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林产化学与工业 ›› 2019, Vol. 39 ›› Issue (4): 27-34.doi: 10.3969/j.issn.0253-2417.2019.04.004

• 研究报告 • 上一篇    下一篇

(Z)-/(E)-马鞭草烯酮肟醚的合成及抑菌活性

王晓宇1,段文贵1,*(),林桂汕1,康国强1,商明昊1,雷福厚2   

  1. 1. 广西大学 化学化工学院, 广西 南宁 530004
    2. 广西林产化学与工程重点实验室, 广西 南宁 530008
  • 收稿日期:2019-04-15 出版日期:2019-08-25 发布日期:2019-08-23
  • 通讯作者: 段文贵 E-mail:wgduan@gxu.edu.cn
  • 作者简介:王晓宇(1992-),女,河北石家庄人,硕士生,从事天然产物改性及有机合成研究
  • 基金资助:
    国家自然科学基金资助项目(31560194);广西林产化学与工程重点实验室开放基金资助项目(GXFC16-03);广西大学大学生创新创业训练计划资助项目(201810593037)

Synthesis and Antifungal Activity of (Z)-/(E)-Verbenone Oxime Ether Compounds

Xiaoyu WANG1,Wengui DUAN1,*(),Guishan LIN1,Guoqiang KANG1,Minghao SHANG1,Fuhou LEI2   

  1. 1. College of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
    2. Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Nanning 530008, China
  • Received:2019-04-15 Online:2019-08-25 Published:2019-08-23
  • Contact: Wengui DUAN E-mail:wgduan@gxu.edu.cn
  • Supported by:
    国家自然科学基金资助项目(31560194);广西林产化学与工程重点实验室开放基金资助项目(GXFC16-03);广西大学大学生创新创业训练计划资助项目(201810593037)

摘要:

α-蒎烯选择性氧化制备马鞭草烯酮,对羰基进行肟化和分离,再发生亲核取代反应,合成得到40个新型(Z)-/(E)-马鞭草烯酮肟醚(4a~4t,包括20对Z/E异构体),采用1H NMR、13C NMR、FT-IR、UV-vis和ESI-MS对目标化合物进行了结构表征,并测试其抑菌活性。研究结果表明:在质量浓度50 mg/L下,目标化合物对8种植物病原菌均显示出不同程度的抑菌活性,其中化合物(E)-4r(R=2,6-Cl)对苹果轮纹病菌的抑制率为77.8%,化合物(E)-4s(R=2,6-F)对水稻纹枯病菌的抑制率为72.7%,化合物(E)-4n(R=p-CN)对玉米小斑病菌的抑制率为70.8%,(Z)-/(E)-异构体对一些植物病原菌的抑制活性显示一定差异。建立了(E)-马鞭草烯酮肟醚化合物对水稻纹枯病菌抑制活性的CoMFA模型(r2=0.992,q2=0.507),进行3D-QSAR研究,结果表明建立的模型可用于设计具有潜在高活性的先导化合物。

关键词: α-蒎烯, 马鞭草烯酮, 肟醚, Z-E异构体, 抑菌活性, 3D-QSAR

Abstract:

Verbenone was prepared by selective oxidation of α-pinene at first. Then, by oximation of the carbonyl group (Z)-and(E)-verbenone oxime compounds were synthesized and separaed, followed by the nucleophilic substitution reaction to afford forty novel (Z)-and (E)-verbenone oxime ether compounds 4a-4t, including twenty couples of Z/E isomers. The structures of the target compounds were characterized by 1H NMR, 13C NMR, FT-IR, UV-vis, and ESI-MS. The antifungal activities of the target compounds were evaluated. The results showed that, at the mass concentration of 50 mg/L, all the target products exhibited certain inhibition activities against the eight kinds of plant pathogens. Compound(E)-4r(R=2, 6-Cl) had inhibition rates of 77.8% against Physalospora piricola. Compound(E)-4s(R=2, 6-F) had inhibition rates of 72.7% against Rhizoctonia solani. Compound (E)-4n(R=p-CN) had inhibition rates of 70.8% against Helmithosporium maydis. Certain difference were found in inhibition activity of Z-E isomers against some plant pathogens. The CoMFA model(r2=0.992, q2=0.507) of (E)-verbenone oxime ether compounds for inhibiting Rhizoctonia solani was established for the study of 3D-QSAR, and the results could provide a basis for the design of potential lead compounds with higher activity.

Key words: α-pinene, verbenone, oxime ether, Z-E isomer, antifungal activity, 3D-QSAR

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