功能化离子液体催化Fries重排合成对羟基芳基酮的工艺研究

P-hydroxyarylketones compounds is one of the imprtant intermediates in chemical industry, medicine and other industries which were found wide applications. There are many synthesis methods. Fries rearrangement method was the one for industrial production. However, catalysts still pose some promble during synthesis process such as toxicity, volatilization and difficult recycling, etc. The emergence of functionalized ionic liquids for p-hydroxyarylketones compounds "green" catalytic synthesis provides a new choice. In this research, functionalized ionic liquids were designed, synthesized and screened to be applied in the synthesis p-hydroxyarylketones compounds. The catalytic synthesis process route will be explored and optimized in the presence of functional ionic liquid throught different experiment conditions. Further more,the study of regeneration and recycling of ionic liquids will be realized. Fries rearrangement reaction mechanism will be explored by means of spectrum.and dynamics and thermodynamics The above study will provide new materials, new methods and new technology for the synthesis of p-hydroxyarylketones compounds.

对羟基芳基酮类化合物是化工、医药等行业的重要中间体，具有广泛应用。其合成方法很多，Fries重排法为目前工业化生产的主要合成方法。然而，此法存在催化剂有毒、易挥发、不可循环利用、遇水敏感和环境污染等问题。功能化离子液体的出现为对羟基芳基酮类化合物的“绿色”化合成提供新的选择。本研究设计、合成和筛选适合于催化对羟基芳基酮类化合物合成的功能化离子液体。通过实验条件因素的研究，总结规律，探索和优化功能化离子液体催化合成对羟基芳基酮类化合物的工艺路线，进而实现离子液体再生和循环使用。借助核磁谱图、原位红外等综合谱学表征手段以及动力学、热力学相结合的分析手段，探索离子液体催化下的Fries重排反应机理。为对羟基芳基酮类化合物的合成和回收提供新材料、新方法和新工艺。

本项目合成了一系列Brönsted 酸性功能化离子液体，用此类离子液体催化O-乙酰苯酯的Fries 重排反应。考察了离子液体阴阳离子的结构对催化活性的影响，优化出最佳催化剂、离子液体用量、反应温度等条件。结果表明，使用2.0eq的离子液体9作为催化剂和溶剂，在无外加溶剂作用下，温度60 ˚C条件下反应，最高收率可达到75%，该反应体系操作简单，绿色安全，产物易于提取，并且催化剂容易再生后循环使用，邻对位选择性高。通过红外谱图、核磁谱图以及采用B3LYP/6-31G+(d,p)理论计算等手段，探索离子液体催化条件下的Fries重排反应机理。