NH2-Ga-MIL-53催化剂对Strecker反应的底物选择性
Substrate-Selectivity of Strecker Reaction Based on Amino-Functionalized Ga-MIL-53 Catalyst
作者单位E-mail
王鹏程 吉林大学化学学院, 长春 130012  
吴淑杰 吉林大学化学学院, 长春 130012  
单梁 安阳工学院化学与环境工程学院, 安阳 455000  
姜岩松 吉林大学化学学院, 长春 130012  
范勇 吉林大学化学学院, 长春 130012  
王莉 吉林大学化学学院, 长春 130012  
陈晓东 吉林大学化学学院, 长春 130012  
徐家宁 吉林大学化学学院, 长春 130012 xujn@jlu.edu.cn 
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。
关键词: 金属有机骨架配合物    非均相催化  Strecker反应  底物选择性
基金项目: 国家自然科学基金(No.21171065,21201077和21401005)资助项目
Abstract: 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.
Keywords: metal-organic frameworks  gallium  heterogeneous catalysis  Strecker reaction  substrate-selectivity
投稿时间:2019-09-26 修订日期:2019-11-27
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王鹏程,吴淑杰,单梁,姜岩松,范勇,王莉,陈晓东,徐家宁.NH2-Ga-MIL-53催化剂对Strecker反应的底物选择性[J].无机化学学报,2020,36(3):547-554.
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