NH2-Ga-MIL-53催化剂对Strecker反应的底物选择性（英文）  

Substrate-Selectivity of Strecker Reaction Based on Amino-Functionalized Ga-MIL-53 Catalyst

作　　者：王鹏程 吴淑杰[1] 单梁 姜岩松 范勇[1] 王莉[1] 陈晓东[1] 徐家宁[1] WANG Peng-Cheng;WU Shu-Jie;SHAN Liang;JIANG Yan-Song;FAN Yong;WANG Li;CHEN Xiao-Dong;XU Jia-Ning(College of Chemistry,Jilin University,Changchun 130012,China;College of Chemical and Environmental Engineering,Anyang Institute of Technology,Anyang,Henan 455000,China)

机构地区：[1]吉林大学化学学院,长春130012 [2]安阳工学院化学与环境工程学院,安阳455000

出　　处：《无机化学学报》2020年第3期547-554,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21171065,21201077和21401005)资助项目

摘　　要：研究了金属有机骨架化合物NH2-Ga-MIL-53对多种N-苯基亚胺底物的Strecker反应的催化性能,研究结果表明:(1)NH2-Ga-MIL-53具有高度催化活性和良好的底物普适性;(2)亚胺底物上取代基的电子效应是影响催化反应速率的关键因素,在亚胺底物上引入给电子取代基团(如甲氧基和苯基)可以加快反应速率,引入吸电子取代基团(如三氟甲基和硝基)可降低反应速率;(3)亚胺底物上取代基的位置对于催化反应速率同样具有重要影响,在亚胺底物的邻位引入甲氧基取代基团时,反应速率加快得最明显;(4)作为非均相催化剂,NH2-Ga-MIL-53可循环使用9次而不失活且保持骨架结构不变;(5)NH2-Ga-MIL-53和Ga-MIL-53催化性能的对比结果表明,NH2-Ga-MIL-53结构中的氨基可以作为路易斯碱活性中心协同路易斯酸催化中心(Ga3+)有效促进strecker反应的进行。此外,由NH2-Ga-MIL-53、六水合硝酸镓和2-氨基对苯二甲酸对Strecker反应的催化效果的对比可知,NH2-Ga-MIL-53的孔结构是提高反应产物专一性的重要因素。This work focuses on Strecker reactions catalyzed by metal-organic framework(MOF)of amino-functionalized Ga-MIL-53(NH2-Ga-MIL-53)in regard to substrates of a series of N-Ph aldimines,and the results showed that:(1)NH2-Ga-MIL-53 exhibited excellect catalytic activity and good univisality among various substrates;(2)the electronic effect of substituents for substrates primarily affects the catalytic reaction rate,and the electron-donating substituted groups(i.e.,MeO,Ph)and electron-withdrawing substituted groups(i.e.,CF3,NO2)show promotion and suppression effects on the reaction,respectively;(3)the substituted position of substituents in respect of substrates secondarily influences the reaction rate,and the ortho-substituted MeO group perform the strongest promotion effects on the reaction;(4)as a heterogeneous catalyst,NH2-Ga-MIL-53 can be reused for 9 runs without obvious loss of conversion efficiencies and collapse of MOF structure;(5)contrasting the catalytic performances between NH2-Ga-MIL-53 and Ga-MIL-53,it is indicated that the amino groups of NH2-Ga-MIL-53 can be served as Lewis base moieties,facilating the reaction according to Lewis acid-base synergistic mechanism.Furthermore,comparing the catalytic effects among NH2-Ga-MIL-53,Ga(NO3)3·6H2O and 2-aminoterephthalic acid,it is concluded that the pore structure of NH2-Ga-MIL-53 framework plays a significant role in avoiding the side reactions with respect to Strecker reaction.

关 键 词：金属有机骨架配合物 镓 非均相催化 Strecker反应 底物选择性 

分 类 号：O614.371[理学—无机化学] O625[理学—化学]