Synthesis, Insecticidal Activities, and Structure-Activity Relationship Studies of Novel Diamide Compounds Containing (Halogenated) Alkoxy Group

doi:10.6023/cjoc202311015

Abstract

In order to discover new pesticide with novel structure, good activity and environmental friendliness, a series of new diamide compounds containing (halogenated) alkoxy group were designed and synthesized through introducing (halogenated) alkoxy group based on the structure of cyproflanilide. Their structures were confirmed by ¹H NMR, ¹³C NMR and HRMS. The bioassay results showed that most of the compounds exhibit excellent insecticidal activity against Plutella xylostella. Such as N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenz- amido)-2-fluorobenzamide (4a), N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethoxy)phenyl)-3-(N-(cyclopropylmethyl)- 4-fluorobenzamido)-2-fluorobenzamide (4b), N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-3-(N-(cyclo- propylmethyl)benzamido)-2-fluorobenzamide (4h), N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-3-(4- cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide (4j)~N-(3-((2-bromo-6-(difluoromethoxy)-4-(perfluoropropan- 2-yl)phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)isonicotinamide (4o), N-(3-((2-bromo-6-(difluoromethoxy)- 4-(perfluoropropan-2-yl)phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)-2,4-difluorobenzamide (4q) and N-(3-((2- bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)-2-fluoroiso-nicotinamide (4t) showed 100% mortality at 1 mg/L. Moreover, compound 4a not only has good insecticidal activities against Plutella xylostella and Chilo suppressalis close to cyproflanilide, but also shows better activities against Aphis craccivora and Tetranychus cinnabarinus than cyproflanilide, exhibiting a broader insecticidal spectrum. The field trials of compound 4a are ongoing.

Key words: diamide compounds, synthesis, insecticidal activity, structure-activity relationship

Cite this article

Jiyong Liu, Minghui Wu, Juncheng Xiang, Huailin Pang, Bin Li, Liang Lü. Synthesis, Insecticidal Activities, and Structure-Activity Relationship Studies of Novel Diamide Compounds Containing (Halogenated) Alkoxy Group[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1584-1591.

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References 22

[1]	Zhou, S.; Gu, Y. C.; Liu, M.; Wu, C. C.; Zhou, S.; Zhao, Y.; Jia, Z. H.; Wang, B. L.; Xiong, L. X.; Yang, N.; Li, Z. M. J. Agric. Food Chem. 2014, 62, 11054.
[2]	Zhou, S.; Yan, T.; Li, Y. X.; Jia, Z. H.; Wang, B. L.; Zhao, Y.; Qiao, Y. Y.; Xiong, L. X.; Li, Y. Q.; Li, Z. M. Org. Biomol. Chem. 2014, 12, 6643. doi: 10.1039/c4ob00716f pmid: 25026986
[3]	Li, Y. H.; Zhu H. J; Chen, K.; Liu, R.; Khallaf A; Zhang X. J; Ni, J. P. Org. Biomol. Chem. 2013, 11, 3979.
[4]	Guo, L.; Liang, P.; Zhou, X. G.; Gao, X. W. Sci. Rep. 2014, 4, 6924.
[5]	Hu, Z. D.; Chen, H. Y.; Li, Z. Y.; Zhang, D. Y.; Yin, F.; Lin, Q. S.; Bao, H. L.; Zhou, X. M.; Feng, X. Guangdong Agric. Sci. 2012, 1, 79 (in Chinese).
	( 胡珍娣, 陈焕瑜, 李振宇, 张德雍, 尹飞, 林庆胜, 包华理, 周小毛, 冯夏, 广东农业科学, 2012, 1, 79.)
[6]	Qi, H. L.; Cui, L.; Wang, Q. Q.; Liu, F.; Rui, C. H. Plant Prot. 2017, 43, 112 (in Chinese).
	( 齐浩亮, 崔丽, 王芹芹, 刘峰, 芮昌辉, 植物保护, 2017, 43, 112.)
[7]	Muriel, B.; Gagnebin, A.; Waser, J. Chem. Sci. 2019, 10, 10716.
[8]	Menear, K. A.; Adcock, C.; Boulter, R.; Cockcroft, X.; Copsey, L.; Cranston, A.; Dillon, K. J.; Drzewiecki, J.; Garman, S.; Gomez, S.; Javaid, H.; Kerrigan, F.; Knights, C.; Lau, A.; Vincent, M.; Moore, S.; Smith, J. C.; Martin, N. M. J. Med. Chem. 2008, 51, 6581. doi: 10.1021/jm8001263 pmid: 18800822
[9]	Chang, F.; Dutta, S.; Becnel, J. J.; Estep, A. S.; Mascal, M. J. Agric. Food Chem. 2014, 62, 476.
[10]	Liu, A. C.; He, X. L.; Feng, J. L.; Yu, C. H.; Zhang, S. K. Agrochemicals 2015, 54, 790 (in Chinese).
	( 刘安昌, 贺晓璐, 冯佳丽, 余彩虹, 张树康, 农药, 2015, 54, 790.)
[11]	Ozoe, Y.; Kita, T.; Ozoe, F.; Nakao, T.; Sato, K.; Hirase, K. Pestic. Biochem. Physiol. 2013, 107, 285.
[12]	Katsuta, H.; Nomura, M.; Wakita, T.; Daido, H.; Kobayashi, Y.; Kawahara, A.; Banba, S. J. Pestic. Sci. 2019, 44, 120.
[13]	Lorenzo, M.; Moldes, D.; Rodriguez Couto, S.; Sanroman, M. A. Chemosphere 2005, 60, 1124. pmid: 15993161
[14]	Huang, P. M.; Wu, M. H.; Lv, L.; Zhou, L. Q.; Liu, X. W.; Liu, J. Y. Tetrahedron Lett. 2022, 96, 153743.
[15]	Rosconi, F.; Fraguas, L. F.; Martínez-Drets, G.; Castro-Sowinski, S. Enzyme Microb. Technol. 2005, 36, 800.
[16]	Huang, P. M.; Liu, X. W.; Liu, M. H.; Zhou, L. Q.; Wu, M. H.; Liu, J. Y. Lett. Drug Des. Discovery 2024, 21, 496.
[17]	Dai, H.; Hong, Y.; Ye, L. Y.; Zhong, S. L.; Cao, X. F.; Shi, Y. J.; Li, C. J.; Shi, J.; Shi, L. Chin. J. Org. Chem. 2017, 37, 3006 (in Chinese).
	( 戴红, 洪宇, 叶林玉, 仲苏林, 曹雄飞, 石玉军, 李春建, 石健, 施磊, 有机化学, 2017, 37, 3006.) doi: 10.6023/cjoc201707022
[18]	Liu, J. Y.; Zhou, L. Q.; Xiang, J. C.; Ni, J. P.; Li, Z. C.; Pang, H. L.; Lv, L. World Pestic. 2021, 43, 34 (in Chinese).
	( 刘吉永, 周丽琪, 相君成, 倪珏萍, 李宗成, 庞怀林, 吕亮, 世界农药, 2021, 43, 34.)
[19]	Zhu, B. C.; Xu, T. M.; Kong, X. L.; Wei, W.; Li, X. N. Agrochemicals 2009, 48, 712 (in Chinese).
	( 朱冰春, 许天明, 孔小林, 韦伟, 李小年, 农药, 2009, 48, 712.)
[20]	Luo, C. Y.; Ma, W. J.; Lv, L.; Pang, H. L.; Xiang, J. C.; Zhou, L. Q.; Yin, D. L.; Liu, J. Y. Chin. J. Org. Chem. 2020, 40, 2963 (in Chinese).
	( 罗春艳, 马文静, 吕亮, 庞怀林, 相君成, 周丽琪, 尹笃林, 刘吉永, 有机化学, 2020, 40, 2963.) doi: 10.6023/cjoc202003025
[21]	Pitner, T.; Stoller, A.; Edmunds, A. WO2015097094, 2015 [Chem. Abstr. 2015, 90, 078815 ].
[22]	Liu, J. Y.; Lv, L.; Zhou, L. Q.; Du, Y. L.; Xiang, J. C.; Ni, J. P. CN 112661665, 2021 (in Chinese).
	( 刘吉永, 吕亮, 周丽琪, 杜永磊, 相君成, 相君成, 倪珏萍, CN 112661665B, 2021.)

