以甲酸为CO来源的钯催化卤代芳烃的羰基化反应研究

发布时间：2018-07-17 22:22

【摘要】：作为最便宜的C1源之一,CO在工业领域中占据了不可替代的地位,但其高毒性和无色无味性质以及高压设备的要求阻碍了其在学术领域的广泛应用。近年来,开发和利用新的CO替代品吸引了有机化学家的越来越多的关注,并成为羰基化化学的研究热点。根据CO产生的方式,已经报道的方法可以分为两类:异位和原位。原位生成CO是指在同一反应管中产生并反应CO,以这种方式,已经开发了许多金属羰基络合物和有机化合物例如Mo(CO)6,甲酰胺,(CH2O)n和甲酸酚酯作为CO替代物。本论文以甲酸为CO来源的钯催化卤代芳烃的羰基化反应研究,具有操作简便、原料经济易得、反应条件温和、对底物适用范围广等优点。论文主要内容如下:1.首次实现了一锅法以甲酸为羰源的钯催化的羰基化Sonogashira反应。以Pd(OAc)2为催化剂,PPh3为配体,Et3N为碱,一系列的碘苯和苯乙炔均能反应并且有中等到良好的产率。2.发展了首例以甲酸为羰源的钯催化的羰基化Suzuki反应。以Pd(OAc)2为催化剂,PPh3为配体,K2CO3为碱,各类芳基碘代物和苯硼酸均能发生反应并且有中等到良好的产率。芳基溴代物也能在该反应条件下反应。3.本论文工作研究了钯催化或者路易斯酸催化羰基化合成甲酸芳基酯。我们希望用钯催化羰基化即甲酸作为甲酰基源,在室温下合成甲酸芳基酯衍生物。值得注意的是,这是钯催化羰基化合成甲酸芳基酯衍生物的第一例报道。然而,在后续研究中,我们发现上述钯催化剂体系中真正作用是路易斯酸,已经实现了用路易斯酸催化剂代替昂贵的钯催化剂,使该方法更加实用。4.本论文工作研究了一种高效、便捷的羰源:1,3,5-均三甲酸苯酚酯(TFBen)。TFBen在释放出CO后的产物间苯三酚不会和其他亲电试剂反应并且我们已经成功的把TFBen作为羰源应用在一系列的羰基化反应中。间苯三酚是便宜的和大量存在于植物中的化学品,并且还可以回收重新利用。
[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.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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