SiO2微球负载的CeCl3·7H2O-NaI催化邻氨基苯硫酚与高位阻α,β-不饱和酮的Michael加成及其串联反应
收稿日期: 2015-04-30
修回日期: 2015-07-06
网络出版日期: 2015-07-10
基金资助
国家自然科学基金(No. 20972040)资助项目.
Michael Addition and Tandem Reaction of Aminothiphenols with α,β- Unsaturated Ketones with High Steric Hindrance Catalyzed by CeCl3·7H2O-NaI Supported on SiO2 Microsphere
Received date: 2015-04-30
Revised date: 2015-07-06
Online published: 2015-07-10
Supported by
Project supported by the National Natural Science Foundation of China (No. 20972040).
以粒径为5 μm的SiO2微球为载体, 制备了CeCl3·7H2O-NaI/SiO2负载催化剂, 用SEM、EDS和XRD对其结构进行表征, 并考察了该催化剂对邻氨基苯硫酚和高位阻α,β-不饱和酮的Michael加成及Michael加成-胺酮缩合串联反应的催化性能. 研究结果表明, 该催化体系能够很好地催化邻氨基苯硫酚类亲核试剂与高位阻α,β-不饱和酮反应, 得到中等及优良的产率; 催化剂使用5次, 其形貌不变, 但金属铈有少量流失, 致使其催化活性有所下降. 研究还发现, 该催化剂对该串联反应的催化模式为, 既催化Michael加成又催化胺酮缩合反应.
张艺扬 , 穆博帅 , 李媛 . SiO2微球负载的CeCl3·7H2O-NaI催化邻氨基苯硫酚与高位阻α,β-不饱和酮的Michael加成及其串联反应[J]. 有机化学, 2015 , 35(11) : 2347 -2357 . DOI: 10.6023/cjoc201504047
Using SiO2 microsphere with size of 5 μm as support, CeCl3·7H2O-NaI/SiO2 supported catalyst was prepared and characterized by SEM, EDS and XDR techniques and its catalytic performance for Michael addition and tandem Michael addition/condensation reactions between aminothiophenols and α,β-unsaturated ketones with high steric hindrance were investigated. The experimental results showed that CeCl3·7H2O-NaI/SiO2 can catalyzed above reactions in moderate to good yields. When the catalyst was used fifth times, its morphology was largely unchanged, but its catalytic activity decreased for losing of small amounts of metal cerium in the process of catalyzing. It was also found that CeCl3·7H2O-NaI/SiO2 can catalyze both the Michael addition of aminothiophenols to α,β-unsaturated ketones and the condensation reaction between ketones and amines.
Key words： Michael addition; tandem reaction; CeCl3·; 7H2O-NaI; SiO2 microsphere; supported catalyst
[1] En, D.; Zou, G. F.; Guo, Y.; Liao, W. W. J. Org. Chem. 2014, 79(10), 4456.
[2] Bartoli, G.; Bartolacci, M.; Giuliani, A.; Marcantoni, E.; Massaccesi, M.; Torregiani, E. J. Org. Chem. 2005, 70(1), 169.
[3] Garg, S. K.; Kumar, R.; Chakraborti, A. K. Tetrahedron Lett. 2005, 46(10), 1721.
[4] Kawatsura, M.; Komatsu, Y.; Yamamoto, M.; Hayase, S.; Itoh, T. Tetrahedron 2008, 64(16), 3488.
[5] Keithellakpam, S.; Laitonjam, W. S. Chin. Chem. Lett. 2014, 25, 767.
[6] Li, Z.-F.; Hou, H.-L.; Ying, A.-G.; Xu, S. -L. Chin. J. Org. Chem. 2014, 34, 1074 (in Chinese)(李志峰, 侯海亮, 应安国, 许松林, 有机化学, 2014, 34, 1074.)
[7] Hou, X.-H.; Ma, Z.-W.; Wang, J.-L.; Liu, H.-M. Chin. J. Org. Chem. 2014, 34, 1509 (in Chinese).(侯学会, 马志伟, 王建玲, 刘宏民, 有机化学, 2014, 34, 1509.)
[8] Ma, A.; Ma, D. W. Org. Lett. 2010, 12(16), 3634.
[9] Hong, B. C.; Kotame, P.; Tsai, C. W.; Liao, J. H. Org. Lett. 2010, 12(4), 776.
[10] Enders, D.; Wang, C.; Bats, J. W. Synlett 2009, 1777.
[11] Wang, W.; Li, H.; Wang, J.; Zu, L. J. Am. Chem. Soc. 2006, 128, 10354.
[12] Tan, B.; Lu,Y.; Zeng, X.; Chua, P. J.; Zhong, G. Org. Lett. 2010, 12(12), 2682.
[13] Zheng, D.; Li, S.; Luo, Y.; Wu, J. Org. Lett. 2011, 13(24), 6402.
[14] Ye, L.; Sun, X.; Zhu, C.; Tang, Y. Org. Lett. 2006, 8(17), 3853.
[15] Yu, L.; Wu, L. L.; Xie, M. H.; Shi, L.; Huang, X. Chin. J. Struct. Chem. 2005, 24(12), 1408.
[16] Yu, L.; Chen, Z. H. Synth. Commun. 2005, 35, 1253.
[17] Dai, X. Y.; Wu, X. Y.; Fang, H. H.; Nie, L. L.; Chen, J.; Deng, H. M.; Cao, W. G.; Zhao, G. Tetrahedron 2011, 67(17), 3034.
[18] Wu, X. Y.; Fang, H. H.; Liu, Q.; Nie, L. L.; Chen, J.; Cao, W. G.; Zhao, G. Tetrahedron 2011, 67(38), 7251.
[19] Qiu, Z. -L.; Li, W. -H.; Zhu, H. -F.; Liu, Q.; Li, Y. Chem. J. Chin. Univ.2013, 34(3), 579 (in Chinese). (邱召来, 李文红, 朱海菲, 刘倩, 李媛, 高等学校化学学报, 2013, 34(3), 579.)
[20] Franzén, J.; Fisher, A. Angew. Chem., Int. Ed. 2009, 48, 787.
[21] Zhang, W.; Franzén, J. Adv. Synth. Catal. 2010, 352, 499.
[22] Wu, X. Y.; Zhang, Y.; Dai, X. Y.; Fang, H. H.; Chen, J.; Cao, W. G.; Zhao, G. Synthesis 2011, 3675.
[23] Liu, Q.; Li, W.-H.; Qiu, Z.-L.; Li, Y. Chem. J. Chin. Univ.2014, 35(3), 538 (in Chinese). (刘倩, 李文红, 邱召来, 李媛, 高等学校化学学报, 2014, 35(3), 538.)
[24] Gao, L.-Y. M.S. Dissertation, Hebei Normal University, Shijiazhuang, 2014 (in Chinese).(高丽叶, 硕士论文, 河北师范大学, 石家庄, 2014.)
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