碳酸钾参与肟类化合物氮—氧键断裂重排合成吡啶酚的反应研究

发布时间：2019-01-20 08:31

【摘要】：重排反应不仅是构建新的碳-碳键、碳-杂键的重要工具,而且在有机合成领域尤其是从简单原料合成复杂产物中也有着至关重要的作用。这些反应被广泛地运用在有机精细化学品合成、药物合成以及农药化学中。除了克莱森反应等广为人知的碳-碳键断裂重排,氮-氧键断裂重排反应在合成有特殊用途的多取代呋喃、吡啶和吡咯等杂环化合物也有着不可忽视的作用。但是相对于碳-碳键断裂重排,氮-氧键断裂重排反应报导较少且大多局限在反应条件苛刻、底物范围窄、产率和选择性不高等问题上;除此之外,这类反应还经常用到过渡金属或者毒性较高的溶剂,这对经济性与环境影响有着不好的影响。因此,发展一种条件温和、官能团容忍性好、产物结构有价值的氮-氧键断裂重排反应对于重排反应研究以及有机合成方法学发展都是十分重要的。在本篇论文里,作者阐述了氮-氧键断裂重排以及相关反应;并且,基于本课题组对肟类化合物的转化以及发展新颖、简便、环保的氮-氧键断裂重排反应的兴趣,报导了全新的γ,δ-炔基肟类化合物环化-重排合成吡啶酚的方法。该反应通过肟的亲和加成环化和氮-氧键断裂[1,3]重排过程得到了较难合成、且大多依赖于现有吡啶骨架结构转化的3-吡啶酚。反应过程无需过渡金属催化剂和氧化剂,并且没有用到强碱引发亲核反应,仅仅加入碳酸钾即可。该反应官能团容忍性高,底物范围广,原子经济性好,条件温和,选用丙三醇作为溶剂更使得这个反应具备了成本低,毒性小,环境友好等优点。
[Abstract]:Rearrangement reaction is not only an important tool to construct new carbon-carbon bond and carbon-heterogeneity bond, but also plays an important role in the field of organic synthesis, especially in the synthesis of complex products from simple raw materials. These reactions are widely used in the synthesis of organic fine chemicals, drug synthesis and pesticide chemistry. In addition to the well-known carbon-carbon bond breaking rearrangements such as the Clayson reaction, the nitrogen-oxygen bond break-rearrangement also plays an important role in the synthesis of polysubstituted furans, pyridine and pyrrole, and other heterocyclic compounds with special applications. However, compared with carbon-carbon bond fracture rearrangement, nitrogen-oxygen bond fracture rearrangement is less reported and mostly confined to such problems as harsh reaction conditions, narrow substrate range, low yield and low selectivity. In addition, these reactions are often used in transition metals or solvents with high toxicity, which have negative effects on economy and environment. Therefore, it is very important to develop a kind of nitrogen-oxygen bond breaking rearrangement reaction with mild conditions, good functional tolerance and valuable product structure for the study of rearrangement reaction and the development of organic synthesis methodology. In this paper, the rearrangement of nitrogen-oxygen bond and the related reactions are discussed. Furthermore, based on the interest of our team in the conversion of oxime compounds and the development of novel, simple and environmentally friendly nitrogen-oxygen bond breaking rearrangement reaction, a new cyclization and rearrangement method for the synthesis of pyridinol from 纬, 未 -alkynyl oxime compounds is reported. Through the affinity addition cyclization of oxime and the nitrogen-oxygen bond breaking process, 3-pyridinol, which is mainly dependent on the existing pyridine skeleton structure, was obtained. There is no transition metal catalyst and oxidant in the reaction process, and no strong alkali is used to initiate the nucleophilic reaction, only potassium carbonate can be added. The reaction has the advantages of high tolerance of functional groups, wide substrate range, good atomic economy and mild conditions. The use of glycerol as solvent makes the reaction have the advantages of low cost, low toxicity and environmental friendliness.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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