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2020 , Vol. 40 >Issue 9: 2971 - 2979

DOI: https://doi.org/10.6023/cjoc202005075

研究简报

含1,2,3-噻二唑环(E)-β-farnesene类似物的设计、合成及生物活性研究

  • 张景朋 ,
  • 杨朝凯 ,
  • 秦耀果 ,
  • 杨新玲
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  • a 中国农业大学理学院应用化学系 北京 100193;
    b 中国林业科学研究院木材工业研究所 北京 100091

收稿日期: 2020-05-28

  修回日期: 2020-06-12

  网络出版日期: 2020-07-01

基金资助

国家重点研发计划基金（No.2017YFD0200504）资助项目.

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Design, Synthesis and Biological Activity of (E)-β-Farnesene Analogues Containing 1,2,3-Thiadiazole

  • Zhang Jingpeng ,
  • Yang Zhaokai ,
  • Qin Yaoguo ,
  • Yang Xinling
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  • a Department of Applied Chemistry, College of Science, China Agricultural University, Beijing 100193;
    b Research Institute of Wood Industry, Chinese Academy of Forestry, Beijing 100091

Received date: 2020-05-28

  Revised date: 2020-06-12

  Online published: 2020-07-01

Supported by

Project supported by the National Key Research and Development Plan (No. 2017YFD0200504).

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摘要

为了发现控制蚜虫的新型高活性化合物，以蚜虫报警信息素（E）-β-farnesene（EBF）为先导化合物，用1，2，3-噻二唑环替代EBF结构中不稳定的共轭双键，设计、合成了15个EBF类似物，所有化合物结构均通过1H NMR、13C NMR、IR及HRMS确证.生物活性测试结果表明：化合物对桃蚜表现出较好的驱避活性，其中以N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（2-萘基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8d）、N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（4-甲基-吡啶-2-基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8l）和N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（5-甲基-吡啶-2-基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8m）最为显著，驱避率分别为63.1%、61.3%和63.4%；化合物对桃蚜的毒杀活性均高于EBF，其中N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（4-氰基-苯基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8b）、N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（6-甲基-吡啶-2-基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8g）、N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（吡啶-2-基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8j）、N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（3-甲基-吡啶-2-基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8k）、8l、8m和N-（（E）-3，7-二甲基-2，6-辛二烯-1-基）-N-（5-甲基-1，3，4-噻二唑-2-基）-4-甲基-1，2，3-噻二唑-5-甲酰胺（8o）的杀蚜活性比较突出（LC50分别是10.2、9.0、25.1、31.7、8.4、12.8和9.6 μg/mL），但活性略低于对照药剂吡蚜酮（LC50值7.1 μg/mL）.

关键词： 1,2,3-噻二唑; EBF类似物; 合成; 驱避活性; 杀虫活性

本文引用格式

张景朋 , 杨朝凯 , 秦耀果 , 杨新玲 . 含1,2,3-噻二唑环(E)-β-farnesene类似物的设计、合成及生物活性研究[J]. 有机化学, 2020 , 40(9) : 2971 -2979 . DOI: 10.6023/cjoc202005075

Abstract

In order to discover novel compounds with high-activity to control aphid, aphid alarm pheromone (E)-β-farnesene (EBF) was chosen as lead compound and 15 EBF analogues were designed and synthesized by replacing unstable conjugated double bond of EBF with 1,2,3-thiadiazole. Their structures were confirmed by 1H NMR, 13C NMR, IR and HRMS analysis. Repellent activity results indicated that analogues displayed better repellent activity against Myzus persicae (Sulzer). Among which compounds N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(2-naphthyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8d), N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(4-methyl-pyridine-2-yl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8l) and N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(5-methyl-pyridine-2-yl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8m) exhibited excellent repellent activity of 63.1%, 61.3% and 63.4% respectively. The aphicidal bioassay results showed that most analogues exhibited considerable aphicidal activity against Myzus persicae. Especially, analogues N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(4-CN-phenyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8b), N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(6-methyl-pyridine-2-yl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8g), N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(2-pyridyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8j), N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(3-methyl-pyridine-2-yl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8k), 8l, 8m and N-((E)-3,7-dimethyl-2,6-octadien-1-yl)-N-(5-methyl-1,3,4-thiadiazole-2-yl)-4-methyl-1,2,3-thiadiazole-5-carboxamide (8o) exhibited high activity with LC50 values of 10.2, 9.0, 25.1, 31.7, 8.4, 12.8 and 9.6 μg/mL, respectively, which were higher than the lead compound (E)-β-farnesene, but lower than commercial insecticide pymetrozine with LC50 of 7.1 μg/mL.

Key words： 1,2,3-thiadiazole; EBF analogues; synthesis; repellent activity; insecticidal activity

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