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
收稿日期: 2015-01-29
修回日期: 2015-02-28
网络出版日期: 2015-07-24
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
Received date: 2015-01-29
Revised date: 2015-02-28
Online 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8～11. 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%.
张浩 , 刘瑞全 , 李奇博 , 李青阳 , 陈亚红 , 刘克昌 , 刘尚钟 . 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[J]. 有机化学, 2015 , 35(7) : 1506 -1513 . DOI: 10.6023/cjoc201501040
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 8～11. 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.
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