炔官能化高效绿色合成芳基卤化物的反应探究  

Efficient Green Synthesis of Aryl Halides by Alkyne Functionalization

作　　者：张号 程东 ZHANG Hao;CHENG Dong(School of Chemistry and Material Engineering,Chaohu University,Chaohu Anhui 238024)

机构地区：[1]巢湖学院化学与材料工程学院,安徽巢湖238024

出　　处：《巢湖学院学报》2021年第3期86-94,共9页Journal of Chaohu University

基　　金：巢湖学院专业综合改革试点项目(项目编号:ch18zygg01)。

摘　　要：芳基卤化物广泛用于合成天然产物、功能材料、医药农药等功能性结构分子。目前,芳基卤化物的结构表征和应用研究较多,而通过构建C-X键合成芳基卤化物的路径较少。炔烃芳构化加成反应(HexadehydroDiels-Alder,HDDA)作为一种新型的D-A反应,可以通过三炔或四炔环化得到苯炔中间体,发生亲核加成、环化加成等反应,一步构建多个碳碳键、碳杂原子键,形成复杂的稠合芳环结构。本研究利用HDDA反应,探究稠合芳卤结构化合物的合成,结果显示在100℃条件下,以DMF与水(V:V=10:1)为混合溶剂,四炔和烯丙基卤代烃反应12 h后成功构建了碳碳键和碳卤键,高效合成了一系列新的稠合芳基卤化物。该反应无需金属催化剂、辅助剂和添加剂,也不需要惰性气体气氛的保护,可操作性强,产率高,具有一定的原子经济性,符合绿色化学理念,为合成芳基卤化物提供了新的方法。Aryl halides are widely used in the synthesis of natural products,functional materials,pharmaceutical pesticides and other functional structural molecules.At present,there are many studies on the structure characterization and application of aryl halides,but there are few ways to construct C-X bond to synthesize aryl halides.As a new type of D-A reaction,the aromatization addition reaction of alkynes(Hexadehydro-Diels-Alder,HDDA)can produce intermediate of phenylacetylene through the cyclization of triynes or tetraynes,and then nucleophilic addition,cyclization addition and other reactions take place,multiple C-C bonds and C-H bonds are constructed in one step to form a complex fused aromatic ring structure.In this study,HDDA reaction was used to explore the synthesis of fused aryl halides.The results show that under the condition of 100℃,DMF and water(V:V=10:1)were used as the mixed solvent,C-C bonds and C-X bonds were successfully constructed after the reaction of tetrayne and allyl halides for 12 h,and a series of new fused aryl halides were synthesized efficiently.This reaction does not need metal catalyst,auxiliary agent and additive,nor does it need the protection of inert gas atmosphere.It has strong operability,high yield,certain atomic economy,and conforms to the concept of green chemistry.It provides a new method for the synthesis of aryl halides.

关 键 词：四炔 C-X偶联 稠合芳卤结构 HDDA反应 

分 类 号：O621.3[理学—有机化学] O625.21[理学—化学]