3-芳基-4,5-二氢异噁唑-5-甲酸环戊烷多氢菲酯类衍生物的合成与杀虫活性

单喜杰; 李海洁; 李天泽; 徐晖; 吕敏

doi:10.16801/j.issn.1008-7303.2022.0066

3-芳基-4,5-二氢异噁唑-5-甲酸环戊烷多氢菲酯类衍生物的合成与杀虫活性

doi: 10.16801/j.issn.1008-7303.2022.0066

1.
西北农林科技大学植物保护学院，陕西杨凌 712100

基金项目: 国家自然科学基金 (31872013).

详细信息

作者简介:
单喜杰，SXJ18438615950@163.com

通讯作者:
吕敏，lvmin@nwsuaf.edu.cn

中图分类号: O625.15；TQ450.11
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- 文章访问数: 247
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- 被引次数: 0
出版历程
- 收稿日期: 2022-05-05
- 录用日期: 2022-07-12
- 网络出版日期: 2022-07-18
- 刊出日期: 2022-12-02

Synthesis and pesticidal activities of cyclopentanoperhydrophenanthrene 3-aryl-4,5-dihydroisoxazole-5-formate derivatives

1.
College of Plant Protection, Northwest A&F University, Yangling 712100, Shaanxi Province, China

Funds: the National Natural Science Foundation of China (31872013).

摘要

摘要: 为了寻找具有较高杀虫活性的胆固醇衍生物，将异噁唑啉片段引入母体胆固醇( 1 )的C-3位，制备了20个新的3-芳基-4,5-二氢异噁唑-5-甲酸环戊烷多氢菲酯类衍生物 Ia~It ，并经氢谱、红外光谱和高分辨质谱确证结构。化合物 Ie (R = 3-BrPh) 对小菜蛾Plutella xyllostella幼虫具有较好的杀虫活性，其48 h LC₅₀值为 0.940 mg/mL，是母体胆固醇 (LC₅₀值2.566 mg/mL) 的2.7倍；化合物 Ig (R = 3-FPh) 和 Ij (R = 4-CF₃Ph) 对苹果黄蚜Aphis citricola具有较好的杀虫活性，其48 h LD₅₀值为0.042与0.041 μg/头，是胆固醇 (LD₅₀值0.228 μg/头) 的5.4和5.6倍。初步构效关系表明，在苯环间位引入溴原子可提高对小菜蛾的杀虫活性；在苯环对位或间位引入氟原子、或者在对位引入三氟甲基可提高对苹果黄蚜的杀虫活性。
- 环戊烷多氢菲 /
- 结构修饰 /
- 异噁唑啉 /
- 杀虫活性
Abstract: In order to find cholesterol derivatives with high insecticidal activities, isoxazoline fragments were introduced into the C-3 position of cholesterol ( 1 ), and twenty novel cyclopentanoperhydrophenanthrene 3-aryl-4,5-dihydroisoxazole-5-formate derivatives ( Ia - It ) containing the isoxazoline fragment were prepared. Their structures were characterized by ¹H NMR, IR and HRMS. Among them, compound Ie (R = 3-Br-Ph) exhibited good insecticidal activity against Plutella xyllostella with a LC₅₀ value of 0.940 mg/mL at 48 h, which was 2.7 times of that of 1 (LC₅₀: 2.566 mg/mL). Compounds Ig (R = 3-F-Ph) and Ij (R = 4-CF₃-Ph) showed the potent aphicidal activity against Aphis citricola with LD₅₀ values of 0.042 and 0.041 μg/nymph at 48 h, respectively, which were 5.4 and 5.6 times of that of 1 (LD₅₀: 0.228 μg/nymph). The preliminary study of structure-activity relationships (SARs) indicated that introduction of the bromine atom at the C-3 position of phenyl can improve the insecticidal activity against P. xyllostella; introduction of the fluorine atom at the C-3 or C-4 position of phenyl, or introduction of the CF₃ at the C-4 position of phenyl can improve the aphicidal activity against A. citricola.
- cyclopentanoperhydrophenanthrene /
- structural modification /
- isoxazoline /
- insecticidal activity

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1 目标化合物I的设计

1. Design of target compounds I

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2 目标化合物Ia~It的合成路线

2. Synthetic route of target compounds Ia-It

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表 1 化合物1、2和Ia~It在1 mg/mL下对小菜蛾幼虫的杀虫活性

Table 1. Insecticidal activity of compounds 1, 2 and Ia-It against the larvae of P. xylostella at 1 mg/mL

