芳基吡唑氟尿嘧啶类化合物的设计、合成与杀虫活性研究
收稿日期: 2014-03-15
修回日期: 2014-05-05
网络出版日期: 2014-06-03
基金资助
江苏省科技厅科技支撑计划（农业）（No. BE2011352）资助项目.
Design, Synthesis, Insecticidal Activity and Structure-Activity Relationship of Aryl Pyrazole 5-Fluorouracil Derivatives
Received date: 2014-03-15
Revised date: 2014-05-05
Online published: 2014-06-03
Supported by
Project supported by the Key Technology R&D Program of the Science and Technology Department of Jiangsu Province (No. BE2011352).
利用以γ-氨基丁酸（GABA）受体抑制剂芳基吡唑类杀虫剂的关键结构5-氨基-3-氰基-1-（取代苯基）吡唑为基本母核，设计、合成了26个创新结构芳基吡唑氟尿嘧啶化合物. 目标化合物结构均采用1H NMR，FTIR和元素分析进行了结构确证，以小菜蛾和库蚊为靶标进行了杀虫活性测试. 评价结果表明创制化合物具有优越的杀虫活性：在浓度为1000 mg·L-1时，化合物5a～5c， 5e，5m及5u对库蚊具有100%的杀虫活性；在浓度为400 mg·L-1时，化合物5p对小菜蛾具有94.5%的杀虫活性. 初步构效关系研究表明：苯环上取代基种类及位置等对化合物的生物活性有重要的影响.
傅晓东 , 陈月 , 杨阳 , 贺书泽 , 沈陈 , 万嵘 . 芳基吡唑氟尿嘧啶类化合物的设计、合成与杀虫活性研究[J]. 有机化学, 2014 , 34(10) : 2090 -2098 . DOI: 10.6023/cjoc201403035
On the basis of the key structure of γ-amino butyric acid (GABA) receptor inhibitor aryl pyrazole pesticides, a series of novel aryl pyrazole derivatives containing 5-fluorouracil were designed and synthesized via the key intermediate 5-amino-3-cyano-1-(substituted phenyl)pyrazole. The structures of target compounds were confirmed by 1H NMR, FTIR and elemental analysis, and their insecticidal activities were evaluated against diamondback moth (Plutella xylostella) and mosquito (Culex pipiens). The results of bioassays indicated that aryl pyrazole 5-fluorouracil derivatives exhibited satisfactory insecticidal activities. The insecticidal activities of compounds 5a～5c, 5e, 5m and 5u against mosquito were all 100% at 1000 mg·L-1. Moreover, the compound 5p exhibited good lethal activity (94.45%) against P. xylostella at the concentration of 400 mg·L-1. The results also indicated that the type and position of substituent on the phenyl ring play crucial roles on the biological activities of the compounds.
Key words： aryl pyrazole; 5-fluorouracil; synthesis; insecticidal activity
[1] Chou, D. T.; Bastiaans, H. M. M.; Kuhlmann, A. WO 2003074493, 2003 [Chem. Abstr. 2003, 139, 246029].
[2] Zhan, Q.; Li, Y.; Xiong, L.; Wang, Q. J. Agric. Food Chem. 2010, 58, 4992.
[3] Sun, Y.; Qiao, H.; Ling, Y.; Yang, S. J. Agric. Food. Chem. 2011, 59, 2456.
[4] Cheng, J. L.; Wei, F. L.; Zhu, L.; Zhao, J. H.; Zhu, G. L. Chin. J. Org. Chem. 2008, 28, 622 (in Chinese).
(程敬丽, 魏方林, 朱烈, 赵金浩, 朱国念, 有机化学, 2008, 28, 622.)
[5] Finkelstein, B. L.; Taggi, A. E.; Long, J. K. WO 2008124092, 2008 [Chem. Abstr. 2008, 149, 464723].
[6] Heil, M.; Lui, N.; Erdelen, C. DE 4405207, 1995 [Chem. Abstr. 1995, 124, 8808].
[7] Ito, S; Noritake, C; Iwata, A. WO 2002090335, 2002 [Chem. Abstr. 2002, 137, 370114].
[8] Murakami, H.; Io, T.; Takii, S. JP 2005008628, 2005 [Chem. Abstr. 2005, 142, 88233].
[9] Szabo, G.; Fischer, J. J. Med. Chem. 2008, 51, 142.
[10] Stevens, M. M.; Helliwell S.; Warren G. N. Field Crop. Res. 1998, 57, 195.
[11] Les, G.; Don, R.; Michael, K. R. J. Agric. Urban Entomol. 2003, 20, 221.
[12] Durier, V.; Rivauh, C. Med. Vet. Entomol. 2000, 14, 410.
[13] Dominik, H.; John, E. C. Proc. Natl. Acad. Sci. 1996, 93, 12764.
[14] Wu, T. T. US 5814652, 1998 [Chem. Abstr. 1998, 129, 256473].
[15] Longley, D. B.; McDermott, U.; Johnston, P. G. Clin. Colorectal Cancer 2003, 2, 223.
[16] Wyatt, M. D.; Wilson, D. M. Ⅲ Cell. Mol. Life Sci. 2009, 66, 788.
[17] Wan, R.; Zhang, J.; Han, F.; Wang, P. Nucleoside Nucleotide Nucleic 2011, 30, 280.
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