新型吡咯-2-甲酸及其衍生物的设计、合成和杀虫、杀螨活性

doi:10.6023/cjoc202211010

摘要/Abstract

为发现具有良好生物活性的吡咯类新农药候选化合物, 基于高效杀虫杀螨剂虫螨腈(Chlorfenapyr)化学结构, 采用活性亚结构拼接法, 设计并合成了3种关键中间体吡咯-2-甲酸和26种新型吡咯类化合物, 通过改变吡咯环N位取代基, 探究不同取代基对吡咯类化合物生物活性的影响. 生物活性测试结果表明, 大部分化合物对小菜蛾(Plutella xylostella)和甜菜夜蛾(Spodoptera exigua Hiibner)表现出良好的杀虫活性, 部分化合物对朱砂叶螨(Tetranychus cinnabarinus)表现出一定程度的杀螨活性. 其中3-溴-1-(丁氧基甲基)-5-(4-氯苯基)-4-氰基-N-(2,4-二甲基苯基)-吡咯-2-甲酰胺(6r)、3-溴-5-(4-氯苯基)-4-氰基-1-乙基-N-(2-甲基-4-全氟丙烷苯基)-吡咯-2-甲酰胺(6v)和3-溴-5-(4-氯苯基)-4-氰基-N-(2,5-二氯-4-(1,1,2,3,3,3-六氟丙氧基)苯基)-1-乙基-吡咯-2-甲酰胺(6z)在浓度为100 mg•L^－1下, 杀虫效果与除虫脲相近, 低于虫螨腈的杀虫杀螨活性, 杀螨效果优于商品化杀螨剂炔螨特.

关键词: 吡咯, 虫螨腈, 新农药, 生物活性

To discover new pyrrole pesticide candidates with good biological activity, based on the chemical structure of the highly efficient insecticidal and acaricidal agent chlorfenapyr, three key intermediates pyrrole-2-carboxylic acid and 26 new pyrrole compounds were designed and synthesized by active substructure splicing method. The effects of different substituents on the biological activity of pyrrole compounds were explored by changing the N substituents of pyrrole ring. The bioassay results showed that most of the compounds showed good insecticidal activity against Plutella xylostella and Spodoptera exigua Hiibner, and some compounds showed a certain degree of acaricidal activity against Tetranychus cinnabarinus. 3-Bromo-1- (butoxymethyl)-5-(4-chlorophenyl)-4-cyano-N-(2,4-dimethylphenyl)-1H-pyrrole-2-carboxamide (6r), 3-bromo-5-(4-chloro- phenyl)-4-cyano-1-ethyl-N-(2-methyl-4-(perfluoropropan-2-yl)phenyl)-1H-pyrrole-2-carboxamide (6v), and 3-bromo-5-(4-ch- lorophenyl)-4-cyano-N-(2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl)-1-ethyl-1H-pyrrole-2-carboxamide (6z) are insecticidal at a concentration of 100 mg•L^－1. The effect is similar to that of diflubenzuron, which was lower than the insecticidal acaricidal activity of chlorfenapyr, and the acaricidal effect was better than that of the commercial acaricide propargite.

Key words: pyrrole, chlorfenapyr, new pesticide, biological activity

引用此文

光明甲, 姜硕, 朱宝玉, 张如松, 王鲲鹏, 王明慧, 许良忠. 新型吡咯-2-甲酸及其衍生物的设计、合成和杀虫、杀螨活性[J]. 有机化学, 2023, 43(8): 2895-2904.

Mingjia Guang, Shuo Jiang, Baoyu Zhu, Rusong Zhang, Kunpeng Wang, Minghui Wang, Liangzhong Xu. Design, Synthesis and Insecticidal, Acaricidal Activities of Novel Pyrrole-2-carboxylic Acid and Their Derivatives[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2895-2904.

