為兩類:異位和原位。原位生成CO是指在同一反應(yīng)管中產(chǎn)生并反應(yīng)CO,以這種方式,已經(jīng)開發(fā)了許多金屬羰基絡(luò)合物和有機化合物例如Mo(CO)6,甲酰胺,(CH2O)n和甲酸酚酯作為CO替代物。本論文以甲酸為CO來源的鈀催化鹵代芳烴的羰基化反應(yīng)研究,具有操作簡便、原料經(jīng)濟易得、反應(yīng)條件溫和、對底物適用范圍廣等優(yōu)點。論文主要內(nèi)容如下:1.首次實現(xiàn)了一鍋法以甲酸為羰源的鈀催化的羰基化Sonogashira反應(yīng)。以Pd(OAc)2為催化劑,PPh3為配體,Et3N為堿,一系列的碘苯和苯乙炔均能反應(yīng)并且有中等到良好的產(chǎn)率。2.發(fā)展了首例以甲酸為羰源的鈀催化的羰基化Suzuki反應(yīng)。以Pd(OAc)2為催化劑,PPh3為配體,K2CO3為堿,各類芳基碘代物和苯硼酸均能發(fā)生反應(yīng)并且有中等到良好的產(chǎn)率。芳基溴代物也能在該反應(yīng)條件下反應(yīng)。3.本論文工作研究了鈀催化或者路易斯酸催化羰基化合成甲酸芳基酯。我們希望用鈀催化羰基化即甲酸作為甲酰基源,在室溫下合成甲酸芳基酯衍生物。值得注意的是,這是鈀催化羰基化合成甲酸芳基酯衍生物的第一例報道。然而,在后續(xù)研究中,我們發(fā)現(xiàn)上述鈀催化劑體系中真正作用是路易斯酸,已經(jīng)實現(xiàn)了用路易斯酸催化劑代替昂貴的鈀催化劑,使該方法更加實用。4.本論文工作研究了一種高效、便捷的羰源:1,3,5-均三甲酸苯酚酯(TFBen)。TFBen在釋放出CO后的產(chǎn)物間苯三酚不會和其他親電試劑反應(yīng)并且我們已經(jīng)成功的把TFBen作為羰源應(yīng)用在一系列的羰基化反應(yīng)中。間苯三酚是便宜的和大量存在于植物中的化學(xué)品,并且還可以回收重新利用。
[Abstract]:As one of the cheapest sources of C1, CO occupies an irreplaceable position in the industrial field, but its high toxicity, colorless and odorless properties and high pressure equipment have hindered its wide application in the academic field. In recent years, the development and utilization of new CO substitutes attracted more and more attention from organologists and became carbonylation. According to the method produced by CO, the methods reported can be divided into two categories: heterotopic and in-situ. In situ generation of CO refers to the production and reaction of CO in the same reaction tube. In this way many metal carbonyl complexes and organic compounds such as Mo (CO) 6, formamide, (CH2O) n and formate carboxylate have been developed as CO alternatives. In this paper, the carbonylation of aryl aromatic hydrocarbons with formic acid as the source of CO has been studied. It has the advantages of simple operation, easy material economy, mild reaction conditions and wide application to the substrate. The main contents of the paper are as follows: 1. the first realization of a one pot palladium catalyzed carbonylation Sonogashira reaction with formic acid as the carbonyl source. Pd (OAc) 2 as a catalyst. Chemicals, PPh3 as ligands, Et3N as bases, a series of iodides and acetylene can react and have medium to good yield,.2. developed the first case of palladium catalyzed carbonylation Suzuki reaction with formic acid as a carbonyl source. Pd (OAc) 2 as a catalyst, PPh3 as a ligand, K2CO3 as a base, all kinds of aryl iodides and phthalic acid can react and have medium to wait. A good yield. The aryl bromide can also be reacted under this reaction condition.3.. This paper has studied palladium catalysis or carbonylation of Lewis acid to the synthesis of aryl formate. We hope that palladium catalyzes carbonylation, formic acid, as a formyl source, to synthesize aryl ester derivatives at room temperature. It is worth noting that this is a palladium catalyzed carbonyl group. The first report on the synthesis of aryl ester derivatives of formate. However, in a follow-up study, we found that the real role of the above-mentioned palladium catalyst system is Lewis acid, which has realized the use of the Lewis acid catalyst instead of the expensive palladium catalyst, making the method more practical.4. in the work of the study of a efficient, convenient carbonyl source: 1,3,5- Phenols (TFBen).TFBen (TFBen), after release of CO, can not react with other electrophilic reagents, and we have successfully applied TFBen as a carbonyl source in a series of carbonylation reactions. Benzol three is a cheap and large number of chemicals in plants and can be reused and reused.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O621.251
