N-叔丁基-N'-氟代苯甲酰基-取代吡啶甲酰肼衍生物的合成与杀虫活性研究

doi:10.6023/cjoc201510019

摘要/Abstract

为改进双酰肼类杀虫剂的性能,将氟代苯基和吡啶环同时引入双酰肼的基本结构中,设计合成了20个新型的N-叔丁基-N'-氟代苯甲酰基-取代吡啶甲酰肼衍生物,经¹H NMR、¹³C NMR、IR和HRMS确证了分子结构.生物活性测试表明,在浓度为500mg/L时,大部分化合物对粘虫(Mythimna separata)的致死率都达到80%以上.其中N-叔丁基-N'-(2,6-二氟苯甲酰基)-2-氯烟酰肼(6bb)和N-叔丁基-N'-(2,6-二氟苯甲酰基)-2,5-二氯烟酰肼(6gb)在浓度为10mg/L时对粘虫的致死率分别为100%和80%.化合物6bb对东方粘虫的半致死浓度(LC₅₀值)为8.77mg/L,对东方粘虫的毒力约为虫酰肼的0.51倍,对小菜蛾(Plutella xylostella)的毒力为虫酰肼的1.5倍.

关键词: 双酰肼, 吡啶甲酰肼, 合成, 杀虫活性

In order to find novel diacylhydrazine derivatives which possessed high activities against pests, 20 novel N-(tert-butyl)-N'-fluorobenzoyl-substitutedpyridylcarbonyl hydrazide derivatives were synthesized by introducing fluoro-contained phenyl and pyridine into the basic structure of diacylhydrazines. Their structures were confirmed by ¹H NMR, ¹³C NMR, IR and HRMS. The bioassay results indicated that most of the compounds exhibited more than 80% mortality against Mythimna separateat the concentration of 500 mg/L. Among these compounds, N-(tert-butyl)-N'-(2,6-difluorobenzoyl)-N-2-chloronico-tinohydrazine (6bb)andN-(tert-butyl)-N'-(2,6-difluorobenzoyl)-N-2,5-dichloronicotinohydrazine (6gb)exhibited 100% and 80% mortality against Mythimna separateat 10 mg/L, respectively. The LC₅₀ of compound 6bb against Mythimna separatawas 8.77 mg/L, and it showed about 0.51 times of toxicity against Mythimna separatethan tebufenozide and had 1.5 times of toxicity against Plutella xylostella than tebufenozide.

Key words: diacylhydrazine, pyridylcarbonyl hydraziden, synthesis, insecticidal activity

引用此文

胡崇波, 刘建华, 杜晓华. N-叔丁基-N'-氟代苯甲酰基-取代吡啶甲酰肼衍生物的合成与杀虫活性研究[J]. 有机化学, 2016, 36(5): 1051-1059.

Hu Chongbo, Liu Jianhua, Du Xiaohua. Synthesis and Insecticidal Activities of N-(tert-Butyl)-N'-fluorobenzoyl-substitutedpyridylcarbonyl Hydrazide Derivatives[J]. Chin. J. Org. Chem., 2016, 36(5): 1051-1059.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

-氟代苯甲酰基-取代吡啶甲酰肼衍生物的合成与杀虫活性研究”的文章，特向您推荐。请打开下面的网址：https://sioc-journal.cn/Jwk_yjhx/CN/abstract/abstract345395.shtml' name="neirong"> -氟代苯甲酰基-取代吡啶甲酰肼衍生物的合成与杀虫活性研究'>

()

