To search for novel pesticides, the synthesis around commercialized insecticide tebufenpyrad accidentally led us to the discovery of the fungicidal lead compound, 3-ethyl-1-methyl-N-((2-phenylthiazol-4-yl)methyl)-1H-pyrazole-5-carboxamide (1a) and its pyrimidin-4-amine-based optimization derivative 5-chloro-2,6-dimethyl-N-(1-(2-(p-tolyl)thiazol-4-yl)ethyl)pyrimidin-4-amine (2a). Compound 2a not only demonstrates fungicidal activity superior to commercial fungicides such as diflumetorim but also exhibits the good features that come with pyrimidin-4-amines, such as unique modes of action and no cross-resistance to other pesticide classes. However, 2a is highly toxic to rats. Further optimization of 2a by introducing pyridin-2-yloxy substructure finally led to the discovery of 5b5-6 (HNPC-A9229) (5-chloro-N-(1-((3-chloropyridin-2-yl)oxy)propan-2-yl)-6-(difluoromethyl)pyrimidin-4-amine). HNPC-A9229 exhibits excellent fungicidal activities with EC50 values of 0.16 mg/L against Puccinia sorghi and 1.14 mg/L against Erysiphe graminis, respectively. Not only that its fungicidal potency is significantly superior to or comparable to commercial fungicides including diflumetorim, tebuconazole, flusilazole, and isopyrazam, HNPC-A9229 possesses low toxicity to rats.

作为γ-氨基丁酸门控氯离子通道别构调节剂,溴虫氟苯双酰胺(Broflanilide)是目前唯一获得登记的双酰胺类杀虫剂,它不仅具有广谱、高效等活性特点,且能有效防治抗性害虫.为获得结构多样性新型双酰酰胺类杀虫活性化合物,对溴虫氟苯双酰胺进行先导结构多样性衍生,设计合成了系列新型双酰胺类化合物,其结构经1H NMR和MS等表征确证.研究结果表明,该类化合物对粘虫等鳞翅目害虫和蚜虫等半翅目害虫均具有高活性,对害螨棉红蜘蛛也具有显著活性.

为研究嗪虫唑酰胺(Dimpropyridaz)的生物活性,以3-甲基-2-丁酮和3,4,5-三氯哒嗪为原料,经7步反应合成了嗪虫唑酰胺,其结构经质谱和核磁共振氢谱等表征确证.室内测定了嗪虫唑酰胺对蚕豆蚜虫(Aphis fabae)、稻褐飞虱(Nilaparvata lugens)、粘虫(Mythimna separate)和棉红蜘蛛(Tetranychius urticae)的生物活性,结果表明嗪虫唑酰胺对蚕豆蚜虫表现出高活性,其LC50值为0.039 mg/L,对褐飞虱表现出一定活性,对粘虫和棉红蜘蛛没有表现出明显活性.

A series of novel pyridazinone derivatives were designed and synthesized by replacing 4-(tert-butyl)phenyl moiety of pyridaben with 2-phenylthiazole or oxazole fragments via activity substructure connecting approach. The structures of all target compounds were characterized through NMR, MS, and elemental analysis. Bioassay results exhibit that most compounds showed potent bioactivities againstAphis fabae,Tetranychus urticae,Erysiphe graminis, and/orPuccinia polysora. Among the newly synthesized compounds, 2-(tert-butyl)-4-chloro-5-(((2-phenylthiazol-4-yl)methyl)thio)pyridazin-3(2H)-one (12b) displays remarkable insecticidal activity againstA fabae. Its LC(50)value (2.73 mg/L) is better than that of pyridaben (5.46 mg/L), although inferior to that of imidacloprid (0.51 mg/L). In addition to its extraordinary insecticidal activity, compound12balso exerts 96.9% fungicidal activities againstP polysoraat 500 mg/L in vivo, significantly superior to that of pyridaben (50.0%), while slightly lower than that of tebuconazole (100%). This article discusses the synthesis, bioassay results, and structure-activity relationship of this series of novel pyridazinone derivatives.

以2,3-二氯丁烯醛酸和4-叔丁基苄氯为原料,采用一锅法合成新型哒嗪酮类杀螨剂哒螨灵(Pyridaben),其结构经质谱和核磁等确证.生测结果表明,哒螨灵不仅具有较好的杀螨活性,而且也具有较好的杀蚜虫和粘虫活性.

[目的]对丙硫菌唑原药进行全分析,明确质量分数大于0.1％的有机杂质的结构及含量.[方法]采用液质联用仪和气质联用仪分别对丙硫菌唑进行定性分析,以高效液相色谱和气相色谱等分析手段对原药及杂质进行定量分析或最低被检测质量分数.[结果]丙硫菌唑原药杂质为甲苯、杂质307和杂质309,而相关杂质硫酮菌唑的最低被检测质量分数为0.002％.[结论]试验不仅提供了一种丙硫菌唑全组分分析,而且对该产品的合成优化具有重要参考价值.

通过室内、温室及田间试验,评价了新型杀菌剂HNPC-A3107的生物活性.室内杀菌活性试验结果表明HNPC-A3107在25 mg·L-1浓度下对所供试的8种靶标病害均具有抑制作用;温室盆栽试验表明HNPC-A3107对水稻稻瘟病、水稻纹枯病和小麦叶枯病等具有良好防治效果;田间试验进一步确证了HNPC-A3107对小麦叶枯病的良好防治效果.

