磺酸功能化介孔聚合物催化“一锅法”无溶剂合成3,4-二氢嘧啶-2(1H)-酮  

One-pot Synthesis of 3,4-Dihydropyrimidin-2(1h)-ones Catalyzed by SO_3H-Functionalized Mesopolymer under Solvent-free Conditions

作　　者：邢蓉[1] 张彤[1] 张钺[1] 

机构地区：[1]盐城师范学院化学化工学院,盐城224051

出　　处：《高分子学报》2014年第5期613-618,共6页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21143009);江苏省"青蓝工程"资助;盐城市科技项目(项目号YK2009028);华东师范大学上海市绿色化学与化工过程绿色化重点实验室资助项目;江苏省大学生创新项目(项目号201310324063X)资助

摘　　要：通过软模剂合成方法合成了高度有序具有二维六方(p6mm)的FDU-15介孔聚合物材料.利用气固相磺化法制备得到新型磺酸基功能化介孔聚合物固体酸(FDU-SO3H).通过X-射线衍射(XRD)、扫描电镜(SEM)及元素分析等测试手段对FDU-SO3H介孔材料的物化性能进行了表征.在无溶剂条件下,FDU-SO3H能有效地催化以芳香醛、乙酰乙酸甲酯和尿素(或硫脲)的三组分一锅法的Biginelli反应.在优化实验的条件下,合成了一系列3,4-二氢嘧啶-2(1H)-酮衍生物.考察了加料顺序、溶剂及反应底物对Biginelli反应的影响.苯甲醛、乙酰乙酸甲酯和尿素在无溶剂,90℃加热1 h的条件下反应,3,4-二氢嘧啶-2(1H)-酮的产率为91%.探讨了Biginelli可能的反应机理.实验结果证明,FDU-SO3H不仅具有催化活性高、对环境友好及在空气中稳定等优点,而且重复使用后仍能保持优异的催化活性.The well-ordered 2D hexagonal structure FDU-15 mesoporous polymer with the P6mm space group has been synthesized by soft template method. Novel sulfonic acid group-functionalized FDU-15 mesoporous polymer solid acid （FDU-SO3H） catalyst was successfully prepared through vapour-phase transfer sulfonation of FDU-15. Various techniques such as X-ray diffraction （XRD） , scanning electron microscopy （SEM） and elemental analysis have been adopted to track the functionalization processes, and to characterize the physicochemical properties of the FDU-SO3H. The FDU-SO3H catalyst was tested in the Biginelli reactions of aromatic aldehydes, ethyl acetoacetate and urea （ or thiourea） under solvent-free conditions. In order to find the optimal reaction conditions for the FDU-SO3H catalyst, the effects of additive sequence, solvents, reaction substrates in the Biginelli reaction have been investigated. 3,4-Dihydropyrimidinones/thiones and their derivatives have been synthesized under the optimum reaction conditions. A high yield of 3, 4- dihydropyrimidin-2（ 1H ）-ones as 91% was achieved when Biginelli reaction of benzaldehyde, ethyl acetoacetate and urea was carried out at 90℃ for 1 h under solvent-free conditions. The FDU-SO3H catalyst exhibited similar catalytic activity even after four cycles for Biginelli reaction of benzaldehyde, ethyl acetoacetate and urea. The possible mechanisms of Biginelli reaction have been discussed. The experimental results verified that the FDU-SO3H was able to act as a highly active, eco-friendly, stable and resusable heterogeneous catalyst.

关 键 词：介孔聚合物 固体酸 BIGINELLI反应 一锅法 

分 类 号：O626.41[理学—有机化学]