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

doi:10.6023/cjoc202211021

摘要/Abstract

运用活性亚结构拼接的原理, 以杀虫剂氯虫苯甲酰胺为先导结构, 引入异噁唑环单元, 合成了16个含异噁唑环取代的新型吡唑酰胺化合物, 采用¹H NMR、¹³C NMR、元素分析等方法对其目标物的结构进行了表征. 初步生物活性测试数据显示, 大多数化合物在500 μg/mL浓度下对粘虫呈现出100%的杀死率. 其中3个化合物在100 μg/mL浓度下对粘虫的杀死率达80%~100%, 在浓度降至20 μg/mL时, 3个化合物对粘虫仍表现出40%~50%的杀虫活性. 3个化合物在500 μg/mL浓度下对蚜虫显示出100%的杀虫效果, 在100 μg/mL浓度下对蚜虫仍有70%~100%的杀虫活性. 另外, 2个化合物在500 μg/mL时对朱砂叶螨的防效为90%~100%.

关键词: 异噁唑, 吡唑酰胺, 合成, 杀虫活性

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

引用此文

张紫婵, 孙洋, 华晟, 徐宝琳, 张敏, 赵勤, 郑丹丹, 王杨, 鞠剑峰, 石玉军, 戴红. 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[J]. 有机化学, 2023, 43(4): 1435-1443.

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.

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参考文献 35

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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