A series of original pyrimidinamine derivatives containing a biphenyl ether moiety were designed and synthesized. Their structures were confirmed by H-1 NMR, MS, and elemental analyses. Their insecticidal activities against lepidopteran and hemiptera insects and acaricidal activities were tested. The results of bioassay demonstrated that 9k showed the best activity (LC50 = 2.08 mg/L) against Tetranychus urticae, which is comparable with the positive control, spirotetramat (LC50 = 2.27 mg/L), and 9g showed better activity (LC50 = 0.52 mg/L) against Aphis fabae than the positive control, imidacloprid (LC50 = 1.02 mg/L), and relatively good activity (LC50 = 2.49 mg/L) against T urticae. Their structure-activity relationships indicated that both an ethyl group on the 4-position of the pyrimidine ring and alkyl chain as a para-substituent group of the benzene ring showed good biological activity.

通过室内、温室及田间试验,评价了新型杀菌剂HNPC-A073的生物活性.室内杀菌活性试验结果表明HNPC-A073在10～25 μg·mL-1浓度下对供试的29种靶标病害中90％以上靶标均有抑制作用;温室及田间试验表明HNPC-A073对灰霉、菌核等多种病害具有良好防治效果.

采用高效液相色谱-质谱联用对不同啶氧茵酯原药中的有机杂质进行定性分析.制备了啶氧茵酯原药中的主要杂质标准品.本方法建立了啶氧菌酯原药中有机杂质定性的分析方法,为啶氧茵酯原药质量分析和控制提供了依据.

采用高效液相色谱-质谱联用和液相色谱法对草铵膦原药中的有机杂质进行定性和定量分析.建立了草铵膦有机杂质的定量分析方法:采用高效液相色谱法,使用ZORBAX-SAX色谱柱和紫外检测器,以13.6 9磷酸二氢钾溶于970 mL水中,加30 mL甲醇为流动相,在195 nm波长下测定杂质3-氨基-4-甲氧基4-羰基丁基(甲基)膦酸铵的含量.该分析方法的线性相关系数为0.999 98,标准偏差为0.009,变异系数为0.71％,平均回收率为99.42％,最低检出浓度为0.01％.建立了草铵膦原药中有机杂质的定性和定量的分析方法,可以为草铵膦原药质量分析和控制提供依据.

To study the insecticidal and acaricidal activities of HNPC-A202, the insecticidal activity of HNPCA202 against Mythimma separata was tested by a nebulization method, and the biological activity of HNPC-A202 against homoptera pests including Tetranychus urticae and Aphis fabae was tested by an impregnation method. The results of bioassays indicated that HNPC-A202 showed high activity against the Mythimma separata and prominent insecticidal activity against Aphis fabae at the value of LC50 0. 42 mg·L-1, which was superior to that of imidacloprid LC50 value. In summary, HNPC-A202 was valuable for further research.

To research the fungicidal activity of HNPC-A15269,the fungicidal activity of HNPC-A15269 against Blumeria graminis (DC.) was tested in greenhouse trials,and the field trail of HNPC-A15269 against Pyricularia oryzae was carried out.The greenhouse trial results indicate that HNPC-A15269 had excellent activity against Blumeria graminis (DC.),EC50 value was 1.48 mg/L,better than that of Tebufloquin EC50 value 5.22 mg/L and comparable to that of Tricyclazole (EC50 1.51 mg/L).Field trial results showed that HNPC-A15269 can control Pyricularia oryzae at the dosage of 125～175 g a.i./hm2,and it was safe to the tested crops.HNPC-A15269 may be further developed as a fungicide to control Pyricularia oryzae,Blumeria graminis (DC.),etc.

In order to study the acaricidalactivity of HNPC-A14073,the optimization compound of HNPC-A13351,the acaricidal activity against tetranychus cinnabarinus of HNPC-A14073 by immersion method was studied,and its acaricidal activity against Panonychuscitri McGregor was confirmed in the field trials.The results indicated that HNPC-A14073 exhibited high levels of acaricidal activity against tetranychus cinnabarinusat the value of LC50 0.056 mg/L.The field trials also showed that the efficacy of HNPC-A14073 against Panonychuscitri McGregor was a little better than that of cyflumetofen at the same dosage,and HNPC-A14073 was valuable for further research and development.

建立了茶叶和土壤中啶虫脒的气相色谱残留检测方法,啶虫脒最低检出量为0.02 ng,最低检出浓度为0.01 mg/kg.在0.01～1.0 mg/kg添加水平范围内,啶虫脒在茶叶中的平均添加回收率为78.9％～103.8％,相对标准偏差1.37％～3.92％;在土壤中的平均添加回收率为81.8％～91.4％,相对标准偏差2.58％～6.83％.采用田间实验方法研究了啶虫脒的降解动态规律,啶虫脒在湖南、浙江、四川3地的茶叶和土壤中的消解半衰期分别为3.36～8.77 d和1.23～16.5 d,属于极低残留农药.

A method for separation and identification of Azoxystrobin technical was developed.Rhe Azoxystrobin and 3 relative impurities in Azoxystrobin technical were separated and identified.The chemical structure of these impurities were confirmed.

A method for separation and quantitative analysis of Saijunmao by HPLC with methanol and water(1‰Orthophosphoric acid)as mobile phase,SHIMADZU VP-ODS column and DAD at 280nm wavelength was described.The result showed that the linear correlation coefficient was 1.000 0,the standard deviation was 0.27,the variation coefficient was 0.29%,the average recovery was 100.0%.