本文編號：2131112
[Abstract]:As one of the cheapest sources of C1, CO occupies an irreplaceable position in the industrial field, but its high toxicity, colorless and odorless properties and high pressure equipment have hindered its wide application in the academic field. In recent years, the development and utilization of new CO substitutes attracted more and more attention from organologists and became carbonylation. According to the method produced by CO, the methods reported can be divided into two categories: heterotopic and in-situ. In situ generation of CO refers to the production and reaction of CO in the same reaction tube. In this way many metal carbonyl complexes and organic compounds such as Mo (CO) 6, formamide, (CH2O) n and formate carboxylate have been developed as CO alternatives. In this paper, the carbonylation of aryl aromatic hydrocarbons with formic acid as the source of CO has been studied. It has the advantages of simple operation, easy material economy, mild reaction conditions and wide application to the substrate. The main contents of the paper are as follows: 1. the first realization of a one pot palladium catalyzed carbonylation Sonogashira reaction with formic acid as the carbonyl source. Pd (OAc) 2 as a catalyst. Chemicals, PPh3 as ligands, Et3N as bases, a series of iodides and acetylene can react and have medium to good yield,.2. developed the first case of palladium catalyzed carbonylation Suzuki reaction with formic acid as a carbonyl source. Pd (OAc) 2 as a catalyst, PPh3 as a ligand, K2CO3 as a base, all kinds of aryl iodides and phthalic acid can react and have medium to wait. A good yield. The aryl bromide can also be reacted under this reaction condition.3.. This paper has studied palladium catalysis or carbonylation of Lewis acid to the synthesis of aryl formate. We hope that palladium catalyzes carbonylation, formic acid, as a formyl source, to synthesize aryl ester derivatives at room temperature. It is worth noting that this is a palladium catalyzed carbonyl group. The first report on the synthesis of aryl ester derivatives of formate. However, in a follow-up study, we found that the real role of the above-mentioned palladium catalyst system is Lewis acid, which has realized the use of the Lewis acid catalyst instead of the expensive palladium catalyst, making the method more practical.4. in the work of the study of a efficient, convenient carbonyl source: 1,3,5- Phenols (TFBen).TFBen (TFBen), after release of CO, can not react with other electrophilic reagents, and we have successfully applied TFBen as a carbonyl source in a series of carbonylation reactions. Benzol three is a cheap and large number of chemicals in plants and can be reused and reused.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O621.251
【參考文獻】
相關(guān)期刊論文 前5條
1 朱芳瑩;董正偉;朱文淵;柳志強;;糖尿病治療藥物及其合成進展[J];發(fā)酵科技通訊;2016年03期
2 魯亞東;王艷華;金子林;;以聚乙二醇為載體的催化劑及為反應(yīng)介質(zhì)的催化反應(yīng)體系[J];有機化學(xué);2006年02期
3 梁誠;4,4'-二氟二苯甲酮的合成與應(yīng)用[J];有機氟工業(yè);2004年03期
4 俞善信,雷存喜;聚乙二醇催化合成正丁基苯基醚[J];日用化學(xué)工業(yè);2002年01期
5 項曼文;莫芬珠;張世春;趙鳴;;氟苯桂嗪的合成[J];南京藥學(xué)院學(xué)報;1984年02期
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