新型异核双阳离子型磺酸功能化离子液体的合成及其催化活性
收稿日期: 2014-09-24
修回日期: 2014-12-01
网络出版日期: 2015-01-06
基金资助
甘肃省自然科学基金(No. 1107RJZK243)资助项目.
Synthesis and Catalytic Activity of Novel Heternuclear Dication Brønsted Acidic Ionic Liquids
Received date: 2014-09-24
Revised date: 2014-12-01
Online published: 2015-01-06
Supported by
Project supported by the Natural Science Foundation of Gansu Province (No. 1107RJZK243).
合成了三种基于1-吗啉基-3-咪唑基丙烷异核双阳离子的新型二磺酸功能化Brøsted酸性离子液体: 1-[4-(4-磺酸丁基)吗啉基-3-[3-(4-磺酸丁基)咪唑基]丙烷二(三氟甲烷磺酸)盐{A, [(C4SO3H)m(C4SO3H)i]p(OTf)2}、1-[4-(4-磺酸丁基)吗啉基-3-[3-(4-磺酸丁基)咪唑基]丙烷二硫酸氢盐{B, [(C4SO3H)m(C4SO3H)i]p(HSO4)2}及1-[4-(4-磺酸丁基)吗啉基-3-[3-(4-磺酸丁基)咪唑基]丙烷二磷酸二氢盐{C, [(C4SO3H)m(C4SO3H)i]p(H2PO4)2}. 其结构经FT-IR、MS、NMR等确认. 选择吗啉、甲基咪唑单磺酸功能化离子液体作为对照组, 以苯甲醛与环己酮之间的交叉Aldol缩合反应考察了其催化活性. 用Hammett方法测定了其酸性, 实验结果表明, 所合成的三种双磺酸功能化离子液体的催化能力比单磺酸功能化离子液体的强, 其酸性次序与催化活性相一致. 其中, 阴离子为三氟甲烷磺酸根的离子液体对18种Aldol缩合反应底物有极好的适应性, 并且催化活性最强, 产率高达90%, 在重复使用10次后, 仍保持较高的反应活性.
关键词： 二磺酸功能化离子液体; 合成; 催化活性; Hammett方法; 交叉Aldol缩合反应; 重复使用
崔文辉 , 张有明 , 贾如琰 , 王昱 , 魏太保 . 新型异核双阳离子型磺酸功能化离子液体的合成及其催化活性[J]. 有机化学, 2015 , 35(4) : 890 -897 . DOI: 10.6023/cjoc201409040
Three new Brøsted-acidic task-specfic ionic liquids (TSILS) that bear two butane sulfonic acid groups based on 1-(morpholinyl-4-yl)-3-(imidazolyl-1-yl)propane (mip) heternuclear dication: 1-[4-(4-sulfobutyl)morpholinium-4-yl]-3-[3-(4- sulfobutyl)-1H-imidazolium-1-yl]propane bis(trifluoromethane sulfonate) {A, [(C4SO3H)m(C4SO3H)i]p(OTf)2}, 1-[4-(sul- fobutyl)morpholinium-4-yl]-3-[3-(4-sulfobutyl)-1H-imidazolium-1-yl]propane bis(hydrogen sulfate) {B, [(C4SO3H)m(C4SO3- H)i]p(HSO4)2} and 1-[4-(4-sulfobutyl)morpholinium-4-yl]-3-[3-(4-sulfobutyl)-1H-imidazolium-1-yl]propane bis(bihydrogen phosphate) {C, [(C4SO3H)m(C4SO3H)i]p(H2PO4)2} were synthesized and characterized by NMR and FT-IR. The imidazolium-based and morpholinium-based single-SO3H functionalized acidic ionic liquids were used for comparison. Their catalytic activities were investigated in crossed-aldol condensation between cycloalkanone and various aromatic aldehydes. Hammett method has been used to determine the acidity order of these ionic liquids (ILs). The experiment results have shown that the catalytic activities of the three bi-SO3H-functionalized ILs were stronger than those of single SO3H functionalized ILs. Their acidity orders were consistent with their catalytic activities. Good adaptability to the reaction substrate and maximum product yield of 90% was observed when [(C4SO3H)m(C4SO3H)i]p(OTf)2 was used as catalyst and the catalyst can be reused at least ten times without obvious activity loss.
[1] Wilkes, J. S. Green Chem. 2002, 4, 73.
[2] Wasserscheid, P.; Keim, w. Angew. Chem., Int. Ed. 2000, 39, 3772.
[3] Huddleston, J. G.; Visser, A. E.; Reichert, W. M.; Willauer, H. D.; Broker, G. A.; Rogers, R. D. Green. Chem. 2001, 3, 156.
