Synthesis and Insecticidal Activity of Novel Pyrazole Amides Containing an Isoxazole Moiety

doi:10.6023/cjoc202211021

Abstract

Sixteen novel pyrazole amide compounds containing an isoxazole unit were synthesized through introducing an isoxazole moiety to pyrazole amide molecules based on the structure of chlorantraniliprole. The structures of the designed compounds were characterized with ¹H NMR, ¹³C NMR and elemental analysis. Preliminary bioassay showed that most of the target compounds exhibited 100% insecticidal activities against Mythimna separata at the dosage of 500 μg/mL. Three compounds had 80%~100% mortality rate towards M. separata at the dosage of 100 μg/mL, and three compounds still possessed 40%~50% mortality rate against M. separata when the dosage was lowered to 20 μg/mL. Three compounds displayed 100% insecticidal activities towards Aphis medicaginis at 500 μg/mL, and still showed good insecticidal activities against A. medicaginis with 70%~100% at 100 μg/mL. In addition, two compounds demonstrated 90%~100% mortality rates towards Tetranychus cinnabarinus at 500 μg/mL.

Key words: isoxazole, pyrazole amide, synthesis, insecticidal activity

Cite this article

Zichan Zhang, Yang Sun, Sheng Hua, Baolin Xu, Min Zhang, Qin Zhao, Dandan Zheng, Yang Wang, Jianfeng Ju, Yujun Shi, Hong Dai. Synthesis and Insecticidal Activity of Novel Pyrazole Amides Containing an Isoxazole Moiety[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1435-1443.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 5

