铜基金属有机大环催化叠氮-炔烃环加成反应  

A Cu-based metal-organic macrocycle catalyst for azide-alkyne cycloaddition

作　　者：谷雨桐 黄慧琳 何丽娜[1] 景旭[1] GU Yutong;HUANG Huilin;HE Lina;JING Xu(Zhang Dayu School of Chemistry,Dalian University of Technology,Dalian 116024,Liaoning,China)

机构地区：[1]大连理工大学张大煜学院,辽宁大连116024

出　　处：《精细化工》2020年第10期2047-2052,共6页Fine Chemicals

摘　　要：咔唑经过维尔斯迈尔-哈克反应以及席夫碱缩合反应得到含有硫脲基团的咔唑基配体2,2’-[(9-丁基-9H-咔唑-3,6-二基)双(亚甲基亚烷基)]双(肼-1-碳硫酰胺)(DCT),其与铜离子构筑了1例[2+2]型金属有机大环〔[Cu2(DCT)2Br2]·1.6(C3H7NO)·1.6(CH3OH)〕(CuBr-DCT),并通过单晶X射线衍射和固体紫外-可见吸收光谱对产物进行表征。结果表明,CuBr-DCT具有良好的光化学物理性能,考察了其作为非均相催化剂催化叠氮化物-炔烃环加成反应(CuAAC)的性能。对于叠氮化合物、炔烃、三乙胺(电子牺牲剂)及CuBr-DCT组成的反应体系,Cu Br-DCT在反应结束后容易分离回收,且能够避免一价铜盐催化该反应时容易发生的歧化或氧化反应。结果证实,当反应在室温下利用家用节能灯进行照射,产物收率可达100%,且产物具有单一性。Thiourea-group-containing carbazole-based ligand,2,2’-[(9-butyl-9 H-carbazole-3,6-diyl)bis(methanylylidene)]bis(hydrazine-1-carbothioamide)(DCT)was synthesized from carbazole via Vilsmeier-Haack reaction and Schiff base condensation reaction.Subsequently,a case of[2+2]type metal-organic macrocycle,[Cu2(DCT)2Br2]·1.6(C3H7NO)·1.6(CH3OH)(CuBr-DCT),was constructed from ligand DCT with copper ions.The product was characterized by single-crystal X-ray diffraction and solid-state UV-Vis absorption spectra.The results showed that CuBr-DCT had good photochemical physical properties.The catalytic performance of CuBr-DCT as a heterogeneous catalyst for azide-alkyne cycloaddition(Cu AAC)was investigated.For the reaction system composed of azide,alkyne,triethylamine(electron donor)and CuBr-DCT,CuBr-DCT was easy to be separated and recycle after the reaction,which can avoid the disproportionation or oxidation reaction of Cu(Ⅰ)salt in the reaction process.It was found that CuBr-DCT exhibited excellent catalytic effect on CuAAC.When the reaction was performed under irradiation by household energy saving lamps at room temperature and CuBr-DCT was used as catalyst,the yield could reach 100%with no other by-products.

关 键 词：铜 咔唑 金属有机大环 叠氮化物-炔烃环加成 非均相催化 催化技术 

分 类 号：O641.4[理学—物理化学] O621.251[理学—化学]