Synthesis, structure of iron(Ⅲ)-containing imidazolium salts and their catalytic activity in the alkylation of aryl Grignard reagents  

作　　者：XIA Ying YAN ChunHui LI Zhuang GAO HuanHuan SUN HongMei SHEN Qi ZHANG Yong 

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4期493-499,共7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

摘　　要：A series of iron(III)-containing imidazolium salts of the general formula [DRim][FeX 4 ] (R=2,6-diisopropylphenyl, IPr, X=Cl, 1; R=IPr, X=Br, 2; R=tertbutyl, t Bu, X=Cl, 3; R=isopropyl, i Pr, X=Cl, 4; R=benzyl, Bn, X=Cl, 5; R=Bn, X=Br, 6) have been prepared in high yields via reactions of anhydrous ferric halides with equivalent of the corresponding N,N-dihydro- carby-limidazolium halides, where 2-6 are novel ones. All of the complexes were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectroscopy, and X-ray crystallography for 1 and 2. All of them were non-hygroscopic and air-stable, with four of them existing as solids (1-4) and two as liquids (5 and 6) at room temperature. A preliminary catalytic study on the coupling of 4-tolylmagnesium bromide with cyclohexyl bromide revealed that 1 and 3 possessed the highest activity. In comparison, 2, 4 and 5 exhibited moderate activity and the least active complex was 6.A series of iron（Ⅲ）-containing imidazolium salts of the general formula [DRim][FeX4] （R = 2,6-diisopropylphenyl, IPr, X = C1, 1; R = IPr, X = Br, 2; R = tertbutyl, tBu, X = C1, 3; R = isopropyl, ipr, X = C1, 4; R = benzyl, Bn, X = C1, 5; R = Bn, X = Br, 6） have been prepared in high yields via reactions of anhydrous ferric halides with equivalent of the corresponding N,N-dihydro- carby-limidazolium halides, where 2-6 are novel ones. All of the complexes were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectroscopy, and X-ray crystallography for 1 and 2. All of them were non-hygroscopic and air-stable, with four of them existing as solids （1-4） and two as liquids （5 and 6） at room temperature. A preliminary catalytic study on the coupling of 4-tolylmagnesium bromide with cyclohexyl bromide revealed that 1 and 3 pos- sessed the highest activity. In comparison, 2, 4 and 5 exhibited moderate activity and the least active complex was 6.

关 键 词：GRIGNARD试剂 催化活性 鎓盐 咪唑 结构式 烷基化 合成 铁 

分 类 号：O643.36[理学—物理化学]