连续流微反应器中CuCN-TsOH催化合成2-芳基-4,5-二氢-1H-咪唑啉

doi:10.6023/cjoc201604038

摘要/Abstract

应用连续流微反应器，以CuCN^-TsOH为催化剂，通过腈和乙二胺反应合成了一系列2-咪唑啉类化合物.催化剂CuCN^-TsOH在乙二胺中溶解成均相，适用于连续化反应条件.在连续流条件下，只需5 min就可以高产率得到2-咪唑啉产物.利用连续流反应器实现了“在线保留时间梯度（in-tube retention time gradient，IT-RTG）”，并应用于监测反应进程.

关键词: 连续流微反应器, 2-咪唑啉, 催化, 氰化亚铜, 腈, 环合

2-Imidazolines were synthesized via CuCN^-TsOH catalyzed cyclization of nitriles with ethylenediamine in a continuous-flow microreactor. The CuCN^-TsOH dissolves in ethylenediamine homogeneously and is a suitable catalyst for the continuous reactions. Under the flow condition, the 2-imidazolines were obtained with high yields in 5 min for most substrates. The "in-tube retention time gradient" (IT-RTG) is achieved in the continuous-flow microreactor, and it is applied in monitoring the reaction progress.

Key words: continuous-flow microreactor, 2-imidazoline, catalysis, cuprous cyanide, nitrile, cyclization

引用此文

周俊杰, 唐志珂, 张超, 王洞天, 张开, 孙宏滨. 连续流微反应器中CuCN^-TsOH催化合成2-芳基-4,5-二氢-1H-咪唑啉[J]. 有机化学, 2016, 36(11): 2662-2669.

Zhou Junjie, Tang Zhike, Zhang Chao, Wang Dongtian, Zhang Kai, Sun Hongbin. CuCN^-TsOH Catalyzed Synthesis of 2-Aryl-4,5-dihydro-1H-imidazoline in a Continuous-Flow Microreactor[J]. Chin. J. Org. Chem., 2016, 36(11): 2662-2669.

