有机化学 ›› 2019, Vol. 39 ›› Issue (5): 1344-1353.DOI: 10.6023/cjoc201811041 上一篇    下一篇

研究论文

新型特窗酸肼基衍生物的合成、杀菌及杀虫活性

赵宇, 关爱莹, 李婉祯, 王卫伟, 刘鑫磊, 王明安   

  1. 中国农业大学应用化学系 北京 100193
  • 收稿日期:2018-11-30 修回日期:2019-01-28 发布日期:2019-02-22
  • 通讯作者: 王明安 E-mail:wangma@cau.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21772229,21172254)资助项目.

Synthesis, Fungicidal and Insecticidal Activity of Novel Tetronic Acid Hydrazinyl Derivatives

Zhao Yu, Guan Aiying, Li Wanzhen, Wang Weiwei, Liu Xinlei, Wang Ming'an   

  1. Department of Applied Chemistry, China Agricultural University, Beijing 100193
  • Received:2018-11-30 Revised:2019-01-28 Published:2019-02-22
  • Contact: 10.6023/cjoc201811041 E-mail:wangma@cau.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21772229, 21172254).

设计合成了一系列新型3-乙酰基-4-肼基-5,5-二取代特窗酸和(E/Z)-3-(1-肼基亚乙基)-5,5-二取代2,4-呋喃二酮衍生物,意外得到4个5-甲基吡唑-4-羧酸甲酯,它们的结构经过HR-ESI-MS,1H NMR,13C NMR和X射线衍射的表征.这些肼基与氨基衍生物的生物活性测试结果表明,部分化合物显示出对测试植物病原菌中等至优异的杀菌活性.如在400 μg/mL浓度时化合物5G5H5I5i对炭疽病菌有100%的活体抑制活性,化合物5G对霜霉病菌、白粉病菌和锈病病菌的活体抑制活性均为100%.在600μg/mL浓度时化合物5b5E6F对小菜蛾,化合物6A6g6H对桃蚜以及化合物6b对朱砂叶螨的死亡率均为100%.5,5-螺环己基可以显著提高特窗酸衍生物的杀菌活性,取代肼基的引入可以获得更高的杀虫杀螨活性.化合物5G5i是最有潜力作为研发新型杀菌剂进行结构修饰的先导化合物.

关键词: 肼衍生物, 螺环己基特窗酸, 杀菌活性, 杀虫活性

A series of novel 3-acetyl-4-hydrazinyl-5,5-disubstitutedtetronic acid and (E/Z)-3-(1-hydrazinylethyli-dene)-5,5-disubstitutedfuran-2,4-dione derivatives were designed and synthesized, and four methyl 5-methyl pyrazole-4-carboxylate were obtained unexpectedly. Their structures were confirmed by high-resolution mass spectrum (HR-ESI-MS), 1H NMR, 13C NMR spectral data and X-ray diffraction. The bioassay results of the hydrazinyl compounds along with the amino analogues indicated that some compounds exhibited moderate to excellent fungicidal activities against phytopathagens. For example, compounds 5G, 5H, 5I and 5i showed 100% in vivo control efficacy against Colletotrichum lagenarium, and compound 5G also exhibited 100% in vivo control efficacy against Erysiphe graminis, Puccinia polysora and Colletotrichum lagenarium at 400 μg/mL. Compounds 5b, 5E and 6F showed 100% mortality against Plutella xylostella, compounds 6A, 6g and 6H exhibited 100% mortality against Myzus persicae, and compound 6b showed 100% mortality against Tetranychus cinnabarinus at 600 μg/mL. The 5,5-spiro cyclohexyl moiety significantly improved the fungicidal activity of the tetronic acid derivatives, and the introduction of the substituted hydrazino group to the furan-2,4-dione skeleton led to higher insecticidal and acaricidal activities. 5G and 5i were found to have the most potential to be further modified for searching new fungicide as the lead compounds.

Key words: hydrazine derivatives, spirocyclohexyl tetronic acid, fungicidal activity, insecticidal activity