有机化学 ›› 2015, Vol. 35 ›› Issue (7): 1506-1513.DOI: 10.6023/cjoc201501040 上一篇    下一篇

研究论文

N-取代吡啶基-2-酰基四氢哒嗪-1(2H)-硫代甲酰胺的合成及除草活性

张浩a, 刘瑞全a, 李奇博a, 李青阳a, 陈亚红b, 刘克昌a, 刘尚钟a   

  1. a 中国农业大学理学院应用化学系 北京 100193;
    b 北京颖泰嘉和生物科技有限公司 北京 100192
  • 收稿日期:2015-01-29 修回日期:2015-02-28 发布日期:2015-07-24
  • 通讯作者: 刘尚钟 E-mail:shangzho@cau.edu.cn
  • 基金资助:

    “十二五”科技支撑计划(No. 2011BAE06B03)、国家自然科学基金(No. 21172256)资助项目.

Synthesis and Herbicidal Activities of N-Substituted Pyridyl-2- acyltetrahydropyridazine-1(2H)-carbothioamides

Zhang Haoa, Liu Ruiquana, Li Qiboa, Li Qingyanga, Chen Yahongb, Liu Kechanga, Liu Shangzhonga   

  1. a Department of Applied Chemistry, College of Science, China Agricultural University, Beijing 100193;
    b Nutrichem Co., Ltd, Beijing 100192
  • Received:2015-01-29 Revised:2015-02-28 Published:2015-07-24
  • Supported by:

    Project supported by the National Key Technologies R&D Program (No. 2011BAE06B03), and the National Natural Science Foundation of China (No. 21172256).

以取代氨基吡啶为原料, 经二步反应合成关键中间体--取代吡啶基异硫氰酸酯, 再分别与4个制备的取代六氢哒嗪中间体缩合, 合成了4个系列共22个新型N-取代吡啶基-2-酰基四氢哒嗪-1(2H)-硫代甲酰胺类化合物811. 所有目标产物的结构均经过1H NMR, 13C NMR和HRMS的确证. 初步的除草活性测试表明, 部分化合物在375 g·ha-1剂量下, 对双子叶杂草苘麻及反枝苋和单子叶杂草马唐具有约100%芽前抑制活性. 进一步活性筛选发现, 2-[(5-氯吡啶-2-基)硫代氨基甲酰基]四氢哒嗪-1(2H)-甲酸乙酯(9e)在45 g·ha-1 剂量下对苘麻的抑制率仍达到95%.

关键词: 酰氨基硫脲, 六氢哒嗪, 吡啶, 合成, 除草活性

Key intermediates-substituted pyridyl isothiocyanates, which were prepared from starting material substituted pyridyl amines via two steps, were further condensed with four substituted hexahydropyridazine intermediates to afford four series of novel N-substituted pyridyl-2-acyltetrahydropyridazine-1(2H)-carbothioamides 811. The structures of all compounds have been confirmed by 1H NMR, 13C NMR and HRMS techniques. The preliminary bioassay results indicated that some of the title compounds exhibited approximately 100% inhibition against Abutilon theophrasti, Amaranthus retroflexus and Digitaria sanguinalis at a dose of 375 g·ha-1. In particular, ethyl 2-((5-chloropyridin-2-yl)carbamothioyl)tetrahydropy- ridazine-1(2H)-carboxylate (9e) displayed the best pre-emergence herbicidal effect against Abutilon theophrasti with 95% inhibitory activity even at 45 g·ha-1.

Key words: acyl thiosemicarbazides, hexahydropyridazine, pyridine, synthesis, herbicidal activity