Development of Fe(Ⅲ)-containing ether-functionalized imidazolium ionic liquids for aryl Grignard cross-coupling of alkyl halides  

作　　者：WANG LinLin LU Bing ZHU AiDi SUN HongMei SHEN Qi 

机构地区：[1]The Key Laboratory of Organic Synthesis of Jiangsu Province,College of Chemistry,Chemical Engineering and Materials Science,Soochow University

出　　处：《Chinese Science Bulletin》2013年第30期3624-3629,共6页

基　　金：supported by the National Natural Science Foundation of China(21172164),the Key Laboratory of Organic Chemistry of Jiangsu Province;the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)

摘　　要：A series of Fe(Ⅲ)-containing imidazolium-based ionic liquids containing ether substituents,including[C3OMim][FeCl4](1,[C3OMim]=1-(2-methoxyethyl)-3-methylimidazolium),[C3OiPim][FeCl4](2,[C3OiPim]=1-isopropyl-3-(2-methoxyethyl)imidazolium),[C3OBim][FeCl4](3,[C3OBim]=1-butyl-3-(2-methoxyethyl)imidazolium),[(C3O)2im][FeCl4](4,[(C3O)2im]=1,3-bis(2-methoxyethyl)imidazolium),[C3OMim][FeBr4](5)and[(C3O)2im][FeBr4](6),were prepared and characterized by elemental analysis,Raman spectroscopy and electrospray ionization mass spectrometry.The catalytic performances of 1–6 and related Fe(III)-based catalysts in the cross-coupling of aryl Grignard reagents with alkyl halides bearing-hydrogens were studied,revealing that mono(ether)functionality improves the catalytic activity and that bis(ether)functionality improves the reusability.After simply decanting the product contained in the ethereal layer,complex 4,which containing bis(ether)-functionalized imidazolium cation,could be successfully recycled seven times.A series of Fe（Ⅲ）-containing imidazolium-based ionic liquids containing ether substituents, including [C3OMim][FeCl4] （1, [C3OMim] = 1-（2-methoxyethyl）-3-methylimidazolium）, [C3OiPim][FeCl4] （2, [C3OiPim] = 1-isopropyl-3-（2-methoxyethyl） imidazolium）, [C3OBim][FeCl4] （3, [C3OBim] = 1-butyl-3-（2-methoxyethyl）imidazolium）, [（C3O）2im][FeCl4] （4, [（C3O）2im] = 1,3-bis（2-methoxyethyl）imidazolium）, [C3OMim][FeBr4] （5） and [（C3O）2im][FeBr4] （6）, were prepared and characterized by elemental analysis, Raman spectroscopy and electrospray ionization mass spectrometry. The catalytic performances of 1-6 and related Fe（Ⅲ）-based catalysts in the cross-coupling of aryl Grignard reagents with alkyl halides bearing fl-hydrogens were studied, revealing that mono（ether） functionality improves the catalytic activity and that bis（ether） functionality improves the reusability. After simply decanting the product contained in the ethereal layer, complex 4, which containing bis（ether）-functionalized imidaz- olium cation, could be successfully recycled seven times.

关 键 词：交叉耦合 离子液体 咪唑基 乙醚 Fe 卤代烷 官能化 电喷雾电离质谱 

分 类 号：O627.81[理学—有机化学]