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设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.
A series of synthesis routes were designed to prepare 1,3,5-tris [(4’-ethynylphenyl) ethynyl] benzene, an aromatic alkynyl dendrimer. Comparing a series of synthetic routes and reaction conditions, it was found that When multiple Sonogashira reactions occur between multi-functional terminal alkyne compounds and aryl bromides, polar similar compounds with different degrees of substitution are often formed and are difficult to separate. The use of polyfunctional terminal alkyne compounds to react with aryl iodonium compounds To avoid this situation.Finally determine the 1,3,5-tribromobenzene and 2-methyl-3-butyn-2-ol as the raw material, to obtain the intermediate product 1,3,5-triethynylbenzene; and then Using p-iodoaniline and trimethylsilylacetylene as raw materials, 4-trimethylsilyl ethynyl iodobenzene was obtained by diazotization and halogenation. The latter was reacted with 1,3,5-triethynylbenzene by Sonogashira reaction , Cleavage to deprotect the reaction to obtain the compound 1,3,5-tris [(4’-ethynylphenyl) ethynyl] benzene.IH NMR, 13C NMR, elemental analysis and other characterization procedures confirmed the intermediates and the final product Structure.