新型N-取代苯基-2-吡唑基烟酰胺类化合物的合成及其生物活性

Synthesis and Biological Activities of Novel N-Substitutedphenyl-2-pyrazolylnicotinamides

基于含吡啶基吡唑的邻甲酰氨基苯甲酰胺类农药分子结构,采用“酰基移位”的策略,以2-氯-3-氰基吡啶和4-溴吡唑或3,5-二甲基吡唑为起始原料,简便合成了14个结构新颖的N-取代苯基-2-吡唑基烟酰胺类目标化合物.通过1H NMR、13C NMR和HRMS对新化合物进行了结构表征.初步生物活性测试结果表明,目标化合物在200mg/L浓度下大多具有明显的杀虫活性,其中N-[4-氯-2-(乙氨基甲酰基)-6-甲基苯基]-2-(3,5-二甲基-1H-吡唑-1-基)烟酰胺(Il)对东方粘虫(Mythimna separata Walker)具有70%的致死率;部分化合物在50mg/L浓度下对苹果轮纹病菌(Physalospora piricola)和番茄早疫病菌(Alternaria solani Sorauer)表现出较好的杀菌活性,其中2-(4-溴-1H-吡唑-1-基)-N-[2-(环丙氨基甲酰基)-4-碘-6-甲基苯基]烟酰胺(If)和2-(4-溴-1H-吡唑-1-基)-N-[4-氯-2-(乙氨基甲酰基)-6-甲基苯基]烟酰胺(Ih)对苹果轮纹病菌的抑制率分别达到62.9%和54.3%,2-(4-溴-1H-吡唑-1-基)-N-[4-氯-2-(正丙氨基甲酰基)苯基]烟酰胺(Id)对番茄早疫病菌具有54.5%的抑制率.研究结果为今后新型2-吡唑基烟酰胺类衍生物的深入研究提供了重要参考信息.

Based on the agrochemical structure of anthranilic diamides, fourteen novel N-substitutedphenyl-2-pyrazolyl- nicotinamides were conveniently synthesized with 2-chloro-3-cyanopyridine and 4-bromopyrazole or 3,5-dimethylpyrazole as starting materials, via an "acyl transposing" design strategy. Their structures were characterized by 1H NMR, 13C NMR and HRMS. The preliminary bioassay tests indicated that most of these compounds exhibited obvious insecticidal activity at the test concentration of 200 mg/L, among which N-(4-chloro-2-(ethylcarbamoyl)-6-methylphenyl)-2-(3,5-dimethyl-1H-pyra- zol-1-yl)nicotinamide (Il) possessed a 70% mortality rate against Mythimna separata Walker;some of the compounds displayed favorable fungicidal activities at 50 mg/L towards Physalospora piricola and Alternaria solani Sorauer, especially 2-(4-bromo-1H-pyrazol-1-yl)-N-(2-(cyclopropylcarbamoyl)-4-iodo-6-methylphenyl)nicotinamide (If) and 2-(4-bromo-1H- pyrazol-1-yl)-N-(4-chloro-2-(ethylcarbamoyl)-6-methylphenyl)nicotinamide (Ih) against Physalospora piricola, and 2-(4- bromo-1H-pyrazol-1-yl)-N-(4-chloro-2-(propylcarbamoyl)phenyl)nicotinamide (Id) against Alternaria solani Sorauer had growth inhibitory rates of 62.9%, 54.3% and 54.5%, respectively. These research results provide important reference for the further study of novel 2-pyrazolylnicotinamide derivatives.