新型氨基功能化碱性离子液体1-(2-氨基乙基)-3-甲基咪唑咪唑盐催化四类取代2-氨基-4H-色烯衍生物的合成  

Improved Synthesis of Substituted 2-Amino-4H-chromene Deriva-tives Catalyzed by a New Amino-functionalized Basic Ionic Liquid 1-(2-Aminoethyl)-3-methylimidazolium Imidazolide

作　　者：窦辉[1] 高思旖[1] 付召龙[1] 刘士忠[1] 

机构地区：[1]南京航空航天大学材料科学与技术学院,南京210016

出　　处：《有机化学》2011年第7期1056-1063,共8页Chinese Journal of Organic Chemistry

基　　金：南京航空航天大学中央高校基本科研业务费专项资金(No.NS2010154)资助项目

摘　　要：设计合成了阴阳离子均具有碱性位点的新型氨基功能化碱性离子液体1-(2-氨基乙基)-3-甲基咪唑咪唑盐([2-aemim]im,3),经ESIMS和1H NMR确定了结构.[2-aemim]im的碱性与氨基功能化的阳离子([2-amim]+)有关,但主要取决于咪唑阴离子(im-).TG-DSC分析显示[2-aemim]im具有高的热稳定性.将[2-aemim]im用于催化水相介质中芳香醛、丙二腈和酚的三组分一锅法反应制备2-氨基-4H-色烯衍生物,阴阳离子之间表现出协同促进催化作用.该催化剂具有高效和底物作用范围广的特点,应用不同的酚类及类似物,如1-萘酚、2-萘酚、间苯二酚和环己二酮,以高产率得到了相应的不同官能团取代的2-氨基-4H-苯并[h]色烯(4a～4e),2-氨基-4H-苯并[f]色烯(5a～5e),2-氨基-4H-色烯(6a～6e)和2-氨基-4H-四氢色烯(7a～7e)四类2-氨基-4H-色烯衍生物.离子液体至少可以循环使用5次,催化活性无显著降低.1-（2-Aminoethyl）-3-methylimidazolium imidazolide （[2-aemim]im, 3）, a new amino-functionalized basic ionic liquid with two basic groups individually located in cation and anion, was prepared and its structure was elucidated on the basis of the ESIMS and 1H NMR spectra. The basicity of [2-aemim]im is related to not only the amino-functioned cation （[2-aemim]＋）, but also the imidazolide anion （im-）. The TG-DSC analysis indicated the high thermal stability of [2-aemim]im. For the one-pot three-component reactions of aromatic aldehydes, malononitrile and activated phenols in aqueous medium, the ionic liquid [2-aemim]im exhibited synergistically catalytic behavior between the cation and anion. And [2-aemim]im proved to be an active and universal catalyst for the reactions of different activated phenols and analogues such as 1-naphthol, 2-naphthol, resorcinol and dimedone to afford the corresponding substituted 2-amino-4H-benzo[h]chromenes （4a - 4e）, 2-amino-4H-benzo[f]chromenes （5a - 5e）, 2-amino-4H- chromenes （6a-6e） and 2-amino-4H-tetrahydrochromene （Ta-7e）. The ionic liquid could be reused for at least five recycles without appreciable loss of efficiency.

关 键 词：氨基功能化 碱性离子液体 1-甲基-3-(2-氨基乙基)咪唑咪唑盐 2-氨基-4日-苯并f剀色烯 2-氨基-4H-苯并阴色烯 2-氨基-4H-色烯 2-氨基-4H四氢色烯 

分 类 号：O626.23[理学—有机化学]