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  

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

作　　者：秦耀果 杨朝凯 张以涵 周雨蓓 潘世香 刘彦 石卓 杨新玲[1] QIN Yaoguo;YANG Zhaokai;ZHANG Yihan;ZHOU Yubei;PAN Shixiang;LIU Yan;SHI Zhuo;YANG Xinling(Innovation Center of Pesticide Research,Department of Applied Chemistry,College of Science,China Agricultural University,Beijing 100193,China;Department of Entomology,College of Plant Protection,China Agricultural University,Beijing 100193,China)

机构地区：[1]中国农业大学理学院农药创新研究中心,北京100193 [2]中国农业大学植物保护学院昆虫学系,北京100193

出　　处：《农药学学报》2022年第5期1179-1188,共10页Chinese Journal of Pesticide Science

基　　金：国家自然科学基金(31801739);国家重点研发计划课题(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(^(1)H 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5μg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。In order to discover aphid behavioral control agents with new structures,15 novel geranyl 2-alkoxy-substitutedbenzoate aphid alarm pheromone(E)-β-Farnesene(EβF)derivatives were designed and synthesized by using the method of linking active substructures based on the lead compound 3e(geranyl 2-hydroxy-3-methoxybenzoate).The structures of the target compounds were confirmed by ^(1)H NMR,IR and HRMS.Preliminary bioassay results showed that some target compounds had varied repellent activity against the pea aphid Acyrthosiphon pisum at the dosage of 5μg.Among them,the compound 6i exhibited the highest repellent proportion of 60.9%,which was not significantly different from that of the lead 3e.The target protein binding experiments showed that some target compounds had good binding activities with the odorant binding proteins of ApisOBP9.Particularly,compound 6i displayed the best binding constant of(4.92±0.18)μmol/L with ApisOBP9.Further molecular docking study revealed that the representative compound 6i had a good binding affinity to the ApisOBP9,wherein it had the similar binding mode with ApisOBP9 like 3e.This study provides important clues for the further structure optimization.

关 键 词：蚜虫行为控制剂 蚜虫报警信息素 (E)-β-farnesene衍生物 合成 驱避活性 气味结合蛋白 蛋白结合活性 

分 类 号：TQ453.4[化学工程—农药化工]