微波辅助负载碘催化Knoevenagel反应
|
摘要
开发了微波辐射下蒙脱土负载碘催化的Knoevenagel反应,考察催化剂、溶剂、碱添加剂、反应时间、温度及原料物质的量比对产率的影响。产物结构经IR,1H NMR,MP进行了表征。结果表明,蒙脱土与分子碘具有协同催化的效果。该方法操作简单、速度快,40℃条件下微波辐射2 min即可完成,产率最高可达97.0%。
A microwave-assisted Knoevenagel reaction catalysized by I2 loaded montmorillonite was developed using malonitrile and aromaticaldehyde as raw material. Influences of solvents,catalysts,reaction temperature,microwave time,quivalency of starting materials on yields were investigated. The products were characterized by1 H NMR,IR and MP. The result showed that montmorillonite and molecular iodine has a synergistic catalytic effect. Yields up to 97. 0% under optimized conditions.
A microwave-assisted Knoevenagel reaction catalysized by I2 loaded montmorillonite was developed using malonitrile and aromaticaldehyde as raw material. Influences of solvents,catalysts,reaction temperature,microwave time,quivalency of starting materials on yields were investigated. The products were characterized by1 H NMR,IR and MP. The result showed that montmorillonite and molecular iodine has a synergistic catalytic effect. Yields up to 97. 0% under optimized conditions.
引文
[1]Yue C,Mao A,Wei Y,et al.Knoevenagel condensation reaction catalyzed by task-specific ionic liquid under solvent-free conditions[J].Cat Comm,2008,9(7):1571-1574.
[2]周颖,闫鹏飞,李光明,等.碘作为Lewis酸催化剂在合成中的应用进展[J].有机化学,2009,29(11):1719-1727.
[3]赵巾巾,高文超,常宏宏,等.单质碘促进的有机反应研究进展[J].有机化学,2014(10):1941-1957.
[4]Ren Y,Cai C.Iodine catalysis in aqueous medium:an improved reaction system for Knoevenagel and nitroaldol condensation[J].Catal Lett,2007,118(1):134-138.
[5]Li Z X,Liu X P,Qiu Z,et al.An efficient iodine-catalysed Knoevenagel condensation reaction in the presence of acetic anhydride[J].J Chem Res,2011,35(1):35-36.
[6]Yang X J,Zhang Y S.Molecular iodine:A powerful catalyst for the Knoevenagel condensation of isatins with malononitrile[J].J Chem,2013(2013):1-4.
[7]Sai Mingze,Rui Guo,Lu Chen,et al.Research on the preparation and characterization of chitosan grafted polyvinylpyrrolidone gel membrane with iodine[J].J App Poly Sci,2015,132(14):41782-41797.
[8]冯敏,付如刚,邱东.活性炭负载单质碘催化合成环己酮乙二醇缩酮[J].化工管理,2015,26(9):108-109.
[9]杨水金,童文龙,尹国俊.碘掺杂聚苯胺催化剂催化合成缩醛(酮)[J].北京科技大学学报,2006,28(3):278-281.
[10]殷杰,白文华,刘万毅,等.硅胶负载碘催化合成苹果酯-A[J].石油化工应用,2006,25(6):18-20.
[11]Bandgar B P,Shaikh K A.Molecular iodine-catalyzed efficient and highly rapid synthesis of bis(indolyl)methanes under mild conditions[J].Tetrahedron Lett,2003,44(9):1959-1961.
[12]Varadwaj G B B,Surjyakanta R,Parida K M.Amine functionalized K10 montmorillonite:a solid acid-base catalyst for the Knoevenagel condensation reaction[J].J Chem Soc,Dalton Trans,2013,42(14):5122-5129.
[13]边延江,秦英,肖立伟,等.Knoevenagel缩合反应研究的新进展[J].有机化学,2006,26(9):1165-1172.
[14]杨凯,汪朝阳,傅建花,等.物理技术辅助的Knoevenagel反应[J].化学进展,2010,22(11):2126-2133.
[15]刘卉闵,刘卉凌,袁永军,等.超声波作用下芳亚甲基丙二酸异丙酯的合成[J].有机化学,2003,23(10):1159-1161.
[16]宫红,王琦,姜恒.氟化钾催化研磨法促进Knoevenagel缩合反应[J].化工科技,2010,18(6):34-36.
[17]Gedye R,Smith F,Westaway K,et al.The structures of spirasine V and pirasine VI[J].Tetrahedron Lett,1986,27(3):279-292.
