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新型2-烷氧基取代苯甲酸香叶酯类蚜虫报警信息素类似物的设计、合成及生物活性

秦耀果 杨朝凯 张以涵 周雨蓓 潘世香 刘彦 石卓 杨新玲

秦耀果, 杨朝凯, 张以涵, 周雨蓓, 潘世香, 刘彦, 石卓, 杨新玲. 新型2-烷氧基取代苯甲酸香叶酯类蚜虫报警信息素类似物的设计、合成及生物活性[J]. 农药学学报, 2022, 24(5): 1179-1188. doi: 10.16801/j.issn.1008-7303.2022.0103
引用本文: 秦耀果, 杨朝凯, 张以涵, 周雨蓓, 潘世香, 刘彦, 石卓, 杨新玲. 新型2-烷氧基取代苯甲酸香叶酯类蚜虫报警信息素类似物的设计、合成及生物活性[J]. 农药学学报, 2022, 24(5): 1179-1188. doi: 10.16801/j.issn.1008-7303.2022.0103
QIN Yaoguo, YANG Zhaokai, ZHANG Yihan, ZHOU Yubei, PAN Shixiang, LIU Yan, SHI Zhuo, YANG Xinling. Design, synthesis, bioactivities of novel geranyl 2-alkoxy-substitutedbenzoate as aphid alarm pheromone derivatives[J]. Chinese Journal of Pesticide Science, 2022, 24(5): 1179-1188. doi: 10.16801/j.issn.1008-7303.2022.0103
Citation: QIN Yaoguo, YANG Zhaokai, ZHANG Yihan, ZHOU Yubei, PAN Shixiang, LIU Yan, SHI Zhuo, YANG Xinling. Design, synthesis, bioactivities of novel geranyl 2-alkoxy-substitutedbenzoate as aphid alarm pheromone derivatives[J]. Chinese Journal of Pesticide Science, 2022, 24(5): 1179-1188. doi: 10.16801/j.issn.1008-7303.2022.0103

新型2-烷氧基取代苯甲酸香叶酯类蚜虫报警信息素类似物的设计、合成及生物活性

doi: 10.16801/j.issn.1008-7303.2022.0103
基金项目: 国家自然科学基金(31801739);国家重点研发计划课题 (2017YFD0200504).
详细信息
    作者简介:

    秦耀果,qinyg1018@163.com

    杨朝凯,yangzhaokai@cau.edu.cn

    通讯作者:

    杨新玲,yangxl@cau.edu.cn

  • 中图分类号: TQ453.4

Design, synthesis, bioactivities of novel geranyl 2-alkoxy-substitutedbenzoate as aphid alarm pheromone derivatives

Funds: the National Natural Science Foundation of China (31801739); the National Key Research and Development Plan (2017YFD0200504).
  • 摘要: 为了发现结构新颖的蚜虫行为控制剂,以课题组发现的高活性化合物 3e (2-羟基-3-甲氧基苯甲酸香叶酯)为先导,利用活性亚结构拼接的方法,设计合成了15个未见文献报道的新型2-烷氧基取代苯甲酸香叶酯类蚜虫报警信息素(E)-β-farnesene (EβF)衍生物,其结构经过核磁共振氢谱(1H NMR)、红外光谱(IR)和高分辨质谱(HRMS)的确证。蚜虫驱避活性测定结果表明,部分目标化合物在5 µg剂量下对豌豆蚜Acyrthosiphon pisum表现出不同程度的驱避活性,其中化合物 6i 活性最高,驱避率达到60.9%,与先导化合物 3e 的活性没有显著性差异。靶标蛋白结合实验证明,部分目标化合物与气味结合蛋白ApisOBP9具有较好的结合活性,尤其是化合物 6i 与ApisOBP9的结合常数达到(4.92±0.18) µmol/L。进一步的分子对接结果表明, 6i 与靶标ApisOBP9具有较好的结合作用力,能很好地结合到靶标蛋白的活性位点,其结合模式和先导化合物相似。本研究对后续化合物的结构优化具有重要参考价值。
  • 1  (E)-β-farnesene的结构

    1.  The structure of (E)-β-farnesene

    2  目标化合物的设计策略

    2.  Design strategy of the target compounds

    3  目标化合物的合成路线

    3.  Synthetic routes of the target compounds

    (i) benzyl bromide, TABA, DCM, H2O, r.t., 5 h; NaOH, EtOH, reflux, 4 h; HCl, H2O, pH = 4.0; (ii) t-BuOK, THF, DMF, 0 °C for 30 mins and then r.t. for 4 h; (iii) DCC, DMAP, 0 °C for 30 mins; r.t., 8 h.

    图  1  目标化合物与ApisOBP9的荧光竞争结合曲线

    Figure  1.  Fluorescence competitive binding curves of the target compounds to ApisOBP9

    图  2  目标化合物与ApisOBP9的结合活性

    Figure  2.  Binding activity of the target compounds with ApisOBP9 from A. pisum

    图  3  目标化合物6i与豌豆蚜气味结合蛋白ApisOBP9的结合模式

    Figure  3.  Binding mode of the compound 6i with ApisOBP9

    表  1  目标化合物的豌豆蚜驱避活性

    Table  1.   The aphid repellent activity against A. pisum

    化合物
    Compd.
    取代基
    R1
    取代基
    R2
    驱避率*
    Repellent proportion*/%
    化合物
    Compd.
    取代基
    R1
    取代基
    R2
    驱避率*
    Repellent proportion*/%
    5a 3-OCH3 CH2CH3 42.5 ± 9.3 de 6d 3-CH3 CH2Ph 42.9 ± 6.4 de
    5b 3-OCH3 (CH2)2CH3 33.9 ± 4.7 e 6e 4-CH3 CH2Ph 57.4 ± 5.6 bc
    5c 3-OCH3 (CH2)3CH3 20.1 ± 5.9 f 6f 5-CH3 CH2Ph 51.8 ± 6.6 cd
    5d 3-OCH3 (CH2)4CH3 18.5 ± 3.0 f 6g 3-OCH3 CH2Ph 38.2 ± 4.2 de
    5e 3-OCH3 (CH2)5CH3 18.9 ± 3.7 f 6h 4-OCH3 CH2Ph 51.3 ± 5.4 cd
    5f 3-OCH3 (CH2)6CH3 21.2 ± 9.6 f 6i 5-OCH3 CH2Ph 60.9 ± 3.5 bc
    6a H CH3 36.5 ± 6.1 e 3e 3-OCH3 OH 66.5 ± 3.8 ab
    6b H CH2CH3 48.0 ± 1.8 cde EβF 75.7 ± 1.2 a
    6c H CH2Ph 59.3 ± 1.2 bc
    注:*驱避率数值为平均值±标准偏差。不同字母表示在α = 0.05的水平上各处理间的差异显著。 Note: *Repellent proportion values are mean ± standard deviation. Different letters indicate significant differences at the level of α = 0.05.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-08-24
  • 录用日期:  2022-09-08
  • 网络出版日期:  2022-09-17
  • 刊出日期:  2022-10-10

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