References 35

[1]	Wang, Y. Y.; Xu, F. Z.; Zhu, Y. Y.; Song, B. A.; Liu, D. X.; Yu, G.; Chen, S. H.; Xue, W.; Wu, J. Bioorg. Med. Chem. Lett. 2018, 28, 2979. doi: 10.1016/j.bmcl.2018.06.049
[2]	Zhou, Y. H.; Sun, W.; Peng, J. L.; Yan, H.; Zhang, L.; Liu, X. Y.; Zuo, Z. L. Bioorg. Chem. 2019, 93, 103322. doi: 10.1016/j.bioorg.2019.103322
[3]	Mekky, A. E. M.; Sanad, S. M. H.; Said, A. Y.; Elneairy, M. A. A. Synth. Commun. 2020, 50, 2376. doi: 10.1080/00397911.2020.1778033
[4]	Wang, J. L.; Zhou, Y. Q.; Wang, X. W.; Duan, L. X.; Duan, J.; Li, W. G.; Zhang, A. D. J. Agric. Food Chem. 2020, 68, 3071. doi: 10.1021/acs.jafc.9b08057
[5]	He, B.; Wu, F. X.; Yu, L. K.; Wu, L.; Chen, Q.; Hao, G. F.; Yang, W. C.; Lin, H. Y.; Yang, G. F. J. Agric. Food Chem. 2020, 68, 5059. doi: 10.1021/acs.jafc.0c00051
[6]	Eryilmaz, S.; Celikoglu, E. T.; Idil, O.; Inkaya, E.; Kozak, Z.; Misir, E.; Gul, M. Bioorg. Chem. 2020, 95, 103476. doi: 10.1016/j.bioorg.2019.103476
[7]	Tu, M. T.; Shao, Y. Y.; Yang, S.; Sun, B. L.; Wang, Y. Y.; Tan, C. X.; Wang, X. D. Molecules 2022, 27, 4692. doi: 10.3390/molecules27154692
[8]	Zheng, Z. G.; Dai, A. L.; Jin, Z. C.; Chi. Y. R.; Wu, J. J. Agric. Food Chem. 2022, 70, 11019. doi: 10.1021/acs.jafc.1c08383
[9]	Kiyani, H.; Mosallanezhad, A. Curr. Org. Synth. 2018, 15, 715. doi: 10.2174/1570179415666180423150259
[10]	Soliman, N. N.; Salam, M. A.; Fadda, A. A.; Abdel-Motaal, M. J. Agric. Food Chem. 2020, 68, 5790. doi: 10.1021/acs.jafc.9b06394
[11]	Lin, X. D.; Li, Y.; Zhong, W. Q.; Hong, T.; Li, L. H.; Song, S. Y.; He, D. H. J. Agric. Food Chem. 2021, 69, 9520. doi: 10.1021/acs.jafc.1c01816
[12]	Yuan, Y.; Subedi, L.; Lim, D.; Jung, J. K.; Kim, S. Y. Bioorg. Med. Chem. Lett. 2018, 29, 329. doi: 10.1016/j.bmcl.2018.11.014
[13]	Nagaraju, B.; Shanmukhakumar, J. V.; Seelam, N.; Subbaiah, T.; Prasanna, B. Curr. Org. Synth. 2019, 16, 1161. doi: 10.2174/1570179416666190925125450
[14]	Trivedi, J.; Parveen, A.; Rozy, F.; Mitra, A.; Bal, C.; Mitra, D.; Sharon, A. Eur. J. Med. Chem. 2019, 183, 111699. doi: 10.1016/j.ejmech.2019.111699
[15]	Warda, E. T.; Shehata, I. A.; El-Ashmawy, M. B.; El-Gohary, N. S. Bioorg. Med. Chem. 2020, 28, 115674. doi: 10.1016/j.bmc.2020.115674
[16]	Arya, G. C.; Kaur, K.; Jaitak, V. Eur. J. Med. Chem. 2021, 221, 113511. doi: 10.1016/j.ejmech.2021.113511
[17]	Pascal, B.; Gopal, D.; Wolfgang, V.; Matthias, P.; Franz, J. B. WO 2016102482, 2016
	[Chem. Abstr. 2016, 165, 152398 ]
[18]	Yang, Z. B.; Zhao, Y.; Li, P.; He, Y. J. J. Heterocycl. Chem. 2019, 56, 3042. doi: 10.1002/jhet.v56.11
[19]	Yang, Z. B.; Li, P.; He, Y. J. Molecules 2019, 24, 3766. doi: 10.3390/molecules24203766
[20]	Liu, J. B.; Li, F. Y.; Hao, Z. S.; Wang, Y. H.; Hua, X. W.; Li, Y. X.; Li, Z. M. Bioorg. Med. Chem. 2020, 28, 115829. doi: 10.1016/j.bmc.2020.115829
[21]	Xie, W. B.; Li, H. G.; Meng, X. D.; Li, Z. M.; Zhou, S. Chin. J. Org. Chem. 2021, 41, 1722. (in Chinese) doi: 10.6023/cjoc202012017
	(谢伟彬, 李焕功, 孟祥德, 李正名, 周莎, 有机化学, 2021, 41, 1722.) doi: 10.6023/cjoc202012017
[22]	Yang, D. Y.; Zhao, B.; Fan, Z. J.; Yu, B.; Zhang, N. L.; Li, Z. M.; Zhu, Y. L.; Zhou, J. H.; Kalinina, T. A.; Glukhareva, T. V. J. Agric. Food Chem. 2019, 67, 13185. doi: 10.1021/acs.jafc.9b05751
[23]	Zeng, H. N.; Zhang, W.; Wang, Z. X.; Geng, W.; Feng, G.; Gan, X. H. J. Agric. Food Chem. 2022, 70, 7400. doi: 10.1021/acs.jafc.2c02123
[24]	Nayak, N.; Ramprasad, J.; Dalimba, U. J. Heterocycl. Chem. 2017, 54, 171. doi: 10.1002/jhet.v54.1
[25]	Iqbal, J.; Ejaz, S. A.; Saeed, A.; al-Rashida, M. Eur. J. Pharmacol. 2018, 832, 11. doi: 10.1016/j.ejphar.2018.05.011
[26]	Nithyabalaji, R.; Krishnan, H.; Sribalan, R. J. Mol. Struct. 2019, 1186, 1. doi: 10.1016/j.molstruc.2019.02.095
[27]	Wu, H. X.; Han, M. H.; Jiang, K. J. Agrochemicals 2007, 46, 707. (in Chinese)
	(吴华新, 韩敏晖, 蒋开杰, 农药, 2007, 46, 707.)
[28]	Xu, S. C.; Yu, Y. F.; Wang, X. J.; Wan, Q. Mod. Agrochem. 2008, 7, 8. (in Chinese)
	(徐尚成, 俞幼芬, 王晓军, 万琴, 现代农药, 2008, 7, 8.)
[29]	Zhao, Y.Y.; Gao, L.; Li, H. G.; Sun, P. W.; Meng, F. F.; Zhang, Y.; Xie, Y. T.; Sun, B. Q.; Zhou, S.; Ma, Y.; Xiong, L. X.; Yang, N.; Li, Y. X.; Li, Z. M. J. Agric. Food Chem. 2020, 68, 11282. doi: 10.1021/acs.jafc.9b08090
[30]	Zhang, Y.; Li, Y. X.; Li, H.; Shang, J. F.; Li, Z. M.; Wang, B. L. Chin. Chem. Lett. 2022, 33, 501. doi: 10.1016/j.cclet.2021.05.027
[31]	Liu, J. B.; Li, Y. X.; Zhang, X. L.; Hua, X. W.; Wu, C. C.; Wei, W.; Wan, Y. Y.; Cheng, D. D.; Xiong, L. X.; Yang, N.; Song, H. B.; Li, Z. M. J. Agric. Food Chem. 2016, 64, 3697. doi: 10.1021/acs.jafc.6b00380
[32]	Dai, H.; Chen, J.; Li, G.; Ge, S. S.; Shi, Y. J.; Fang, Y.; Ling, Y. Bioorg. Med. Chem. Lett. 2017, 27, 950. doi: 10.1016/j.bmcl.2016.12.083
[33]	Zhang, J. F.; Xu, J. Y.; Wang, B. L.; Li, Y. X.; Xiong, L. X.; Li, Y. Q.; Ma, Y.; Li, Z. M. J. Agric. Food Chem. 2012, 60, 7565. doi: 10.1021/jf302446c
[34]	Tanaka, A.; Terasawa, T.; Hagihara, H.; Sakuma, Y.; Ishibe, N.; Sawada, M.; Takasugi, H.; Tanaka, H. J. Med. Chem. 1998, 41, 2390. pmid: 9632372
[35]	Shi, Y. J.; Fang, Y.; Li, Y.; Chen, J.; Li, G.; Wang, Q. M.; Dai, H. Chem. J. Chin. Univ. 2017, 38, 421. (in Chinese)
	(石玉军, 方源, 李阳, 陈佳, 李刚, 汪清民, 戴红, 高等学校化学学报, 2017, 38, 421.)

