α,α-二芳基烯丙醇与芳香醛的加成重排反应

发布时间：2018-05-27 02:34

本文选题：无金属催化 + α　；参考：《郑州大学》2017年硕士论文

【摘要】：1,4-二羰基化合物普遍存在于自然界中,在农业、医药、化工等领域是一种十分有价值的化合物。特别的是,1,4-二羰基是合成五元杂环类化合物的重要结构单元,如呋喃、噻吩、吡咯和环戊烯酮等。本论文主要探究了α,α-二芳基烯丙醇和苯甲醛在无金属催化条件下经过氧化重排反应得到1,4-二羰基化合物,研究结果如下:1.本文以α,α-二芳基烯丙醇为底物,TBPB(过氧化苯甲酸叔丁酯)为绿色的氧化剂,以便宜易得的苯甲醛作为酰基化试剂,甲苯为反应溶剂,在120o C下反应24小时,得到1,4-二羰基化合物,产率高达94%。该课题的新颖之处在于无需底物的修饰、没有强酸强碱的参与,具有操作简单、高效、环境友好等优点,并且没有多余的副产物,原子经济效应突出。（？）2.为了阐明反应机理,设计了对比试验,结果显示:α,α-二芳基烯丙醇和苯甲醛在不加入TBPB的标准条件下反应时,没有检测到相应目标产物的存在,说明TBPB对反应的顺利进行起着关键性作用。并在标准条件下,向反应体系中加入2 equiv的自由基捕捉剂TEMPO(2,2,6,6-四甲基哌啶-氮氧化物),没有得到目标产物,说明在该反应机理中可能存在自由基历程。根据对比实验和已发表的相关文献的参考,推测了可能的反应机理:（?）
[Abstract]:1) 4-dicarbonyl compounds are widely found in nature and are valuable compounds in agriculture, medicine, chemical industry and so on. In particular, the 4-dicarbonyl group is an important structural unit for the synthesis of quaternary heterocyclic compounds, such as furan, thiophene, pyrrole and cyclopentenone. In this paper, we studied the oxidation rearrangement of 伪, 伪 -diarylallyl alcohol and benzaldehyde under the condition of non-metal catalysis to obtain 1o 4-dicarbonyl compound. The results are as follows: 1: 1. Using 伪, 伪 -diarylallyl alcohol as substrate, TBPBas as green oxidant, cheap benzaldehyde as acylation reagent, toluene as reaction solvent, and reaction at 120o C for 24 hours, a 1-dimethyl-4-dicarbonyl compound was obtained. The yield is as high as 94. The novelty of this subject lies in the fact that there is no substrate modification, no strong acid and strong base, simple operation, high efficiency, environmental friendliness, and no superfluous by-products, so the atomic economic effect is obvious. In order to elucidate the reaction mechanism, a comparative experiment was designed. The results showed that when 伪, 伪 -diarylallyl alcohol and benzaldehyde reacted without TBPB, the corresponding target products were not detected. It is concluded that TBPB plays a key role in the smooth progress of the reaction. Under the standard conditions, the free radical trapping agent of 2 equiv was added to the reaction system, and the target product was not obtained, indicating the existence of free radical mechanism in the reaction mechanism. According to the comparative experiments and the references of the published literatures, the possible reaction mechanism is deduced.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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