<i>N</i>-取代苯基-1-(2,4-二氟苯基)-2-(1<i>H</i>-1,2,4-三唑-1-基)乙基氨基甲酸酯的合成及生物活性

游江; 高亚强; 周蒲; 郭倩男; 徐志红

doi:10.16801/j.issn.1008-7303.2022.0016

N-取代苯基-1-(2,4-二氟苯基)-2-(1H-1,2,4-三唑-1-基)乙基氨基甲酸酯的合成及生物活性

doi: 10.16801/j.issn.1008-7303.2022.0016

游江^1,,
高亚强¹,
周蒲¹,
郭倩男¹,
徐志红^{1, 2, ,}

1.
长江大学农学院，湖北荆州 434025
2.
长江大学农药研究所，湖北荆州 434025

基金项目: 国家自然科学基金 (31772170).

详细信息

作者简介:
游江，2367885614@qq.com

通讯作者:
徐志红，x_u_78@sina.com

中图分类号: O626.2；TQ450.11
计量
- 文章访问数: 59
- HTML全文浏览量: 20
- PDF下载量: 12
- 被引次数: 0
出版历程
- 收稿日期: 2022-01-14
- 录用日期: 2022-02-16
- 网络出版日期: 2022-02-24
- 刊出日期: 2022-08-03

Synthesis and biological activity of N-substituted phenyl-1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylcarbamate

YOU Jiang^1
,,
GAO Yaqiang¹,
ZHOU Pu¹,
GUO Qiannan¹,
XU Zhihong^{1, 2
, ,}

1.
School of Agriculture, Yangtze University, Jingzhou 434025, Hubei Province, China
2.
Institute of Pesticides, Yangtze University, Jingzhou 434025, Hubei Province, China

Funds: the National Natural Science Foundation of China (31772170).

摘要

摘要: 为了寻找高活性的三唑类苯基氨基甲酸酯衍生物，以 1,2,4-三氮唑、2-氯-2,4-二氟苯乙酮为原料，采用活性亚结构拼接的策略，设计并合成了18个未见文献报道的N-取代苯基-1-(2,4-二氟苯基)-2-(1H-1,2,4-三唑-1-基)乙基氨基甲酸酯衍生物 6a ~ 6r 。其结构均通过 ¹H NMR、¹³C NMR和高分辨质谱（HRMS）的确证。抑菌活性测定结果显示：在100 μmol/L下，化合物 6m 对6种供试真菌具有良好的抑制作用，抑制率均达到50%以上。化合物 6p 对油菜菌核病菌Sclerotinia sclerotiorum的EC₅₀值为7.1 μmol/L，抑菌活性高于对照药剂烯唑醇（EC₅₀值9.1 μmol/L）。杀螨活性测定结果显示，在150 μmol/L时，化合物 6h 、 6k 和 6o 在48 h时对朱砂叶螨Tetranychus cinnabarinus的致死率分别为67.7%、74.9%和57.5%，杀螨活性低于对照药剂阿维菌素B1a(致死率100%)。本研究所合成的化合物 6o 兼具一定杀菌和杀螨活性，可为新型三唑类杀菌杀螨化合物的设计与研究提供参考。
- 1,2,4-三唑 /
- 氨基甲酸酯 /
- 杀菌活性 /
- 杀螨活性
Abstract: In order to find highly active triazole phenyl carbamate derivatives, 1,2,4-triazole and 2-chloro-2,4-difluoroacetophenone were used as raw materials, and the strategy of active substructure splicing was adopted, eighteen N-substituted phenyl-1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethyl carbamate derivatives 6a-6r were designed and synthesized. Their structures were confirmed by ¹H NMR, ¹³C NMR and high resolution mass spectrometry (HRMS). The results of fungicidal activity assay showed that compound 6m had a good inhibitory effect on the 6 tested fungi at 100 μmol/L with a inhibition rate of more than 50%. The EC₅₀ value of compound 6p against Sclerotinia sclerotiorum was 7.1 μmol/L, the fungicidal activity was higher than that of the control compound diniconazole (EC₅₀ value was 9.1 μmol/L). The results of acaricidal activity showed that at 150 μmol/L, the lethal rates of compounds 6h , 6k and 6o were 67.7%, 74.9% and 57.5% for Tetranychus cinnabarinus at 48 h, respectively, and the acaricidal activity was lower than that of the control compound abamectin B1a (100%). The compound 6o synthesized in this study has both fungicidal and acaricidal activities, which can provide a reference for the design and research of novel fungicidal and acaricidal triazole compounds.
- 1,2,4-tiazole /
- carbamate /
- fungicidal activity /
- acaricidal activity

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1 两类2-(1,2,3-三唑-4-基)-甲氨基-1-苯基氨基甲酸酯的化学结构

