2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮的合成与杀菌活性
收稿日期: 2014-07-03
修回日期: 2014-08-20
网络出版日期: 2014-08-29
Synthesis and Fungicidal Activity of 2-Alkylaminosulfonyl-5,6-dihydro-dibenzo[b,e]azephine-6,11-dione
Received date: 2014-07-03
Revised date: 2014-08-20
Online published: 2014-08-29
以蒽醌为原料, 经Schmidt重排为5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮, 再经氯磺酰化和胺化合成了一系列新颖的2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮. 结构经1H NMR, 13C NMR和高分辨质谱确证. 初步的生测结果表明, 它们对棉花立枯病菌、油菜菌核病菌和芦笋茎枯病菌具有一定的杀菌活性. 其中, 2-(3-三氟甲基-4-溴苯基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11二酮(4u)对芦笋茎枯病菌有良好的杀菌活性, 在50 mg/mL浓度下抑制率达96.3%, 与对照药剂百菌清基本相当(在50 mg/mL浓度下的抑制率为98.8%). 初步的构效关系分析指出, 氟原子的引入有利于杀菌活性的提高.
肖炎双 , 张建军 , 闫晓静 , 董燕红 , 袁会珠 , 梁晓梅 , 王道全 . 2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮的合成与杀菌活性[J]. 有机化学, 2014 , 34(12) : 2493 -2498 . DOI: 10.6023/cjoc201407004
A series of novel 2-(alkylaminosulfonyl)-5,6-dihydro-dibenzo[b,e]azephine-6,11-dione derivatives were synthesized starting from anthraquinone by Schmidt rearrangement to 5,6-dihydro-dibenzo[b,e]azephine-6,11-dione, followed by chlorosulfonylation and amination. Their structures were confirmed by 1H NMR, 13C NMR and high-resolution mass spectrometry (HRMS). The preliminary bioassay showed that compounds have some fungicidal activity against Rhizoctonia solani, Sclerotinia sclerotiorum and Phomopsis asparagi. Among them, 2-(3-trifluoromethyl-4-bromophenylaminosulfonyl)-5,6-dihydro-dibenzo[b,e]azepine-6,11-dione (4u) has good fungicidal activity against Phomopsis asparagi and the inhibition rate reached 96.3% at 50 mg/mL, and is comparable with commercial fungicide chlorothalonil. The preliminary structure-activity relationship analysis indicated that introduction of fluorine is favorable to the increase of the activity.
[1] Patrick, G. L. An Introduction to Medicinal Chemistry, Oxford University Press, Oxford, 1995.
[2] Fujita, T. Agrochem. Jpn. 1994, 65, 17.
[3] Tomlin, C. D. S. Flusulfamide, Version 3.0 of the e-Pesticide Manual, BCPC, 2004-05, 394.
[4] Angeta, F.; Vittorio, F.; Aniello, C. Commun. Agric. Appl. Biol. Sci. 2009, 74, 917.
[5] Tomlin, C. D. S. Cyazofamide, Version 3.0 of the e-Pesticide Manual, BCPC, 2004-05, 185.
[6] Wang, X.-P.; Wang, D.-Q. Chem. J. Chin. Univ. 1997, 18, 889 (in Chinese). (汪晓平, 王道全, 高等学校化学学报, 1997, 18, 889.)
[7] Li, X.-H.; Yang, X.-L.; Liang, X.-M.; Kai, Z.-P.; Yuan, H.-Z.; Yuan, D.-K.; Zhang, J.-J.; Wang, R.-Q.; Ran, F.-X.; Qi, S.-H.; Ling, Y.; Chen, F.-H.; Wang, D.-Q. Bioorg. Med. Chem. 2008, 16, 4538.
[8] Zhu, W.-J.; Wu, P.; Liang, X.-M.; Dong, Y.-H.; Zhang, J.-J.; Yuan, H.-Z.; Yuan, H.-Z.; Qi, S.-H.; Wu, J.-P.; Chen, F.-H.; Wang, D.-Q. J. Agric. Food Chem. 2008, 56, 6547.
[9] Li, X.-H.; Qi, Z.-Q; Zhong, C.-J.; Zhang, Y.; Ji, M.-S.; Wang, Y.-Z.; Wang, D.-Q. Chin. J. Pestic. Sci. 2008, 10, 136 (in Chinese). (李兴海, 祁之秋, 钟昌继, 张扬, 纪明山, 王英姿, 王道全, 农药学学报, 2008, 10, 136.)
[10] Liang, X.-M.; Fan, X. Q.; Dong, Y.-H.; Yuan, H.-Z.; Qi, S.-H.; Wang, D.-Q. Wang, D.-Q.; Wu, J.-P. Chin. J. Pestic. Sci. 2008, 10, 156 (in Chinese). (梁晓梅, 方学琴, 董燕红, 袁会珠, 齐淑华, 王道全, 吴景平, 农药学学报, 2008, 10, 156.)
[11] Shi, D.-Q.; Liu, J.-A.; Liu, X.-P.; Wang, J.-P. Chin. J. Appl. Chem. 2003, 20, 130 (in Chinese). (石德清, 刘军安, 刘小鹏, 王今红, 应用化学, 2003, 20, 130.)
[12] Sun, G.-X.; Jiang, X.-L.; Wang, Y.-H.; Shen, D.-L. Modern Agrochem. 2005, 4, 14 (in Chinese). (孙国香, 蒋旭亮, 王煜华, 沈德隆, 现代农药, 2005, 4, 14.)
[13] Jiang, L.; Li, C.-C.; Jia, L.-S.; Lu, F.-S. Chin. J. Org. Chem. 2006, 26, 203 (in Chinese). (姜林, 李长城, 贾立生, 路福绥, 有机化学, 2006, 26, 203.)
[14] Li, C.-C.; Jiang, L.; Wang, L.-Z.; Lu, F.-S. Chem. Reag. 2006, 28, 225 (in Chinese). (李长城, 姜林, 王立增, 路福绥, 化学试剂, 2006, 28, 225.)
[15] Huang, J.-X.; Jia, Y.-M.; Liang, X.-M.; Zhu, W-J.; Zhang, J.-J.; Dong, Y.-H.; Yuan, H.-Z.; Qi, S.-H.; Wu, J.-P.; Chen, F.-H.; Wang, D.-Q. J. Agric. Food Chem. 2007, 55, 10857.
[16] Xiao, Y.-S.; Yan, X.-J.; Xu, Y.-J.; Huang, J.-X.; Yuan, H.-Z.; Liang, X.-M.; Zhang, J.-J.; Wang, D.-Q. Pest Manage. Sci. 2013, 69, 814.
[17] Johnson, T. C.; Wilmonte, C.; Nasutavicus, A. US 5177206, 1993 [Chem. Abstr. 1993, 118, 191760].
[18] Gonzalez, M. A.; Gorman, D. B.; Hamilton, C. T.; Roth, G. A. Proc. Res. Dev. 2008, 12, 301.
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