富氮多孔有机聚合物催化制备α⁃氰基肉桂酸乙酯  

Preparation of Ethylα⁃Cyanocinnamate Catalyzed by Nitrogen-rich Porous Organic Polymers

作　　者：高文秀[1] 吕杰琼 高永平 孔长剑 王雪平 郭胜男 娄大伟[1] GAO Wenxiu;LYU Jieqiong;GAO Yongping;KONG Changjian;WANG Xueping;GUO Shengnan;LOU Dawei(School of Chemical and Pharmaceutical Engineering,Jilin Institute of Chemical Technology,Jilin 132022,China)

机构地区：[1]吉林化工学院,化学与制药工程学院,吉林132022

出　　处：《高等学校化学学报》2022年第6期206-213,共8页Chemical Journal of Chinese Universities

基　　金：吉林省科技发展计划项目(批准号:2020122373JC,202002008JC,20190303116SF);吉林省产业技术研究与开发项目(批准号:No.2020C028-1);吉林省教育厅科研规划项目(批准号:JJKH20200240KJ);吉林省创新创业人才资助项目(批准号:2020030)资助.

摘　　要：α-氰基肉桂酸乙酯作为含多种官能团的缺电子烯烃,是一种极具应用价值的有机合成反应底物,主要通过催化Knoevenagel缩合反应获得.本文以多聚甲醛和三聚氰胺为前驱体,采用溶剂热法制备富氮多孔有机聚合物mPMF,经K_(2)CO_(3)处理得到K_(2)CO_(3)-mPMF-X(X=1,10,50).考察了mPMF在苯甲醛和氰乙酸乙酯Knoevena⁃gel缩合反应中的催化性能,通过mPMF与K_(2)CO_(3)-mPMF-X催化活性的比较,探讨了碱性强弱对Knoevenagel缩合反应的影响,并对催化反应机理进行了探索.结果表明,催化剂中丰富的氮物种为反应提供了碱性环境和大量的碱性活性位点,催化剂碱性强弱的控制是催化合成α-氰基肉桂酸乙酯的关键因素.mPMF在甲醇溶剂中于60℃反应3 h后,苯甲醛转化率为97%,目标产物选择性在99.9%以上.Ethylα-cyanocinnamate,an electron-deficient olefin containing various functional groups,is a highly suitable substrate for organic synthesis reactions.It is mainly obtained by catalytic Knoevenagel condensation reac⁃tion.Nitrogen-rich porous organic polymer mPMF was prepared by the solvothermal method using paraformaldehyde and melamine as substrates,and K_(2)CO_(3)-mPMF-X(X=1,10,50)was obtained by K_(2)CO_(3) treatment.The catalytic per⁃formance of mPMF in the Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate was discussed.To investigate the effect of basicity on the Knoevenagel condensation reaction by comparing the catalytic activity of mPMF and K_(2)CO_(3)-mPMF-X.The catalytic reaction mechanism was initially explored.The experimental performance indicates that the abundance of nitrogen species in the catalyst provides a basic environment and a lot of basic active sites for the reaction.Control of catalyst basicity is an essential factor in the catalytic synthesis of ethylα-cyanocin⁃namate.The reaction of mPMF in methanol solvent at 60℃for 3 h resulted in 97%conversion of benzaldehyde and over 99.9%selectivity of the target product.

关 键 词：富氮多孔有机聚合物 催化 KNOEVENAGEL缩合反应 

分 类 号：O643.32[理学—物理化学]