1. The structures of two classes of 2-(1,2,3-triazol-4-yl)-methylamino-1-phenylcarbamate

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2 两类1,2,4-三唑-5-氨基甲酸乙酯的化学结构

2. The structures of two classes of ethyl 1,2,4-triazole-5-carbamate

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3 目标化合物的合成路线

3. Synthetic route of target compounds

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表 1 目标化合物对6种植物病原真菌的抑制作用

Table 1. Inhibition of target compounds against six pathogenic fungi in vitro

化合物 Compound	抑制率 Inhibition rate/%
化合物 Compound	水稻纹枯病菌 R. solani	小麦赤霉病菌 F. graminearum	番茄早疫病菌 A. solani	油菜菌核病菌 S. sclerotiorum	棉花枯萎病菌 F. oxysporium	辣椒疫病菌 P. capsici
6a	43.5 ± 1.7	19.9 ± 1.1	13.9 ± 0.6	7.8 ± 0.6	11.0 ± 1.1	0
6b	13.5 ± 0.9	0	4.4 ± 0.6	2.5 ± 0.6	11.0 ± 1.1	0
6c	13.0 ± 1.5	17.3 ± 0.5	8.2 ± 0.6	12.6 ± 1.1	5.7 ± 1.1	0
6d	40.0 ± 1.5	19.6 ± 0.9	18.4 ± 1.0	15.0 ± 0.6	12.4 ± 0.6	0
6e	45.5 ± 0.8	21.8 ± 1.4	32.0 ± 0.5	49.3 ± 1.1	13.1 ± 1.1	0
6f	43.5 ± 1.7	16.9 ± 0.9	28.2 ± 0.6	22.9 ± 1.8	12.0 ± 1.1	0
6g	44.5 ± 1.5	26.2 ± 0.5	19.6 ± 0.6	18.7 ± 1.1	20.8 ± 2.2	10.0 ± 0.1
6h	20.0 ± 1.7	20.2 ± 1.4	11.4 ± 0.6	17.3 ± 0.6	9.5 ± 1.6	11.0 ± 0.6
6i	38.0 ± 0.8	30.4 ± 0.9	22.8 ± 1.5	38.0 ± 0.6	14.8 ± 1.6	8.3 ± 0.6
6j	42.5 ± 1.7	25.3 ± 0.5	15.8 ± 1.5	12.7 ± 0.6	9.5 ± 1.2	6.2 ± 0.6
6k	56.0 ± 1.7	22.0 ± 1.4	29.8 ± 1.0	41.6 ± 0.6	13.8 ± 1.6	5.2 ± 0.6
6l	31.0 ± 0.1	20.2 ± 1.4	9.2 ± 0.6	6.7 ± 1.2	17.3 ± 1.1	6.2 ± 0.6
6m	51.0 ± 1.7	51.8 ± 1.4	53.5 ± 1.0	66.6 ± 1.6	50.3 ± 0.6	51.7 ± 0.6
6n	31.0 ± 1.5	10.8 ± 0.5	12.3 ± 0.5	6.7 ± 0.6	5.6 ± 1.1	0
6o	49.0 ± 1.5	28.3 ± 1.1	57.0 ± 2.4	67.4 ± 1.1	21.1 ± 1.6	21.0 ± 1.2
6p	44.5 ± 1.5	44.0 ± 1.6	48.7 ± 0.6	67.6 ± 1.6	21.2 ± 0.6	12.4 ± 1.2
6q	42.5 ± 0.8	28.6 ± 0.9	7.9 ± 0.1	20.8 ± 1.1	13.1 ± 1.1	16.9 ± 1.6
6r	35.5 ± 1.5	20.2 ± 0.5	15.8 ± 1.5	8.1 ± 1.1	13.8 ± 1.6	0
烯唑醇 diniconazole	86.0 ± 0.9	84.6 ± 0.9	97.8 ± 0.6	70.1 ± 1.6	79.9 ± 1.1	81.4 ± 1.1
注：化合物浓度为 100 μmol/L。每个处理重复 3 次(平均值 ± 标准差)。Note: The compound concentration was 100 μmol/L. Each treatment had three replicates (Mean ± SD).

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表 2 部分化合物对油菜菌核病菌的EC₅₀值

Table 2. The EC₅₀ value of some compounds against S. sclerotiorum

化合物 Compound	取代基 R	回归方程 Regression equation	相关系数 Correlation cofficient, r	EC₅₀/(μmol/L)	95% 置信限 95% Confidence limit/(μmol/L)
6m	4-CH(CH₃)₂	y = 0.4931x + 5.9931	0.9959	9.7	8.4~11.1
6o	4-OCH₃	y = 1.3279x + 6.6398	0.9967	58.2	51.7~65.6
6p	4-CH₂CH₃	y = 0.6884x + 6.4814	0.9964	7.1	6.0~8.2
烯唑醇 diniconazole	—	y = 0.9198x + 6.8791	0.9980	9.1	8.2~10.0
注：每个处理重复3次。Note: Each treatment had three replicates.

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表 3 目标化合物对朱砂叶螨的杀螨活性

Table 3. Insecticidal activities of target compounds against T. cinnabarinu

化合物 Compound	校正死亡率 Corrected mortality/%
化合物 Compound	24 h	48 h
6a	22.9 ± 0.7	25.8 ± 1.1
6b	43.1 ± 1.4	45.4 ± 1.0
6c	4.8 ± 0.7	14.2 ± 0.3
6d	19.1 ± 0.9	23.4 ± 0.8
6e	18.3 ± 1.1	36.1 ± 0.9
6f	14.6 ± 0.5	40.2 ± 0.3
6g	7.7 ± 0.6	39.2 ± 1.5
6h	54.6 ± 1.3	67.7 ± 1.4
6i	20.3 ± 0.9	23.3 ± 1.3
6j	13.1 ± 1.0	27.8 ± 0.4
6k	58.0 ± 1.1	74.9 ± 0.9
6l	48.8 ± 1.4	50.5 ± 1.5
6m	6.5 ± 0.6	9.1 ± 0.9
6n	9.5 ± 0.4	16.3 ± 1.0
6o	46.7 ± 1.1	57.5 ± 1.5
6p	15.7 ± 0.6	23.2 ± 1.0
6q	6.9 ± 0.9	21.8 ± 0.6
6r	6.7 ± 0.2	7.9 ± 1.1
阿维菌素 B1a Avermectin B1a	100	100
注：每个处理重复3次，化合物浓度为150 μmol/L。Note: Each treatment had three replicates. Compound concentration of 150 μmol/L.

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