离子液体中哒嗪衍生物的高效、绿色合成方法研究
收稿日期: 2013-10-31
修回日期: 2013-01-08
网络出版日期: 2014-01-10
基金资助
国家自然科学基金（Nos. 21003049，21073064 ）资助项目.
An Efficient and Environmentally Friendly Procedure for Synthesis of Pyridazine Derivatives in Ionic Liquids
Received date: 2013-10-31
Revised date: 2013-01-08
Online published: 2014-01-10
Supported by
Project supported by the National Natural Science Foundation of China (Nos. 21003049, 21073064).
首次报道了以离子液体作为反应介质，通过1，2，4，5-四嗪与亲二烯体的逆Diels-Alder环加成反应合成哒嗪衍生物的方法. 与传统的合成方法相比，以简便易得的传统咪唑离子液体兼作溶剂和催化剂，反应时间从传统方法的13 d缩短为6 h，产物产率从64.0%提高到85.5%. 根据实验结果研究了离子液体与反应物之间的相互作用，并提出可能的催化机理. 该方法反应条件温和，操作简便，避免了有毒挥发性有机溶剂和额外催化剂的使用，离子液体重复使用六次未见产物产率明显降低，更加符合绿色化学和原子经济性的要求.
关键词： 哒嗪衍生物; 1,2,4,5-四嗪; 亲二烯体; 逆Diels-Alder反应; 离子液体
陈婷婷 , 刘昆 , 陈兆祥 , 王媛媛 , 戴立益 . 离子液体中哒嗪衍生物的高效、绿色合成方法研究[J]. 有机化学, 2014 , 34(5) : 968 -972 . DOI: 10.6023/cjoc201310054
Imidazolium ionic liquids have been investigated as reaction media in inverse-type Diels-Alder reactions between 1,2,4,5-tetrazine and a series of dienophiles to synthesize pyridazine derivatives for the first time. Comparing to conventional synthetic methods, using easily accessible imidazolium ionic liquids as solvent and catalyst, the reaction time reduced from 13 d to 6 h and product yields increased from 64.0% to 85.5%. The interaction between ionic liquid and reactants in theoretical way was further researched and the most possible catalytic mechanism was proposed. The reaction condition is mild and easy to operate, avoiding using the volatile organic solvents and additional catalysts. Moreover, ionic liquids can be used for more than six times without obvious loss of product yields. Therefore, the current synthetic approach is more in accordance with green chemistry and atom economy requirements.
[1] Boger, D. L.; Patel, M. Prog. Heterocycl. Chem. 1989, 1, 36.
[2] (a) Wermuth, C. G. Heterocycl. Chem. 1998, 35, 1091.
(b) Xiong, J. R.; Xiang, Q. X.; Chen, J. X.; Zhang, Y. Q. Chin. J. Org. Chem. 2008, 28, 137 (in Chinese).
(熊俊如, 向清祥, 陈稼轩, 张元勤, 有机化学, 2008, 28, 137.)
[3] Xiong, J. R.; Xiang, Q. X. Chin. J. Org. Chem. 2006, 26, 487 (in Chinese).
(熊俊如, 向清祥, 有机化学, 2006, 26, 487).
[4] Naud, S.; Pipelier, M.; Viault, G. Eur. J. Org. Chem. 2007, 20, 3296.
[5] Yu, Z. X.; Dang, Q.; Wu, Y. D. J. Org. Chem. 2001, 66, 6029.
[6] Mann, E.; Moisan, L.; Hou, J. L. Tetrahedron Lett. 2008, 49, 903.
[7] Eicher, T.; Hauptmann, S.; Speicher, A. The Chemistry of Heterocycles——structure, Reactions, Synthesis, and Applications, Wiley- VCH, Weinheim, 2012, p. 512.
[8] Joule,J. A.; Mills, K. Heterocyclic Chemistry, Wiley-Blackwell, United Kingdom, 2010, p. 236.
[9] Bourotte, M.; Pellegrini, N.; Schmitt, M. Synlett 2003, 1482.
[10] Hoogenboom, R.; Moore, B. C.; Schubert, U. S. J. Org. Chem. 2006, 71, 4903.
[11] Xie, H.; Zu, L.; Oueis, H. R. Org. Lett. 2008, 10, 1923.
[12] Ali, Z. H.; Samira, D.; Shahab, A. Fluid Phase Equilib. 2013, 360, 139.
[13] Brennecke, J. F.; Maginn, E. J. AIChE J. 2001, 47, 2384.
[14] Li, W.; Wang, Y.; Dai, L. Y. Catal. Lett. 2011, 141, 1651.
[15] Wang, Y. Y.; Zhou, J. L.; Liu, K. J. Mol. Catal. A: Chem. 2013, 366, 195.
[16] Wang, Y. Y.; Jiang, D.; Dai, L. Y. Catal. Commun. 2008, 9, 2475.
[17] Sauer, J.; Dieter, K.; Hetzenegger, H. J. Eur. J. Org. Chem. 1998, 2885.
[18] Ahmat, X.; Keyume, A.; Shinozaki, H. Chem. Res. Chin. Univ. 2009, 25, 161.
[19] Chiappe, C.; Malvaldi, M.; Pomelli, C. S. Green Chem. 2010, 12, 1330.
[20] Zhang, L. H.; Fu, X.; Gao, G.. H. ChemCatChem 2011, 3, 1359.
[21] Sauer, J. In Comprehensive Heterocyclic Chemistry Ⅱ, Eds: Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V., Pergamom Press, Oxford, 1996, p. 198.
[22] Fleming, I. Molecular Orbitals and Organic Chemical Reactions, Wiley, Chichester, UK, 2010, p. 336.
[23] Wang, X. S.; Zhang, M. M.; Jiang, H. Tetrahedron 2007, 63, 4439.
[24] Dubreuil, J. F.; Bourahlak; Rahmovni, M. Catal. Commun. 2002, 3, 185.
[25] Peng, Y.; Song, G. Catal. Commun. 2007, 8, 111.
[26] Tadeuse, B.; Przemyslaw, K. J. Polym. Sci., Polym. Chem. 2008, 46, 6961.
/
| 〈 |
|
〉 |