参考文献

[1] Nakagawa, Y.; C. Henrich, V. FEBS J. 2009, 276, 6128.
[2] Xu, Z.-H.; Li, J.-K. Jiangsu Agric. Sci. 2015, 45, 5 (in Chinese).
(徐志红, 李俊凯, 江苏农业科学, 2015, 45, 5.)
[3] (a) Zhao, Q.-Q.; Shang, J.; Huang, Z.-Q.; Wang, K.-Y.; Bi, F.-C.; Huang, Y.-Q.; Wang, Q.-M. J. Agric. Food Chem. 2008, 56, 5254.
(b) Wing, K. D. Science 1988, 241, 467.
[4] (a) Oikawa, N.; Nakagawa, Y.; Nishimura, K.; Ueno, T.; Fujita, T. Pestic. Sci. 1994, 41, 139.
(b) Oikawa, N.; Nakagawa, Y.; Nishimura, K.; Ueno, T.; Fujita, T. Pestic. Biochem. Physiol. 1994, 48, 135.
(c) Nakagawa, Y.; Soya, Y.; Nakai, K.; Oikawa, N.; Nishimura, K.; Ueno, T.; Fujita, T.; Kurihara, N. Pestic. Sci. 1995, 43, 339.
[5] (a) Chen, Z.-M. World Pestic. 2007, 29, 12 (in Chinese).
(程志明, 世界农药, 2007, 29, 12.) (b) Nakagawa, Y.; Hattori, K.; Shimizu, B.; Akamatsu, M.; Miyagawa, H.; Ueno, T. Pestic. Sci. 1998, 53, 267.
(c) Soin, T.; Swevers, L.; Kotzia, G.; Iatrou, K.; Janssen, C. R.; Rouge, P.; Harada, T.; Nakagawa, Y.; Smagghe, G. Pest. Manage. Sci. 2010, 66, 1215.
(d) Hormann, R. E.; Smagghe, G.; Nakagawa, Y. QSAR Comb. Sci. 2008, 27, 1098.
[6] (a) Heller, J. J.; Mattioda, H.; Klein, E.; Sagenmuller, A. Brighton Crop Prot. Conf.-Pests Dis. 1992, 1, 59.
(b) Le, D. P.; Thirugnanam, M.; Lidert, Z.; Carlson, G. R.; Ryan, J. B. Brighton Crop Prot. Conf.-Pests Dis. 1996, 2, 481.
(c) Lidert, Z.; Hormann, R. E.; Le, D. P.; Opie, T. R. CA 2103110, 1994 [Chem. Abstr. 1994, 112, 314557].
(d) Cowles, R. S.; Villani, M. G. J. Econ. Entomol. 1996, 89, 1356.
(e) Carlson, G. R.; Aller, H. E. GB 2231268, 1990 [Chem. Abstr. 1990, 114, 180361].
(f) Yanagi, M.; Sugizaki, H.; Toya, T.; Kato, Y.; Shirakura, H.; Watanabe, T.; Yajima, Y.; Kodama, S.; Masui, A.; Yanai, T.; Tsukamoto, Y.; Sawada, Y.; Yokoi, S. EP 496342, 1992 [Chem. Abstr. 1992, 117, 212514].
(g) Yanagi, M.; Watanabe, T.; Masui. Brighton Crop Prot. Conf.-Pests Dis. 2000, 2, 27.
(h) Zhang, X.-N.; Li, Y.-F.; Ni, Y.-P.; Zhu, L.-M.; Hu, J.-B.; Jiang, M.-G. Chin. J. Pestic. 2003, 42, 18 (in Chinese).
(张湘宁, 李玉峰, 倪钰萍, 朱丽梅, 胡嘉斌, 蒋木庚, 农药, 2003, 42, 18.)
[7] Mao, C.-H.; Wang, Q.-M.; Huang, R.-Q. Chin. J. Pestic. Sci. 2004, 6, 1 (in Chinese).
(毛春晖, 汪清民, 黄润秋, 农药学学报, 2004, 6, 1.)
[8] (a) Huang, Z.-Q.; Lv, Z.-J.; Zhu, H.-L.; Liu, B.; Wei, Z.; Shang, Z.-Q.; Shi, J. Chin. J. Pestic. 2014, 53, 161 (in Chinese).
(黄治强, 吕丽娟, 朱华玲, 刘斌, 尉震, 尚志强, 石军, 农药, 2014, 53, 161.) (b) Zhao, H.-W.; Liang, C. Organo-fluorine Ind. 2010, 2, 28 (in Chinese).
(赵红伟, 梁诚, 有机氟工业, 2010, 2, 28.)
[9] Wing, K. D.; Pa, L. US 5424333, 1995[Chem. Abstr. 1995, 123, 313108].
[10] (a) Shang, E.-C.; Liu, C.-L.; Du, Y.-J. Chem. Ind. Eng. Prog. 1996, 5, 11 (in Chinese).
(尚尔才, 刘长令, 杜英娟, 化工进展, 1996, 5, 11.) (b) Yang, J.-C.; Dai, R.-H.; Liu, Y.-P.; Wu, Q.; Liu, C.-L. Chin. J. Pestic. 2011, 50, 625 (in Chinese).
(杨吉春, 戴荣华, 刘允萍, 吴峤, 刘长令, 农药, 2011, 50, 625.)
[11] (a) Hsu, A. C.; Le, D. P. US 5354762, 1994 [Chem. Abstr. 1994, 122, 314457].
(b) Hsu, A. C.; Aller, H. E.; Le, D. P.; Hamp, D. W.; Weinstein, B.; Murphy, R. A. US 6013836, 2000 [Chem. Abstr. 2000, 132, 89489].
[12] Mao, C.-H.; Wang, Q.-M.; Huang, Y.-Q.; Bi, F.-C.; Wang, K.-L. CN 1654464, 2005 [Chem. Abstr. 2005, 144, 468023].
[13] (a) Liu, J.-H. Ph.D. Dissertation, Zhejiang University of Technology, Hangzhou, 2014 (in Chinese).
(刘建华, 博士论文, 浙江工业大学, 杭州, 2014.) (b) Du, X.-H; Liu, J.-H; Hu, C.-B. CN 104744358, 2015 [Chem. Abstr. 2015, 162, 82129].
[14] (a) Huang, Z.-Q.; Cui, Q.-M.; Xiong, L.-X.; Wang, Z.-W.; Wang, K.-Y.; Zhao, Q.-Q.; Bi, F.-C.; Wang, Q.-M. J. Agric. Food Chem. 2009, 57, 2450.
[15] Chen, N.-G.; Liu, X.-Y.; Ren, Z.-P. West China J. Pharm. Sci. 2008, 23, 166 (in Chinese).
(陈年根, 刘新泳, 任兆平, 华西药学杂志, 2008, 23, 166.)
[16] Zhang, X.-N.; Li, Y.-F.; Zhu, L.-M.; Liu, L.-Y.; Sha, X.-Y.; Xu, H.; Ma, H.-J.; Wang, F.-Y.; Ni, Y.-P.; Guo, L.-P. CN 1313276, 2001 [Chem. Abstr. 2001, 137, 294865].
[17] Sawada, Y.; Yanai, T.; Nakagawa, H.; Tsukamoto, Y.; Yokoi, S.; Yanagi, M.; Toya, T.; Sugizaki, H.; Kato, Y.; Shirakura, H.; Watanabe, T.; Yajima, Y.; Kodama, S.; Masui, A. Pest Manage. Sci. 2003, 59, 26.