新型含1,3,4-噁二唑基团的吡唑肟衍生物的合成与生物活性

doi:10.6023/cjoc202212021

摘要/Abstract

为了探寻新的吡唑肟活性物质, 以唑螨酯为农药先导, 依据活性片段拼接原理, 合成出了16个新型含1,3,4-噁二唑杂环结构的吡唑肟衍生物, 并测定了其杀虫活性. 初步活性数据显示, 所有目标化合物在500 μg/mL的浓度下对粘虫均有100%的防效, 其中5种目标化合物在100 μg/mL的浓度下对粘虫表现出80%~100%的杀虫效果. 同时, 在500 μg/mL浓度下, 9种目标化合物对蚜虫的致死率都为100%, 3种化合物在100 μg/mL时对蚜虫的防效在70%~100%. 此外, 在500 μg/mL的浓度下, 有4种目标化合物对朱砂叶螨也呈现出80%以上的杀虫效果.

关键词: 1,3,4-噁二唑, 吡唑肟, 合成, 生物活性

In order to explore new pyrazole oxime compounds possessing satisfactory bioactivities, sixteen pyrazole oxime derivatives containing 1,3,4-oxadiazole group were prepared with fenpyroximate selected as lead structure. Their insecticidal activities were determined. Preliminary bioassay demonstrated that all the target compounds displayed 100% insecticidal activities towards Mythimna separata at 500 μg/mL, of which 5 target compounds possessed 80%~100% insecticidal activities against Mythimna separata at 100 μg/mL. Moreover, at concentration of 500 μg/mL, mortality rates against Aphis medicaginis of 9 target compounds were 100%, those of 3 compounds were 70%~100% at 100 μg/mL. Additionally, 4 target compounds exhibited more than 80% mortality rates against Tetranychus cinnabarinus at 500 μg/mL.

Key words: 1,3,4-oxadiazole, pyrazole oxime, synthesis, bioactivity

引用此文

孙洋, 王杨, 张紫婵, 钱烨, 骆桂成, 周贝贝, 缪丽沙, 陈雨蝶, 戴红, 徐宝琳, 吴正光. 新型含1,3,4-噁二唑基团的吡唑肟衍生物的合成与生物活性[J]. 有机化学, 2023, 43(4): 1584-1590.

Yang Sun, Yang Wang, Zichan Zhang, Ye Qian, Guicheng Luo, Beibei Zhou, Lisha Miao, Yudie Chen, Hong Dai, Baolin Xu, Zhengguang Wu. Synthesis and Bioactivities of Novel Pyrazole Oxime Derivatives Containing 1,3,4-Oxadiazole Group[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1584-1590.

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Entry	Acid scavenger	Solvent	Temp./℃	Yield/%
1	Pyridine	Acetone	Reflux	0
2	Et₃N	Acetone	Reflux	0
3	Na₂CO₃	Acetone	Reflux	23
4	K₂CO₃	Acetone	Reflux	32
5	Cs₂CO₃	Acetone	Reflux	36
6	Pyridine	MeCN	Reflux	20
7	Et₃N	MeCN	Reflux	25
8	Na₂CO₃	MeCN	Reflux	41
9	K₂CO₃	MeCN	Reflux	62
10	Cs₂CO₃	MeCN	Reflux	68
11	Na₂CO₃	DMF	80	39
12	K₂CO₃	DMF	80	52
13	Cs₂CO₃	DMF	80	55

Entry	Acid scavenger	Solvent	Temp./℃	Yield/%
1	Pyridine	Acetone	Reflux	0
2	Et₃N	Acetone	Reflux	0
3	Na₂CO₃	Acetone	Reflux	23
4	K₂CO₃	Acetone	Reflux	32
5	Cs₂CO₃	Acetone	Reflux	36
6	Pyridine	MeCN	Reflux	20
7	Et₃N	MeCN	Reflux	25
8	Na₂CO₃	MeCN	Reflux	41
9	K₂CO₃	MeCN	Reflux	62
10	Cs₂CO₃	MeCN	Reflux	68
11	Na₂CO₃	DMF	80	39
12	K₂CO₃	DMF	80	52
13	Cs₂CO₃	DMF	80	55

Compd.	Mythimna separata			Aphis medicaginis			Tetranychus cinnabarinus
Compd.	500 μg/mL	100 μg/mL	20 μg/mL	500 μg/mL	100 μg/mL	20 μg/mL	500 μg/mL	100 μg/mL
8a	100	80	0	100	60	0	0	—
8b	100	0	—	100	0	—	0	—
8c	100	100	50	100	70	0	80	0
8d	100	0	—	100	0	—	0	—
8e	100	0	—	0	—	—	0	—
8f	100	60	0	100	0	—	0	—
8g	100	100	50	100	100	40	90	0
8h	100	0	—	0	—	—	0	—
8i	100	0	—	0	—	—	0	—
8j	100	0	—	100	0	—	0	—
8k	100	80	0	0	—	—	0	—
8l	100	70	0	0	—	—	100	0
8m	100	0	—	100	0	—	0	—
8n	100	60	0	0	—	—	0	—
8o	100	0	—	0	—	—	0	—
8p	100	100	40	100	90	30	100	0
Tolfenpyrad	100	50	40	—	—	—	—	—
Imidacloprid	—	—	—	100	100	100	—	—
Fenpyroximate	—	—	—	—	—	—	100	100

Compd.	Mythimna separata			Aphis medicaginis			Tetranychus cinnabarinus
Compd.	500 μg/mL	100 μg/mL	20 μg/mL	500 μg/mL	100 μg/mL	20 μg/mL	500 μg/mL	100 μg/mL
8a	100	80	0	100	60	0	0	—
8b	100	0	—	100	0	—	0	—
8c	100	100	50	100	70	0	80	0
8d	100	0	—	100	0	—	0	—
8e	100	0	—	0	—	—	0	—
8f	100	60	0	100	0	—	0	—
8g	100	100	50	100	100	40	90	0
8h	100	0	—	0	—	—	0	—
8i	100	0	—	0	—	—	0	—
8j	100	0	—	100	0	—	0	—
8k	100	80	0	0	—	—	0	—
8l	100	70	0	0	—	—	100	0
8m	100	0	—	100	0	—	0	—
8n	100	60	0	0	—	—	0	—
8o	100	0	—	0	—	—	0	—
8p	100	100	40	100	90	30	100	0
Tolfenpyrad	100	50	40	—	—	—	—	—
Imidacloprid	—	—	—	100	100	100	—	—
Fenpyroximate	—	—	—	—	—	—	100	100