Entry	Base	Solvent	Reaction condition	Yield/%
1	Pyridine	CH₂Cl₂	Room temperature for 10 h	57
2	Pyridine	THF	Room temperature for 10 h	35
3	Pyridine	CH₃CN	Room temperature for 10 h	27
4	Et₃N	CH₂Cl₂	Room temperature for 10 h	64
5	Et₃N	THF	Room temperature for 10 h	53
6	Et₃N	CH₃CN	Room temperature for 10 h	45
7	Et₃N	CH₂Cl₂	Reflux for 10 h	60
8	NaHCO₃	CH₂Cl₂	Room temperature for 10 h	5
9	Na₂CO₃	CH₂Cl₂	Room temperature for 10 h	12
10	K₂CO₃	CH₂Cl₂	Room temperature for 10 h	10

Entry	Base	Solvent	Reaction condition	Yield/%
1	Pyridine	CH₂Cl₂	Room temperature for 10 h	57
2	Pyridine	THF	Room temperature for 10 h	35
3	Pyridine	CH₃CN	Room temperature for 10 h	27
4	Et₃N	CH₂Cl₂	Room temperature for 10 h	64
5	Et₃N	THF	Room temperature for 10 h	53
6	Et₃N	CH₃CN	Room temperature for 10 h	45
7	Et₃N	CH₂Cl₂	Reflux for 10 h	60
8	NaHCO₃	CH₂Cl₂	Room temperature for 10 h	5
9	Na₂CO₃	CH₂Cl₂	Room temperature for 10 h	12
10	K₂CO₃	CH₂Cl₂	Room temperature for 10 h	10

Compd.	Mythimna separata				Aphis medicaginis				Tetranychus cinnabarinus
Compd.	500 μg/mL	100 μg/mL	20 μg/mL	4 μg/mL	500 μg/mL	100 μg/mL	20 μg/mL	4 μg/mL	500 μg/mL	100 μg/mL
10a	100	90	40	0	0	—	—	—	0	—
10b	100	60	0	—	0	—	—	—	0	—
10c	100	70	30	—	0	—	—	—	0	—
10d	100	0	—	—	0	—	—	—	0	—
10e	100	0	—	—	100	100	40	0	100	30
10f	100	50	0	—	0	—	—	—	0	—
10g	100	80	40	0	0	—	—	—	0	—
10h	100	100	50	0	100	70	30	—	90	0
10i	100	50	0	—	0	—	—	—	0	—
10j	0	—	—	—	100	90	0	—	0	—
10k	100	0	—	—	0	—	—	—	0	—
10l	0	—	—	—	0	—	—	—	0	—
10m	0	—	—	—	0	—	—	—	60	0
10n	100	0	—	—	0	—	—	—	0	—
10o	100	60	0	—	0	—	—	—	0	—
10p	100	0	—	—	0	—	—	—	0	—
Chlorantraniliprole	100	100	100	100	—	—	—	—	—	—
Imidacloprid	—	—	—	—	100	100	100	100	—	—
Fenpyroximate	—	—	—	—	—	—	—	—	100	100

Compd.	Mythimna separata				Aphis medicaginis				Tetranychus cinnabarinus
Compd.	500 μg/mL	100 μg/mL	20 μg/mL	4 μg/mL	500 μg/mL	100 μg/mL	20 μg/mL	4 μg/mL	500 μg/mL	100 μg/mL
10a	100	90	40	0	0	—	—	—	0	—
10b	100	60	0	—	0	—	—	—	0	—
10c	100	70	30	—	0	—	—	—	0	—
10d	100	0	—	—	0	—	—	—	0	—
10e	100	0	—	—	100	100	40	0	100	30
10f	100	50	0	—	0	—	—	—	0	—
10g	100	80	40	0	0	—	—	—	0	—
10h	100	100	50	0	100	70	30	—	90	0
10i	100	50	0	—	0	—	—	—	0	—
10j	0	—	—	—	100	90	0	—	0	—
10k	100	0	—	—	0	—	—	—	0	—
10l	0	—	—	—	0	—	—	—	0	—
10m	0	—	—	—	0	—	—	—	60	0
10n	100	0	—	—	0	—	—	—	0	—
10o	100	60	0	—	0	—	—	—	0	—
10p	100	0	—	—	0	—	—	—	0	—
Chlorantraniliprole	100	100	100	100	—	—	—	—	—	—
Imidacloprid	—	—	—	—	100	100	100	100	—	—
Fenpyroximate	—	—	—	—	—	—	—	—	100	100

新型含异噁唑单元的吡唑酰胺类衍生物的合成及杀虫活性