化合物 Compound	校正死亡率 (平均值 ± 标准误差) Corrected mortality rate (mean ± SE)/%
化合物 Compound	24 h	48 h^a
1	17.7 ± 4.4	20.4 ± 4.4 g
2	22.2 ± 5.8	24.9 ± 5.7 fg
Ia	35.5 ± 2.2	47.7 ± 4.4 bc
Ib	22.2 ± 4.4	38.6 ± 3.8 cde
Ic	24.4 ± 5.8	47.7 ± 5.8 bc
Id	20.0 ± 3.8	36.3 ± 4.4 cdef
Ie	35.5 ± 2.2	52.2 ± 0 b
If	24.4 ± 5.8	38.6 ± 3.8 cde
Ig	31.1 ± 2.2	43.1 ± 2.2 bcd
Ih	17.7 ± 2.2	29.5 ± 2.2 efg
Ii	33.3 ± 3.8	34.1 ± 2.2 def
Ij	31.1 ± 2.2	45.4 ± 0 bcd
Ik	22.2 ± 2.2	36.3 ± 2.2 cdef
Il	17.7 ± 4.4	34.1 ± 2.2 def
Im	33.3 ± 3.8	43.1 ± 5.8 bcd
In	20.0 ± 3.8	29.5 ± 4.4 efg
Io	4.4 ± 2.2	18.2 ± 3.8 g
Ip	31.1 ± 2.2	45.4 ± 6.6 bcd
Iq	25.0 ± 3.8	36.3 ± 2.2 cdef
Ir	22.7 ± 2.2	34.1 ± 2.2 def
Is	22.7 ± 2.2	40.9 ± 2.2 bcde
It	31.8 ± 3.8	47.7 ± 2.2 bc
高效氯氰菊酯 β-cypermethrin	42.2 ± 2.2	86.3 ± 0 a
注：^a多重比较用Duncan’s test (p<0.05)，相同字母表示无显著差异。Note: ^aMultiple range test using Ducan’s test (p<0.05). The same letters denote treatments that are not significantly different from each other.

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表 2 化合物1、Ie和高效氯氰菊酯对小菜蛾幼虫的48 h LC₅₀值

Table 2. LC₅₀ values at 48 h of compounds 1, Ie and β-cypermethrin against the larvae of P. xylostella

化合物 Compound	回归方程 Regression equation	致死中浓度 LC₅₀/(mg/mL)	95% 置信区间 Confidence interval 95%/(mg/mL)	相关系数 r
1	y = −0.869 + 2.124x	2.566	2.069~3.212	0.995
Ie	y = 0.043 + 1.612x	0.940	0.711~1.228	0.996
高效氯氰菊酯 β-cypermethrin	y = 1.175 + 1.772x	0.217	0.167~0.278	0.994

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表 3 化合物1、2和Ia~Ip在0.04 μg/头剂量下对苹果黄蚜的杀虫活性

Table 3. Aphicidal activity of compounds 1, 2 and Ia-Ip against A. citricola at 0.04 μg/nymph

化合物 Compound	校正死亡率 (平均值 ± 标准误差) Corrected mortality rate (mean ± SE)/%
化合物 Compound	24 h	48 h^a
1	7.9 ± 2.2	13.8 ± 1.9 g
2	13.4 ± 2.9	28.7 ± 1.1 f
Ia	21.3 ± 1.1	40.2 ± 4.4 bcde
Ib	16.8 ± 2.9	34.5 ± 1.9 def
Ic	12.3 ± 1.9	29.9 ± 2.2 f
Id	11.2 ± 2.2	29.9 ± 2.2 f
Ie	17.9 ± 2.9	34.5 ± 3.3 def
If	29.2 ± 3.8	45.9 ± 2.2 bc
Ig	24.7 ± 1.1	48.8 ± 2.9 b
Ih	20.2 ± 1.1	33.3 ± 1.1 def
Ii	25.8 ± 3.3	37.5 ± 2.2 cdef
Ij	34.8 ± 1.1	48.8 ± 3.3 b
Ik	31.4 ± 2.2	34.1 ± 2.9 def
Il	11.2 ± 2.2	30.6 ± 2.9 ef
Im	13.4 ± 2.2	31.8 ± 5.0 ef
In	29.2 ± 3.3	36.3 ± 2.9 def
Io	11.2 ± 1.1	42.0 ± 3.8 bcd
Ip	25.8 ± 3.8	30.6 ± 2.9 ef
灭多威 methomyl^b	55.0 ± 2.9	72.4 ± 3.3 a
注：^a多重比较用Duncan’s test (p<0.05)，相同字母表示无显著差异；^b 剂量为 0.004 μg/头.Note: ^a Multiple range test using Ducan’s test (p<0.05). The same letters denote treatments that are not significantly different from each other. ^b 0.004 μg/nymph.

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表 4 部分化合物对苹果黄蚜48 h的毒力回归分析

Table 4. Toxicity regression analysis of some compounds against A. citricola at 48 h

化合物 Compound	回归方程 Regression equation	致死中量 LD₅₀/ (μg/nymph)	95% 置信区间 Confidence interval 95%/(μg/nymph)	相关系数 r
1	y = 1.049 + 1.633x	0.228	0.190~0.282	0.975
If	y = 5.472 + 4.069x	0.045	0.042~0.049	0.964
Ig	y = 5.477 + 3.983x	0.042	0.039~0.046	0.971
Ij	y = 7.176 + 5.155x	0.041	0.038~0.043	0.969
灭多威 methomyl	y = 4.310 + 1.391x	0.001	0.000630~0.001218	0.986

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