[4] Zhang, C. Y.; Shi, R. B.; Chen, C. Y.; Jin, C. M. Chin. J. Org. Chem. 2013, 33, 611 (in Chinese).
(张传越, 石若冰, 陈才元, 金传明, 有机化学, 2013, 33, 611.)
[5] Song, C. H.; Liu, H.; Li, Y.; Ge, S.; Wang, H. W.; Zhu, W. S.; Chang, Y. H.; Han, C. R.; Li, H. M. Chin. J. Chem. 2014, 32, 434.
[6] Wu, W. J.; Zhang, X. Y.; Hu, Y.; Jin, B.; Hua, J. L. Chin. J. Chem. 2013, 31, 388.
[7] Kuang, M.; Zhang, Y.; Yang, P. Y.; Lu, H. J. Acta Chim. Sinica 2013, 71, 1007 (in Chinese).
(匡敏, 张莹, 杨芃原, 陆豪杰, 化学学报, 2013, 71, 1007.)
[8] Li, Y. P.; Qi, L.; Shen, Y.; Zhang, H. Z; Ma, H. M. Chin. J. Chem. 2014, 32, 619.
[9] Gao, X.; Fan, J.; Wang, X. L.; Zhang, Y. S. Acta Chim. Sinica 2013, 71, 1411 (in Chinese).
(高霞, 樊静, 王小龙, 张艳树, 化学学报, 2013, 71, 1411.)
[10] Sheng, W. L.; Tian, F. L.; Du, Y. Y.; Wu, C. Y. Chin. J. Org. Chem. 2013, 33, 835 (in Chinese).
(盛万里, 田福利, 杜玉英, 吴春雨, 有机化学, 2013, 33, 835.)
[11] Song, Y. L.; Wang, X. C.; Huang, C. P.; Liang, F. B.; Yu, Z. C.; Chen, B. H. Chin. J. Org. Chem. 2013, 33, 1715 (in Chinese).
(宋彦磊, 王新承, 黄崇品, 梁凤兵, 毓志超, 陈标华, 有机化学, 2013, 33, 1715.)
[12] Zhao, D. W.; Wu, Y. T.; Chen, T. T.; Dai, L. Y.; Wang, Y. Y. Chin. J. Org. Chem. 2013, 33, 1791 (in Chinese).
(赵东旺, 吴悦彤, 陈婷婷, 戴立益, 王媛媛, 有机化学, 2013, 33, 1791.)
[13] Cole, A C.; Jensen, J. L.; Ntai, L.; Tran, K. L. T.; Weaver, K. J.; Forbes, D. C.; Davis, J. H. Jr. J. Am. Chem. Soc. 2002, 124, 5962.
[14] Xing, H. B.; Wang, T.; Zhou, Z. H.; Dai, Y. Y. J. Mol. Catal. A: Chem. 2007, 264, 53.
[15] Huang, B. H.; Wang, Y. F.; Zhang, K.; Fang, Y. X.; Zou, B. L. Chin. J. Catal. 2007, 28, 743 (in Chinese).
(黄宝华, 汪艳飞, 张焜, 方岩雄, 周蓓蕾, 催化学报, 2007, 28, 743.)
[16] Wang, Y. Y.; Wu, Y. T.; Liu, K.; Dai, L. Y. Chin. Chem. Lett. 2012, 23, 1031.
[17] Gui, J. Z.; Cong, X. H.; Liu, D.; Zhang, X. T.; Hu, Z.; Sun, Z. L. Catal. Commun. 2004, 5, 473.
[18] Fang, D.; Zhou, X. L.; Ye, Z. W.; Liu, Z. L. Ind. Eng. Chem. Res. 2006, 45, 7982.
[19] Huang, B. H.; Wang, Y. F.; Du, Z. Y.; Zhang, K.; Fang, Y. X.; Zou, B. L.; Li, Z. J. J. Instrum. Anal. 2007, 26, 478 (in Chinese).
(黄宝华, 汪艳飞, 杜志云, 张焜, 方岩雄, 周蓓蕾, 黎子进, 分析测试学报, 2007, 26, 478.)
[20] Huang, B. H.; Li, Z. J.; Xu, X. L.; Zhang, K.; Fang, Y. X. Chin. J. Org. Chem. 2009, 29, 770 (in Chinese).
(黄宝华, 黎子进, 史娜, 徐效陵, 张焜, 方岩雄, 有机化学, 2009, 29, 770.)
[21] Ling, X. Z.; Gao, S.; Yang, J. G.; He, M. Y. Catal Lett. 2008, 125, 396.
[22] Xu, D. Q.; Wu, J.; Luo, Sh. P.; Zhang, J. X.; Wu, J. Y.; Du, X. H.; Xu, Z. Y. Green Chem. 2009, 11, 1239.