Compd.	Plutella xylostella
Compd.	1 mg/L	0.1 mg/L	0.01 mg/L
4a	100.00	96.67	10.00
4b	100.00	46.67	0.00
4c	0.00	0.00	0.00
4d	90.00	20.00	0.00
4e	96.67	60.00	0.00
环丙氟虫胺	100.00	96.67	10.00

Compd.	Plutella xylostella
Compd.	1 mg/L	0.1 mg/L	0.01 mg/L
4a	100.00	96.67	10.00
4b	100.00	46.67	0.00
4c	0.00	0.00	0.00
4d	90.00	20.00	0.00
4e	96.67	60.00	0.00
环丙氟虫胺	100.00	96.67	10.00

Compd.	Plutella xylostella
Compd.	1 mg/L	0.1 mg/L	0.01 mg/L
4f	0.00	0.00	0.00
4g	0.00	0.00	0.00
4h	100.00	70.00	0.00
4i	83.33	6.67	3.33
4j	100.00	70.00	0.00
4k	100.00	83.33	6.67
4l	100.00	13.33	0.00
4m	100.00	96.67	3.33
4n	100.00	3.33	0.00
4o	100.00	13.33	3.33
4p	96.67	10.00	0.00
4q	100.00	0.00	0.00
4r	96.67	10.00	0.00
4s	0.00	0.00	0.00
4t	100.00	96.67	3.33
环丙氟虫胺	100.00	96.67	10.00

Compd.	Plutella xylostella
Compd.	1 mg/L	0.1 mg/L	0.01 mg/L
4f	0.00	0.00	0.00
4g	0.00	0.00	0.00
4h	100.00	70.00	0.00
4i	83.33	6.67	3.33
4j	100.00	70.00	0.00
4k	100.00	83.33	6.67
4l	100.00	13.33	0.00
4m	100.00	96.67	3.33
4n	100.00	3.33	0.00
4o	100.00	13.33	3.33
4p	96.67	10.00	0.00
4q	100.00	0.00	0.00
4r	96.67	10.00	0.00
4s	0.00	0.00	0.00
4t	100.00	96.67	3.33
环丙氟虫胺	100.00	96.67	10.00

Compd.	Plutella xylostella			Chilo suppressalis			Aphis craccivora			Tetranychus cinnabarinus
Compd.	1 mg/L	0.1 mg/L	0.01 mg/L	400 mg/L	40 mg/L	4 mg/L	400 mg/L	40 mg/L	4 mg/L	400 mg/L	40 mg/L	4 mg/L
4a	100.00	96.67	10.00	100.00	93.33	0.00	100.00	81.00	46.57	100.00	100.00	67.23
环丙氟虫胺	100.00	96.67	10.00	100.00	96. 67	0.00	72. 71	31. 03	6. 06	41.11	8.69	3.33

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