DBN（DBU）、苯丙炔Weinreb酰胺参与的含氮杂环的合成及结构鉴定

发布时间：2018-08-27 13:38

【摘要】：1,5-二氮杂双环[4.3.0]-5-壬烯(DBN)和1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)是两种具有强碱性的有机化合物,自开发以来便广泛应用在异构、消除、缩合、环化等多种化学反应中。越来越多的文献报道“非亲核性试剂”DBU、DBN在一定条件下可作为亲核试剂参与反应。本论文以肉桂酸(酯)为原料,经过酯化、溴加成、消除、酰胺化反应,制备得到N-甲基-N-甲氧基苯丙炔酰胺类化合物。以这类化合物为底物,与DBN、DBU反应得到了不同结构的含氮杂环产物。本文利用核磁共振(1H-NMR、13C-NMR、DEPT-135、1H-1H COSY、HSQC、HMBC和NOESY)和高分辨质谱对产物I、II、III(IV)进行结构确证。同时研究了温度、溶剂、DBN用量对反应的影响。实验结果表明,DBN和DBU与苯丙炔Weinreb酰胺反应,得到了两种不同类型的闭环产物I与III,均同时得到开环产物II(IV)。最后针对性地提出了三种可能的反应机理。在反应中,DBN作为亲核试剂,首先氮进攻苯丙炔Weinreb酰胺的炔键,最后得到产物I;而DBU作为亲核试剂,首先碳进攻苯丙炔Weinreb酰胺的炔键,最后得到产物III。由于外来水分子的影响,在得到闭环产物的同时,发生竞争反应,得到开环产物II或IV。
[Abstract]:(DBN) and (DBU) are two organic compounds with strong alkalinity. They have been widely used in many chemical reactions such as isomerization, elimination, condensation, cyclization and so on. More and more literatures report that "non-nucleophilic reagent" DBU,DBN can participate in the reaction as nucleophilic reagent under certain conditions. Through esterification, bromine addition, elimination and amidation, N-methyl-N-methoxyphenylpropargyl amidation was synthesized from cinnamic acid (ester). The heterocyclic products with different structures were obtained by the reaction of these compounds with DBN,DBU. The structure of the product was characterized by 1H-NMR-13C-NMR-DEPT-135H-1H COSY,HSQC,HMBC and NOESY and high resolution mass spectrometry (HRMS). At the same time, the effects of temperature and the amount of solvent DBN on the reaction were studied. The experimental results show that two kinds of closed loop products, I and III, have been obtained by reacting with phenylpropylidene acetylidene Weinreb amides. Two kinds of closed-loop products, I and III, have been obtained simultaneously to obtain the ring-opening product II (IV). Finally, three possible reaction mechanisms are proposed. In the reaction, DBU was used as nucleophilic reagent, the acetylene bond of phenylpropyne Weinreb amide was first attacked by nitrogen, and finally the product I was obtained, while DBU as nucleophilic reagent first attacked the acetylene bond of Weinreb amide, and finally obtained the product III.. Due to the influence of foreign water molecules, the closed-loop products are obtained at the same time of competitive reaction, and the ring opening products II or IV. are obtained.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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