[23] Liu, X. F.; Xiao, L. F.; Wu, H. G. J. L. T.; Li, Z.; Chen, J.;Xia, C. G. J. Catal. Commun. 2009, 10, 424.
[24] Liu, X. F.; Zhao, Y. W.; Li, Z.; Chen, J. Xia, C. G. Chin. J. Chem. 2010, 28, 2003.
[25] Zeng, H. Y.; Ying, S. F.; Li, Y. Chin. J. Org. Chem. 2007, 27, 528 (in Chinese).
(曾鸿耀, 尹述凡, 李颖, 有机化学, 2007, 27, 528.)
[26] Das, B.; Thirupathi, P.; Mahender, I.; Reddy, K. R. J. Mol. Catal. A: Chem. 2006, 247, 182.
[27] Yang, W. Z.; Li, H. Y.; Huang, S. S. Li, J. T.; Wang, S. X.; Cao, Y. Q. Chin. J. Org. Chem. 2005, 25, 994 (in Chinese).
(杨文智, 李海鹰, 黄顺升, 李记太, 王书香, 曹玉庆, 有机化学, 2005, 25, 994).
[28] Kang, L. Q.; Wei, B. G. Chemistry 2007, 70, 801 (in Chinese).
(康丽琴, 魏邦国, 化学通报, 2007, 70, 801.)
[29] An, L. T.; Zou, J. P.; Zhang, L. L. Catal. Commun. 2008, 9, 349.
[30] Ma, F.; Li, L. Q.; Hao, H. E.; Su, Y.; Liu, W. Y. Chin. J. Org. Chem. 2010, 30, 419 (in Chinese).
(马峰, 李立强, 郝海娥, 苏艳, 刘万毅, 有机化学, 2010, 30, 419.)
[31] Lin, P.; Li, B. L.; Li, J. T.;Wang, H. C.; Bian, X. B.; Wang, X. M. Catal. Lett. 2011, 141, 459.
[32] Zhang, X. Y.; Fan, X. S.; Niu, H. Y.; Wang, J. J. Chin. Chem. Lett. 2003, 14, 1005.
[33] Zheng, X. L.; Zhang, Y. M. Synth. Commun. 2003, 33, 161.
[34] Liu, B. Y.; Zhao, D. S.; Xu, D. Q.; Xu, Z. Y. Chem. Res. Chin. Univ. 2007, 23, 549.
[35] Liu, Y.; Zhang, Y. M.; Hua, M. T.; Liu, M. X.; Wei, T. B. Chin. J. Inorg. Chem. 2011, 27, 1569 (in Chinese).
(刘勇, 张有明, 华茂堂, 刘明霞, 魏太保, 无机化学学报, 2011, 27, 1569.)
[36] Wei, T. B.; Dang, J. P.; Lin, Q.; Yao, H.; Liu, Y.; Zhang, W. Q.; Ming, J. J.; Zhang, Y. M. Sci. China Chem. 2012, 55, 2554.
[37] Zhang, Y. M.; Liu, Y.; Lin, Q.; Hua, M. T.; Wang, W. F.; Ma, Y. J.; Wei, T. B. Sci. China Chem. 2011, 41, 869 (in Chinese).
(张有明, 刘勇, 林奇, 华茂堂, 王伟峰, 马永钧, 魏太保, 中国科学: 化学, 2011, 41, 869.)
[38] Zhang, Y. M.; Cui, W. H.; Wai, T. B. Chin. J. Org. Chem. 2007, 27, 893 (in Chinese).
(张有明, 崔文辉, 魏太保, 有机化学, 2007, 27, 893.)
[39] Wai, T. B, Shi, H. X.; Zhang, Z. R.; Cui, W. H.; Zang, Y. M. Chin. J. Org. Chem. 2007, 27, 1116 (in Chinese).
(魏太保, 师海雄, 张治仁, 崔文辉, 张有明, 有机化学, 2007, 27, 1116.)
[40] Liu, X. F.; Chen, J.; Xia, C. G. J. Mol. Catal. 2008, 22, 392 (in Chinese).
(刘晓飞, 陈静, 夏春谷, 分子催化, 2008, 22, 392.)
[41] Kore, R.; Srivastava, R. J. Mol. Catal. A: Chem. 2011, 345, 117.
[42] Yang, L.; Lu, J.; Bai, Y. J. Chin. J. Org. Chem. 2003, 23, 659 (in Chinese).
(杨玲, 路军, 白银娟, 有机化学, 2003, 23, 659.)
[43] Mohammadi ziarani, G.; Badiei, A.; Abbasi, A.; Farahani, Z. Chin. J. Chem. 2009, 27, 1537.
/
| 〈 |
|
〉 |