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参考文献

[1] Watts, P.; Wiles, C. Chem. Commun. 2007, 443.
[2] Geyer, K.; Codée, J. D. C.; Seeberger, P. H. Chem. Eur. J. 2006, 12, 8434.
[3] Wiles, C.; Watts, P. Chem. Commun. 2011, 47, 6512.
[4] Wiles, C.; Watts, P. Green Chem. 2012, 14, 38.
[5] Jin, J.; Dong, L.; Zhang, K. H.; Liu, J. Chin. J. Org. Chem. 2012, 32, 201 (in Chinese). (金杰, 董玲, 张克华, 刘瑾, 有机化学, 2012, 32, 201.)
[6] Ducry, L.; Roberge, D. M. Angew. Chem. 2005, 117, 8186.
[7] Qiao, L.; Lu, Y.; Liu, B.; Girault, H. H. J. Am. Chem. Soc. 2011, 133, 19823.
[8] Bakker, J. J. W.; Zieverink, M. M. P.; Reintjens, R. W. E. G.; Kapteijn, F.; Moulijn, J. A.; Kreutzer, M. T. ChemCatChem 2011, 3, 1155.
[9] Gutmann, B.; Roduit, J.-P.; Roberge, D.; Kappe, C. O. Chem. Eur. J. 2011, 17, 13146.
[10] Riva, E.; Gagliardi, S.; Martinelli, M.; Passarella, D.; Vigo, D.; Rencurosi, A. Tetrahedron 2010, 66, 3242.
[11] Rueping, M.; Bootwicha, T.; Sugiono, E. Adv. Synth. Catal. 2010, 352, 2961.
[12] Noël, T.; Maimone, T. J.; Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50, 8900.
[13] Hamano, M.; Nagy, K. D.; Jensen, K. F. Chem. Commun. 2012, 48, 2086.
[14] Sedelmeier, J.; Ley, S. V.; Baxendale, I. R.; Baumann, M. Org. Lett. 2010, 12, 3618.
[15] Varas, A. C.; Noël, T.; Wang, Q.; Hessel, V. ChemSusChem 2012, 5, 1703.
[16] Borukhova, S.; Noël, T.; Metten, B.; de Vos, E.; Hessel, V. ChemSusChem 2013, 6, 2220.
[17] Zhang, P.; Russell, M. G.; Jamison, T. F. Org. Process Res. Dev. 2014, 18, 1567.
[18] Bogdan, A. R.; James, K. Chem. Eur. J. 2010, 16, 14506.
[19] Bogdan, A. R.; James, K. Org. Lett. 2011, 13, 4060.
[20] Bogdan, A. R.; Sach, N. W. Adv. Synth. Catal. 2009, 351, 849.
[21] Damm, M.; Glasnov, T. N.; Kappe, C. O. Org. Process Res. Dev. 2010, 14, 215.
[22] Grimmett, M. R. In Comprehensive Heterocyclic Chemistry, Ed.:Rees, C. W., Pergamon, Oxford, 1984, p. 373.
[23] Liu, H.; Du, D. M. Adv. Synth. Catal. 2009, 351, 489.
[24] Zhou, B. Y.; Zhang, J.; Li, X. N.; She, M. Y.; Zhang, J.; Li, J. L.; Shi, Z. Chin. J. Org. Chem. 2013, 33, 423 (in Chinese). (周葆悦, 张金, 李向南, 厍梦尧, 张劲, 李剑利, 史真, 有机化学, 2013, 33, 423.)
[25] Bon, R. S.; Hong, C. G.; Bouma, M. J.; Schmitz, R. F.; de Kanter, F. J. J.; Lutz, M.; Spek, A. L.; Orru, R. V. A. Org. Lett. 2003, 5, 3759.
[26] Bon, R. S.; van Vliet, B.; Sprenkels, N. E.; Schmitz, R. F.; de Kanter, F. J. J.; Stevens, C. V.; Swart, M.; Bickelhaupt, F. M.; Groen, M. B.; Orru, R. V. A. J. Org. Chem. 2005, 70, 3542.
[27] Elders, N.; Schmitz, R. F.; de Kanter, F. J. J.; Ruijter, E.; Groen, M. B.; Orru, R. V. A. J. Org. Chem. 2007, 72, 6135.
[28] Chen, G.-F.; Li, H.-Y.; Xiao, N.; Chen, B.-H.; Song, Y.-L.; Li, J.-T.; Li, Z.-W. Aust. J. Chem. 2014, 67, 1516.
[29] Mikhail, K. Lett. Org. Chem. 2013, 10, 235.
[30] Taketoshi, A.; Tsujimoto, A.; Maeda, S.; Koizumi, T.; Kanbara, T. ChemCatChem 2010, 2, 58.
[31] Huang, S. J.; Shao, Y. L.; Zhang, L. X.; Zhou, X. G. Angew. Chem., Int. Edit. 2015, 54, 14452.
[32] Cason, J. J. Am. Chem. Soc. 1947, 69, 495.
