State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin, China.
Pest Manag Sci. 2019 Dec;75(12):3273-3281. doi: 10.1002/ps.5449. Epub 2019 May 14.
N-Pyridylpyrazole derivatives have received continuous attention in agrochemical research during the last decade owing to their remarkable insecticidal or fungicidal potentials. To look for novel heterocyclic agrochemicals for increasing production of agriculture, a series of novel α-aminophosphonate derivatives containing N-pyridylpyrazole moiety were synthesized.
The structures of the title compounds were confirmed via melting point, IR, H NMR, C NMR, P NMR, HRMS and elemental analysis. The single crystal structure of diethyl (3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)(2,6-dimethylphenylamino)methylphosphonate (compound 12b) was first reported. Moreover, the bioassays displayed that the title compounds exhibited modest or weak insecticidal activities against oriental armyworm at 200 μg mL . The first investigation on the fungicidal potential of chlorantraniliprole showed no significant activities towards the six tested fungi found in this study, however, most of the title compounds displayed apparent in vitro fungicidal activity against some plant fungi, in particular excellent activities towards Physalospora piricola. Compounds 11a and 11b had EC values of 18.8 and 17.4 μg mL , respectively, which were comparable with that of fungicide control triadimefon (EC = 24.7 μg mL ) against Physalospora piricola. In addition, some compounds exhibited modest in vivo control efficacy at 0.5 mg mL towards Sclerotinia sclerotiorum (11b: 30.1(±1.8)%), Rhizoctonia cerealis (11a: 20.4(±2.1)%; 11b: 30.2(±2.2)%), and Erysiphe graminis (11a: 30.3(±1.8)%; 12d: 40.2(±0.9)%).
Compounds 11a, 11b and 12d could be promising new lead structures for the development and discovery of novel fungicides towards Physalospora piricola and Erysiphe graminis. The structure-activity relationship (SAR) analysis provided useful guidance and new understanding for the design of novel pyridylpyrazole-containing agrochemicals. © 2019 Society of Chemical Industry.
由于其显著的杀虫或杀菌潜力，N-吡啶基吡唑衍生物在过去十年的农业化学研究中受到了持续关注。为了寻找增加农业产量的新型杂环农用化学品，我们合成了一系列含有 N-吡啶基吡唑部分的新型α-氨基膦酸酯衍生物。
通过熔点、IR、1H NMR、13C NMR、31P NMR、高分辨质谱和元素分析确证了标题化合物的结构。首次报道了二乙基（3-溴-1-（3-氯吡啶-2-基）-1H-吡唑-5-基）（2,6-二甲基苯基氨基）甲基膦酸酯（化合物 12b）的单晶结构。此外，生物测定结果表明，这些标题化合物对东方粘虫在 200μg/mL 时表现出中等或弱的杀虫活性。氯虫苯甲酰胺杀菌活性的首次研究结果表明，对本研究中发现的六种测试真菌没有显著活性，但大多数标题化合物对一些植物真菌表现出明显的体外杀菌活性，特别是对梨孢叶斑病菌表现出优异的活性。化合物 11a 和 11b 的 EC 值分别为 18.8 和 17.4μg/mL，与杀菌剂对照三唑酮（EC=24.7μg/mL）对梨孢叶斑病菌的 EC 值相当。此外，一些化合物在 0.5mg/mL 时对核盘菌（11b：30.1（±1.8）%）、禾谷丝核菌（11a：20.4（±2.1）%；11b：30.2（±2.2）%）和小麦白粉病（11a：30.3（±1.8）%；12d：40.2（±0.9）%）具有中等的体内防治效果。
化合物 11a、11b 和 12d 可能是开发和发现针对梨孢叶斑病菌和小麦白粉病的新型吡唑嘧啶农用化学品的有前途的新先导结构。构效关系（SAR）分析为设计新型含吡唑嘧啶的农用化学品提供了有用的指导和新的认识。