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

分享此文

图/表 7

参考文献 20

[1]	Xu, S.-C.; Wan, Q.; Jing, M.-G. World Pestic. 2003, 25, 1. (in Chinese)
	( 徐尚成, 万琴, 蒋木庚, 世界农药, 2003, 25, 1.)
[2]	Xu, S.-C.; Jiang, M.-G. Chin. J. Pestic. Sci. 2002, 4, 1. (in Chinese)
	( 徐尚成, 蒋木庚, 农药学学报, 2002, 4, 1.)
[3]	Addor, R. W.; Babcock, T. J.; Black, B. C. Environ. Sci. Nano. 1992, 283.
[4]	Li, Y.-Q.; Wang, Z.-W.; Zhang, P.-X.; Liu, Y.-X.; Xiong, L.-X.; Wang, Q.-M. J. Heterocycl. Chem. 2014, 51, 1410. doi: 10.1002/jhet.v51.5
[5]	Abdelhamid, A. A.; Salama, K. S. M.; Elsayed, A. M.; Gad, M. A.; El-Remaily, M. A. E. A. A. ACS Omega. 2022, 7, 3990. doi: 10.1021/acsomega.1c05049 pmid: 35155894
[6]	Cater, G. T.; Nietsche, J. N.; Goodman, J. J.; Torrey, M. J.; Dunne, T. S.; Borders, D. B.; Testa, R. T. J. Antibiot. 1987, 40, 233. doi: 10.7164/antibiotics.40.233
[7]	Nevil, D.; Nyfeler, R.; Sozzi, D. Brighton Crop Protection Conference—Pests and Diseases-1988, Vol. 1, British Crop Protection Council, 1988, pp. 65-72.
[8]	Zhang, Z.-Z.; Zhang, Y.-B. Shanghai Chem. Ind. 2001, 26, 19. (in Chinese)
	( 张仲贞, 张一宾, 上海化工, 2001, 26, 19.)
[9]	Gehmann, K.; Nyfeler, R.; Leadbeater, A. J.; Nevill, D.; Sozzi, D. Brighton Crop Protection Conference—Pests and Diseases-1990, Vol. 2, British Crop Protection Council, 1990, pp. 399-406.
[10]	Liu, A.-P.; Tang, M.; Yu, S.-Y.; Liu, X.-P.; Wang, X.-G.; Pei, H.; Wu, D.-X.; Hu, L.; Ou, X.-M.; Huang, M.-Z. Sci China: Chem. 2013, 56, 117.
[11]	Charan, R. D.; Schlingmann, G.; Bernan, V. S.; Feng, X.; Carter, G. T. J. Nat. Prod. 2006, 69, 29. doi: 10.1021/np0503404
[12]	Zhao, Y.; Li, Y.-Q.; Ou, X.-M.; Zhang, P.-X.; Huang, Z.-Q.; Bi, F.-C.; Huang, R.-Q.; Wang, Q.-M. J. Agric. Food Chem. 2008, 56, 10176. doi: 10.1021/jf802464d
[13]	Zhao, Y.; Mao, C.-H.; Li, Y.-Q.; Zhang, P.-X.; Huang, Z.-Q.; Bi, F.-C.; Huang, R.-Q.; Wang, Q.-M. J. Agric. Food Chem. 2008, 56, 7326. doi: 10.1021/jf801311h
[14]	Ma, Q.-Q.; Liu, Y.-X.; Zhang, P.-X.; Li, Y.-Q.; Xiong, L.-X.; Wang, Q.-M. J. Agric. Food Chem. 2014, 62, 6072. doi: 10.1021/jf501377t
[15]	Li, Y.-Q.; Zhang, P.-X.; Ma, Q.-Q.; Song, H.-B.; Liu, Y.-X.; Wang, Q.-M. Bioorg. Med. Chem. Lett. 2012, 22, 6858. doi: 10.1016/j.bmcl.2012.09.036
[16]	Ramig, K.; Englander, M.; Kallashi, F.; Livchits, L.; Zhou, J. Tetrahedron Lett. 2002, 43, 7731. doi: 10.1016/S0040-4039(02)01836-1
[17]	David, G.; Kuhn-f, V. M.; Kamhi, J. A.; Furch, R. E.; Diehl, G. T.; Lowent, V. K. Pestic. Sci. 1994, 41, 279. doi: 10.1002/ps.v41:3
[18]	Herron, G. A.; Rophail, J. E. Exp. Appl. Acarol. 2003, 31, 131. pmid: 14756407
[19]	Yu, X.-L.; Liu, Y.-X.; Li, Y.-Q.; Wang, Q.-M. J. Agric. Food Chem. 2016, 64, 3034. doi: 10.1021/acs.jafc.6b00645
[20]	Guidelines for In-house Bioassay Testing of Pesticides, Part 9 of Pesticides: Spray method, NY/T 1154.9-2008, 2008, 07, 01. (in Chinese)
	(农药室内生物测定试验准则杀虫剂第9部分: 喷雾法, NY/T 1154.9-2008, 2008, 07, 01.)

Compd.	y=ax＋b	LC₅₀/(mg•L^－1)	R
6q	y=1.86x＋2.65	18.34	0.97
6r	y=1.62x＋2.97	17.91	0.97
6v	y=1.52x＋3.01	20.38	0.96
6z	y=1.69x＋2.83	19.23	0.98
C-2	y=1.80x＋3.04	12.27	0.98
C-3	y=2.37x＋4.21	2.15	0.97

Compd.	y=ax＋b	LC₅₀/(mg•L^－1)	R
6q	y=1.86x＋2.65	18.34	0.97
6r	y=1.62x＋2.97	17.91	0.97
6v	y=1.52x＋3.01	20.38	0.96
6z	y=1.69x＋2.83	19.23	0.98
C-2	y=1.80x＋3.04	12.27	0.98
C-3	y=2.37x＋4.21	2.15	0.97

Compd.	y=ax＋b	LC₅₀/(mg•L^－1)	R
6q	y=1.51x＋3.24	14.64	0.98
6r	y=1.54x＋3.18	15.20	0.97
6v	y=1.74x＋2.96	14.87	0.97
6z	y=1.61x＋3.09	15.36	0.98
C-2	y=1.72x＋3.29	9.86	0.97
C-3	y=2.11x＋4.27	2.21	0.96

Compd.	y=ax＋b	LC₅₀/(mg•L^－1)	R
6q	y=1.51x＋3.24	14.64	0.98
6r	y=1.54x＋3.18	15.20	0.97
6v	y=1.74x＋2.96	14.87	0.97
6z	y=1.61x＋3.09	15.36	0.98
C-2	y=1.72x＋3.29	9.86	0.97
C-3	y=2.11x＋4.27	2.21	0.96

Compd.	y=ax＋b	LC₅₀/(mg•L^－1)	R
6i	y=1.30x＋3.76	8.99	0.95
6j	y=1.20x＋3.92	7.94	0.97
6r	y=1.29x＋3.83	8.07	0.96
6v	y=1.31x＋3.80	8.24	0.97
6z	y=1.20x＋4.05	6.19	0.96
C-1	y=1.29x＋3.44	16.19	0.96
C-3	y=1.01x＋4.73	1.85	0.96