4-三氟甲基对醌醇的反应性及合成应用研究

发布时间：2018-03-08 06:42

本文选题：三氟甲基化　切入点：4-三氟甲基对醌醇　出处：《东北师范大学》2017年博士论文　论文类型：学位论文

【摘要】：三氟甲基芳烃广泛应用于医药、农药、材料等领域。与其日益广泛的应用相比,天然的三氟甲基芳烃十分罕见,现有的合成方法存在选择性、通用性差等诸多问题。因此,三氟甲基芳烃的合成方法一直备受关注。本论文基于前修饰合成策略,以简单易得的4-三氟甲基对醌醇为原料,发展了简洁、高效的三氟甲基芳烃的新合成策略。论文共分五个章节。第一章主要综述了三氟甲基芳烃的合成方法和4-三氟甲基对醌醇的合成及反应。第二章提出了本论文的选题依据。第三章为基于4-三氟甲基对醌醇的双亲核加成/芳构化反应研究。以4-三氟甲基对醌醇作为双亲电体,通过间位双官能团化新合成策略,高区域选择性地合成了多取代三氟甲基芳烃。第四章研究了通过现场生成的对三氟甲基苄基亲电体与酰胺或富电子芳烃的反应,创建了合成对三氟甲基苄基化合物的新方法。所合成的磺酰胺可作为亲电的三氟甲基苄基化试剂,进一步合成多样的三氟甲基苄基化合物。第五章研究了三价铑催化的N-甲氧基芳甲酰胺与4-三氟甲基对醌醇的反应。反应经串联、形式上的anti-Michael加成/芳构化/内酯化反应,区域选择性的构建了三氟甲基双苯并吡喃酮衍生物。
[Abstract]:Trifluoromethyl aromatics are widely used in medicine, pesticides, materials and other fields. Compared with their increasingly widespread applications, natural trifluoromethyl aromatic hydrocarbons are rare, and the existing synthesis methods have many problems, such as selectivity, poor versatility, and so on. The synthesis of trifluoromethyl aromatics has attracted much attention. In this paper, based on the strategy of pre-modification synthesis, simple and easy to obtain 4-trifluoromethyl p-quinone alcohol was used as raw material. The paper is divided into five chapters. The first chapter summarizes the synthesis methods of trifluoromethyl aromatics and the synthesis and reaction of 4-trifluoromethyl p-quinone alcohols. The third chapter is about the study of the amphiphilic nucleation / aromatization reaction of 4-trifluoromethyl p-quinone alcohol, using 4-trifluoromethyl p-quinone alcohol as the amphiphilic electrobody, Polysubstituted trifluoromethyl aromatics (PAHs) were synthesized selectively in high region by a new synthesis strategy of m-bifunctional group. In Chapter 4th, the reaction of p-trifluoromethyl benzyl electrophilic bodies with amides or electron-rich aromatics was studied. A new method for the synthesis of p-trifluoromethyl benzyl compounds was established. The synthesized sulfonamide can be used as an electrophilic trifluoromethyl benzylation reagent. Further synthesis of various trifluoromethyl benzyl compounds. In Chapter 5th, the reaction of trivalent rhodium catalyzed N-methoxy aromide with 4-trifluoromethyl p-quinone alcohol was studied. The reaction was in series and in the form of anti-Michael addition / aromatization / internal esterification. Trifluoromethyl bisbenzopyranone derivatives were constructed by regioselectivity.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O625.46

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