有机化学 ›› 2020, Vol. 40 ›› Issue (9): 2788-2797.DOI: 10.6023/cjoc202005031 上一篇    下一篇

研究论文

5-酰基巴比妥酸衍生物的设计、合成及除草活性和分子作用机制研究

雷康a, 李攀a, 周晓芸a, 王世本a, 王学堃a, 冀卢莎a, 柳仁民a, 徐效华b   

  1. a 聊城大学药学院 山东聊城 252000;
    b 南开大学元素有机化学国家重点实验室 天津 300071
  • 收稿日期:2020-05-13 修回日期:2020-06-15 发布日期:2020-07-09
  • 通讯作者: 雷康 E-mail:leikang@lcu.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.31701827,81803360)、中国博士后科学基金(No.2020M671984)、聊城大学博士科研启动基金(No.318051647)、聊城大学大学生创新创业训练(No.CXCY2020Y179)和山东省自然科学基金(Nos.ZR2019PC041,ZR2017BH037)资助项目.

Design, Synthesis and Herbicidal Activity of 5-Acylbarbituric Acid Derivatives and Study of Molecular Mode of Action

Lei Kanga, Li Pana, Zhou Xiaoyuna, Wang Shibena, Wang Xuekuna, Ji Lushaa, Liu Renmina, Xu Xiaohuab   

  1. a School of Pharmacy, Liaocheng University, Liaocheng, Shandong 252000;
    b State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071
  • Received:2020-05-13 Revised:2020-06-15 Published:2020-07-09
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 31701827, 81803360), the China Postdoctoral Science Foundation (No. 2020M671984), the Doctoral Research Startup Foundation of Liaocheng University (No. 318051647), the Innovation and Entrepreneurship Training Program for College Students of Liaocheng University (No. CXCY2020Y179) and the Natural Science Foundation of Shandong Province (Nos. ZR2019PC041, ZR2017BH037).

为了开发含有巴比妥酸结构的新型β-三酮类除草剂,设计、合成了一系列5-酰基巴比妥酸衍生物,并测试了其除草活性.温室盆栽测试结果表明,在1500 g·ha-1的剂量下,目标化合物1,3-二甲基-5-(2-(2-氯-4-氟苯氧基)-1-羟基亚乙基)嘧啶-2,4,6(1H,3H,5H)-三酮(BBA-22)和1,3-二甲基-5-(2-(2-溴-4-氟苯氧基)-1-羟基亚乙基)嘧啶-2,4,6(1H,3H,5H)-三酮(BBA-27)对所测杂草均具有优异的抑制活性.其中,化合物BBA-22在苗前处理187.5 g·ha-1的剂量下,对油菜、苋菜和马唐具有很好的抑制活性,其活性优于商品除草剂2,4-二氯苯氧乙酸(2,4-D).另外,以拟南芥为模型植物的分子作用机制研究表明,化合物BBA-22在植物体中被降解为相应的苯氧乙酸,这解释了其与生长素类除草剂具有相似除草机理的原因.本工作的研究结果表明,化合物BBA-22是其相应的苯氧乙酸生长素类除草剂的前药,可以用作进一步开发新型生长素型除草剂的先导化合物.

关键词: β-三酮, 5-酰基巴比妥酸, 合成, 除草剂, 苯氧乙酸

In an effort to develop novel β-triketone herbicides containing a barbituric acid moiety, a series of 5-acylbarbituric acid derivatives were designed, synthesized, and tested for herbicidal activity. The bioassay results showed that some of the target compounds, such as 5-(2-(2-chloro-4-fluorophenoxy)-1-hydroxyethylidene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (BBA-22) and 5-(2-(2-bromo-4-fluorophenoxy)-1-hydroxyethylidene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (BBA-27), exhibited excellent herbicidal activity against all tested weeds at a dosage of 1500 g·ha-1. In particular, compound BBA-22 displayed good pre-emergent herbicidal activity against Brassica campestris, Amaranthus retroflexus and Digitaria sanguinalis even at a dosage of 187.5 g·ha-1,surpassing that of a commercial herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Investigation of the molecular mode of action of compound BBA-22 upon treatment of Arabidopsis thaliana as a model plant revealed that BBA-22 was degraded to the corresponding phenoxyacetic acid, which explains why the herbicidal mechanism is similar to that of auxin-type herbicides. The present study demonstrates that compound BBA-22 is a proherbicide of the corresponding phenoxyacetic acid auxin herbicide and a potential lead compound for further development of novel auxin herbicides.

Key words: β-triketone, 5-acylbarbituric acid, synthesis, herbicide, phenoxyacetic