摘要/Abstract

报道了一类酸促进的非预期的重排反应，合成了6个2-芳基-3-（3-氧代丁烯基）-苯并噁唑化合物6a~6f·提出了各步反应的反应机理，采用密度泛函理论（DFT）方法，从原子布居电荷和分子能量两方面对机理进行理论分析.研究结果表明，理论和实验一致说明本文中的反应机理的正确.重排反应机理的提出，为进一步研究该类反应提供了依据，为氮杂环类化合物的合成提供了方法参考.
关键词: 重排反应, 苯并噁唑衍生物, 合成, 反应机理, 密度泛函理论(DFT)
Novel series of rearrangement reactions were herein reported that enable access to a variety of unique 2-aryl-3-(3'-oxobutenyl)-benzoxazole compounds 6a~6f from 2-aminophenol, aromatic aldehyde and 3-butyn-2-one as materials by nucleophilic conjugate addition, dehydration and rearrangement reactions and intramolecular cyclization in the presence of a catalytic amount of CH₃COOH in CH₂Cl₂ at ambient temperature. On the basis of products and intermediate products, a series of possible mechanism was presented and theoretically verified by density functional theory (DFT) method at B3LYP/6-31G (d,p) level from both molecular energy and atomic charge in Gaussian 03 package. The results show that the theory and experiment consistently explain the rationality of the reaction mechanism. The mechanism of rearrangement provides a basis for further study of this type of reaction. The advantage of this method is that a novel structure of benzoxazole derivative was synthesized successfully via a series of rearrangement reactions. Therefore, this method can be used as an attractive strategy for practical synthesis of nitrogen heterocyclic compounds.
Key words: rearrangement reaction, benzoxazole, synthesis, reaction mechanism, density functional theory (DFT)


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