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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

游江 高亚强 周蒲 郭倩男 徐志红

游江, 高亚强, 周蒲, 郭倩男, 徐志红. 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[J]. 农药学学报, 2022, 24(4): 723-731. doi: 10.16801/j.issn.1008-7303.2022.0016
引用本文: 游江, 高亚强, 周蒲, 郭倩男, 徐志红. 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[J]. 农药学学报, 2022, 24(4): 723-731. doi: 10.16801/j.issn.1008-7303.2022.0016
YOU Jiang, GAO Yaqiang, ZHOU Pu, GUO Qiannan, XU Zhihong. Synthesis and biological activity of N-substituted phenyl-1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylcarbamate[J]. Chinese Journal of Pesticide Science, 2022, 24(4): 723-731. doi: 10.16801/j.issn.1008-7303.2022.0016
Citation: YOU Jiang, GAO Yaqiang, ZHOU Pu, GUO Qiannan, XU Zhihong. Synthesis and biological activity of N-substituted phenyl-1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylcarbamate[J]. Chinese Journal of Pesticide Science, 2022, 24(4): 723-731. 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
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

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

Funds: the National Natural Science Foundation of China (31772170).
  • 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 6h6k6o 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  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

    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

    3  目标化合物的合成路线

    3.  Synthetic route of target compounds

    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/%
    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).
    下载: 导出CSV

    表  2  部分化合物对油菜菌核病菌的EC50

    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)
    6m4-CH(CH3)2y = 0.4931x + 5.99310.99599.78.4~11.1
    6o4-OCH3y = 1.3279x + 6.63980.996758.251.7~65.6
    6p4-CH2CH3y = 0.6884x + 6.48140.99647.16.0~8.2
    烯唑醇
    diniconazole
    y = 0.9198x + 6.87910.99809.18.2~10.0
    注:每个处理重复3次。Note: Each treatment had three replicates.
    下载: 导出CSV

    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/%
    24 h48 h
    6a22.9 ± 0.725.8 ± 1.1
    6b43.1 ± 1.445.4 ± 1.0
    6c4.8 ± 0.714.2 ± 0.3
    6d19.1 ± 0.923.4 ± 0.8
    6e18.3 ± 1.136.1 ± 0.9
    6f14.6 ± 0.540.2 ± 0.3
    6g7.7 ± 0.639.2 ± 1.5
    6h54.6 ± 1.367.7 ± 1.4
    6i20.3 ± 0.923.3 ± 1.3
    6j13.1 ± 1.027.8 ± 0.4
    6k58.0 ± 1.174.9 ± 0.9
    6l48.8 ± 1.450.5 ± 1.5
    6m6.5 ± 0.69.1 ± 0.9
    6n9.5 ± 0.416.3 ± 1.0
    6o46.7 ± 1.157.5 ± 1.5
    6p15.7 ± 0.623.2 ± 1.0
    6q6.9 ± 0.921.8 ± 0.6
    6r6.7 ± 0.27.9 ± 1.1
    阿维菌素 B1a
    Avermectin B1a
    100100
    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.
    下载: 导出CSV
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  • 目标化合物的核磁共振氢谱、碳谱谱图和高分辨质谱图.pdf
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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

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