[18]王官武,王宝亮.微波辐射和加热条件下的无催化剂无溶剂Knoevenagel缩合反应[J].有机化学,2004,24(1):85-87.
[19]李记太,蔺志平.蒙脱土K10-Zn Cl2催化下研磨法合成二吲哚甲烷衍生物[J].有机化学,2008,28(7):1238-1242.
[20]Saeed Balalaie,Navid Nemati.Ammonium acetate-basic alumina catalyzed Knoevenagel condensation under microwave irradiation under solvent-free condition[J].Synth Commun,2000,30:869-875.
[21]Ren Zhongjiao,Cao Wei,Tong Weiqi.The Knoevenagel condensation reaction of aromatic aldehydes with malononitrile by grinding in the absence of solvents and catalysts[J].Synth Commun,2002,32(22):3475-3479.
[2]周颖,闫鹏飞,李光明,等.碘作为Lewis酸催化剂在合成中的应用进展[J].有机化学,2009,29(11):1719-1727.
[3]赵巾巾,高文超,常宏宏,等.单质碘促进的有机反应研究进展[J].有机化学,2014(10):1941-1957.
[4]Ren Y,Cai C.Iodine catalysis in aqueous medium:an improved reaction system for Knoevenagel and nitroaldol condensation[J].Catal Lett,2007,118(1):134-138.
[5]Li Z X,Liu X P,Qiu Z,et al.An efficient iodine-catalysed Knoevenagel condensation reaction in the presence of acetic anhydride[J].J Chem Res,2011,35(1):35-36.
[6]Yang X J,Zhang Y S.Molecular iodine:A powerful catalyst for the Knoevenagel condensation of isatins with malononitrile[J].J Chem,2013(2013):1-4.
[7]Sai Mingze,Rui Guo,Lu Chen,et al.Research on the preparation and characterization of chitosan grafted polyvinylpyrrolidone gel membrane with iodine[J].J App Poly Sci,2015,132(14):41782-41797.
[8]冯敏,付如刚,邱东.活性炭负载单质碘催化合成环己酮乙二醇缩酮[J].化工管理,2015,26(9):108-109.
[9]杨水金,童文龙,尹国俊.碘掺杂聚苯胺催化剂催化合成缩醛(酮)[J].北京科技大学学报,2006,28(3):278-281.
[10]殷杰,白文华,刘万毅,等.硅胶负载碘催化合成苹果酯-A[J].石油化工应用,2006,25(6):18-20.
[11]Bandgar B P,Shaikh K A.Molecular iodine-catalyzed efficient and highly rapid synthesis of bis(indolyl)methanes under mild conditions[J].Tetrahedron Lett,2003,44(9):1959-1961.
[12]Varadwaj G B B,Surjyakanta R,Parida K M.Amine functionalized K10 montmorillonite:a solid acid-base catalyst for the Knoevenagel condensation reaction[J].J Chem Soc,Dalton Trans,2013,42(14):5122-5129.
[13]边延江,秦英,肖立伟,等.Knoevenagel缩合反应研究的新进展[J].有机化学,2006,26(9):1165-1172.
[14]杨凯,汪朝阳,傅建花,等.物理技术辅助的Knoevenagel反应[J].化学进展,2010,22(11):2126-2133.
[15]刘卉闵,刘卉凌,袁永军,等.超声波作用下芳亚甲基丙二酸异丙酯的合成[J].有机化学,2003,23(10):1159-1161.
[16]宫红,王琦,姜恒.氟化钾催化研磨法促进Knoevenagel缩合反应[J].化工科技,2010,18(6):34-36.
[17]Gedye R,Smith F,Westaway K,et al.The structures of spirasine V and pirasine VI[J].Tetrahedron Lett,1986,27(3):279-292.
[18]王官武,王宝亮.微波辐射和加热条件下的无催化剂无溶剂Knoevenagel缩合反应[J].有机化学,2004,24(1):85-87.
[19]李记太,蔺志平.蒙脱土K10-Zn Cl2催化下研磨法合成二吲哚甲烷衍生物[J].有机化学,2008,28(7):1238-1242.
[20]Saeed Balalaie,Navid Nemati.Ammonium acetate-basic alumina catalyzed Knoevenagel condensation under microwave irradiation under solvent-free condition[J].Synth Commun,2000,30:869-875.
[21]Ren Zhongjiao,Cao Wei,Tong Weiqi.The Knoevenagel condensation reaction of aromatic aldehydes with malononitrile by grinding in the absence of solvents and catalysts[J].Synth Commun,2002,32(22):3475-3479.