[33] Guy, L.; Jean-Claude, G.; Monique, P. Synthesis 1981, 963.
[34] David Crouch, R. Tetrahedron 2009, 65, 2387.
[35] Spychala, J. Monatsh. Chem. 2006, 137, 1203.
[36] Pathan, M. Y.; Paike, V. V.; Pachmase, P. R.; More, S. P.; Ardhapure, S. S.; Pawar, R. P. ARKIVOC 2006, 205.
[37] Sun, M.; Wei, H.-T.; Li, D.; Zheng, Y.-G.; Cai, J.; Ji, M. Synth. Commun. 2008, 38, 3151.
[38] Mohammadpoor-Baltork, I.; Moghadam, M.; Tangestaninejad, S.; Mirkhani, V.; Hojati, S. F. Catal. Commun. 2008, 9, 1153.
[39] Mirkhani, V.; Mohammadpoor-Baltork, I.; Moghadam, M.; Tangestaninejad, S.; Abdollahi-Alibeik, M.; Kargar, H. Appl. Catal., A 2007, 325, 99.
[40] Mohammadpoor-Baltork, I.; Mirkhani, V.; Moghadam, M.; Tangestaninejad, S.; Zolfigol, M. A.; Abdollahi-Alibeik, M.; Khosropour, A. R.; Kargar, H.; Hojati, S. F. Catal. Commun. 2008, 9, 894.
[41] Mohammadpoor-Baltork, I.; Moghadam, M.; Tangestaninejad, S.; Mirkhani, V.; Hojati, S. F. Polyhedron 2008, 27, 750.
[42] Shaabani, A.; Seyyedhamzeh, M.; Maleki, A.; Rezazadeh, F. Appl. Catal., A 2009, 358, 146.
[43] Masoud Nasr-Esfahani, M. M.; Majid Moghadam, P. A. ARKIVOC 2010, 97.
[44] Nasr-Esfahani, M.; Montazerozohori, M.; Mehrizi, S. J. Heterocycl. Chem. 2011, 48, 249.
[45] de la Hoz, A.; Díaz-Ortiz, Á.; del Carmen Mateo, M.; Moral, M.; Moreno, A.; Elguero, J.; Foces-Foces, C.; Rodríguez, M. L.; Sánchez-Migallón, A. Tetrahedron 2006, 62, 5868.
[46] An, S. J.; Yin, B.; Liu, P.; Li, X. N.; Li, C.; Li, J. L.; Shi, Z. Synthesis 2013, 45, 2525.
[47] Manikandan, R.; Anitha, P.; Prakash, G.; Vijayan, P.; Viswanathamurthi, P.; Butcher, R. J.; Malecki, J. G. J. Mol. Catal. A:Chem. 2015, 398, 312.
[48] Hojati, S. F.; Mohammadpoor-Baltork, I.; Maleki, B.; Gholizadeh, M.; Shafiezadeh, F.; Haghdoust, M. Can. J. Chem. 2010, 88, 135.
[49] Zhang, J.; Wang, X.; Yang, M. P.; Wan, K. R.; Yin, B.; Wang, Y. X.; Li, J. L.; Shi, Z. Tetrahedron Lett. 2011, 52, 1578.
[50] (a) Sun, H.-B.; Sun, Y.; Chen, W.; Qin, P.; Qi, X. Chin. J. Org. Chem. 2014, 34, 1889 (in Chinese). (孙宏滨, 孙源华, 陈文龙, 秦鹏, 齐轩, 有机化学, 2014, 34, 1889.)
(b) Sun, H.-B.; Li, D.; Xie, W.; Deng, X. Heterocycles 2016, 92, 423.
[51] Huh, D. H.; Ryu, H.; Kim, Y. G. Tetrahedron 2004, 60, 9857.
[52] Li, G.; Wang, M. Chin. J. Pharm. 2008, 39, 88 (in Chinese). (李光壁, 王明刚, 中国医药工业杂志, 2008, 39, 88.)
[53] Nenajdenko, V. G.; Muzalevskiy, V. M.; Shastin, A. V.; Balenkova, E. S.; Kondrashov, E. V.; Ushakov, I. A.; Rulev, A. Y. J. Org. Chem. 2010, 75, 5679.
[54] Mirkhani, V.; Moghadam, M.; Tangestaninejad, S.; Kargar, H. Tetrahedron Lett. 2006, 47, 2129.
[55] Houlihan, W. J.; Kelly, L.; Pankuch, J.; Koletar, J.; Brand, L.; Janowsky, A.; Kopajtic, T. A. J. Med. Chem. 2002, 45, 4097.
[56] Anastassiadou, M.; Danoun, S. d.; Crane, L.; Baziard-Mouysset, G.; Payard, M.; Caignard, D.-H.; Rettori, M.-C.; Renard, P. Biorg. Med. Chem. 2001, 9, 585.
[57] Dash, P.; Kudav, D. P.; Parihar, J. A. J. Chem. Res. 2004, 7, 490.
[58] Piskov, V. B.; Kasperovich, V. P.; Yakovleva, L. M. Khim. Geterotsikl. Soedin. 1976, 8, 1112.