邻氰基二芳基甲烷的合成和β,β-二溴烯烃的叔烷基化反应

发布时间：2018-07-11 15:37

本文选题：芳烃氟 + 芳基腈　；参考：《华东理工大学》2017年硕士论文

【摘要】：由于二芳基甲烷是重要的有机合成砌块,使得二芳基甲烷在医药、染料和超分子中有着广泛的应用,因此研究新的二芳基甲烷的合成方法受到越来越多的关注。另外,氰基很容易转化成其他的官能团,因此芳基腈类化合物是应用广泛的反应中间体。目前,碳氟键的断裂及其官能团化是有机化学的一大研究热点。本论文研究了在温和条件下芳烃的碳氟键的断裂及其氰基化,高效地合成了邻氰基二芳基甲烷类化合物。另外,在论文的第二部分我们还研究了β,β-二溴烯烃的叔烷基化反应。两个系列共合成了 49个目标化合物。在第二章中,我们研究了在室温条件下,以无水四氢呋喃为溶剂,LDA为碱,通过芳基腈和芳烃氟反应生成邻氰基二芳基甲烷的合成方法。该反应具有较好的底物拓展性。我们还将该反应底物拓展到氯苯和溴苯,结果表明反应依然能顺利进行。我们同时对反应的机理进行了初步的探索,并提出了可能的反应机理。本章共合成了 31个结构新颖的邻氰基二芳基甲烷类目标化合物。在第三章中,我们研究了两个新颖的反应体系:(1)在室温条件下,以CuCN为催化剂,无水四氢呋喃为溶剂,通过叔丁基氯化镁与多种β,β-二溴烯烃反应,最终以90%左右的收率得到E-式和Z-式两种异构体的单取代目标产物;(2)在甲苯回流条件下,无需过渡金属催化,实现了叔丁基氯化镁与多种β,β-二溴烯烃反应,结果能以中等收率得到单取代的还原产物。本章共合成了 18个目标化合物。
[Abstract]:As diarylmethane is an important organic synthetic block, diaryl methane has been widely used in medicine, dyes and supramolecular, so more and more attention has been paid to the research of new synthesis method of diaryl methane. In addition, cyanide groups are easily converted into other functional groups, so arylonitrile compounds are widely used as reaction intermediates. At present, the fracture of carbon-fluorine bond and its functionalization is a hot spot in organic chemistry. In this paper, the cleavage of carbon-fluorine bond and cyanoylation of aromatics under mild conditions were studied, and the o-cyano-diarylmethane compounds were synthesized efficiently. In addition, in the second part of the thesis, we studied the tert-alkylation of 尾, 尾 -dibromoalkenes. A total of 49 target compounds were synthesized from two series. In chapter 2, we studied the synthesis of o-cyanodiarylmethane by the reaction of arylonitrile and aromatic fluorine using anhydrous tetrahydrofuran as solvent LDA as base at room temperature. This reaction has good substrate expansibility. We also extended the substrate to chlorobenzene and bromobenzene, and the results showed that the reaction could still proceed smoothly. At the same time, we explored the reaction mechanism and put forward the possible reaction mechanism. In this chapter, a total of 31 novel o-cyano-diarylmethane compounds were synthesized. In chapter 3, we studied two novel reaction systems: (1) in the presence of CuCN as catalyst and anhydrous tetrahydrofuran as solvent, tert Ding Ji magnesium chloride reacted with various 尾, 尾 -dibromoolefins at room temperature. Finally, the monosubstituted target products of E- and Z- isomers were obtained in 90% yield. (2) under the reflux of toluene, the reaction of tert Ding Ji magnesium chloride with various 尾, 尾 -dibromoolefins was realized without transition metal catalysis. Results the monosubstituted reduction products could be obtained in medium yield. In this chapter, 18 target compounds were synthesized.
【学位授予单位】：华东理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.3

【相似文献】