配位催化法合成3-碘噻吩及碘代偶合反应的研究

将配位催化法应用于3-溴噻吩的碘代反应,采用CuI和不同的1,2-二胺配体组成的催化体系,合成了3-碘噻吩。当以正丁醇为溶剂、CuI/N,N′-二甲基乙二胺为催化剂时,在n(3-溴噻吩)∶n(KI)∶n(CuI)∶n(N,N′-二甲基乙二胺)=20∶40∶1∶2、120℃的条件下反应3h,3-碘噻吩的收率达到91.73%,3-碘噻吩的质量分数为97.28%。与传统合成方法相比,配位催化法具有反应条件温和、催化剂用量少、三废排放少的优点。另外,采用配位催化碘代及偶合反应以较高的收率合成了碘苯、二苯醚、3-噻吩苯醚、N-苯基哌啶和N-(3-噻吩基)哌啶。

Synthesis of 3-Iodothiophene by Coordination Catalysis, and Analogous Iodination and Coupling Reaction

3-Iodothiophene was synthesized from 3-bromothiophene and KI by coordination catalytic iodination using CuI/different 1,2-diamine ligands as catalysts.Under the optimal conditions:n-butanol as solvent,reaction temperature 120 ℃,time 3 h,CuI/N,N'-dimethylethylenediamine as catalytic system and n(3-bromothiophene)∶n(KI)∶n(CuI)∶n(N,N'-dimethylethylenediamine)20 ∶40 ∶1 ∶2,yield of 3-iodothiophene can reach 91.73%.The product was analyzed by gas chromatography and its purity is 97.28%.The coordination catalytic synthesizing method is mild under the above reaction conditions,with smaller amount of catalyst and less waste disposal than traditional process.Several other compounds including iodobenzene,diphenyl ether,3-thienyl phenyl ether,N-pheny1 piperidine and N-(3-thienyl)piperidine can also be synthesized with good yield by coordination catalytic iodination and coupling reaction.