Design, synthesis, insecticidal activity and structure-activity relationship of 3,3-dichloro-2-propenyloxy-containing phthalic acid diamide structures

BACKGROUND: Phthalic acid diamide derivatives are among the most important classes of synthetic insecticides. In this study, a 3,3‐dichloro‐2‐propenyloxy group, the essential active group of pyridalyl derivatives, was incorporated into phthalic acid diamide derivatives with the aim of combining the active groups to generate more potent insecticides. RESULTS: Thirty‐one new phthalic acid diamides were obtained, and these were characterised by ¹H and ¹³C NMR. The structure of N²‐[1,1‐dimethyl‐2‐(methoxy)ethyl]‐3‐iodo‐N¹‐[4‐(3,3‐dichloro‐2‐propenyloxy)‐3‐(trifluoromethyl)phenyl]‐1,2‐benzenedicarboxamide was determined by X‐ray diffraction crystallography. The insecticidal activities of the compounds against Plutella xylostella were evaluated. The title compounds exhibited excellent larvicidal activities against P. xylostella. Structure‐activity relationships revealed that varying the combination of aliphatic amide and aromatic amide moieties, or the nature and position of substituent Y on the aniline ring, could aid the design of structures with superior performance. CONCLUSION: A series of novel phthalic acid diamides containing a 3,3‐dichloro‐2‐propenyloxy group at the 4‐position of the aniline ring were designed and synthesised. Structure‐activity relationships with the parent structure provided information that could direct further investigation on structure modification. Copyright © 2012 Society of Chemical Industry     

二化螟对双酰胺类杀虫剂的抗药性监测和交互抗性研究

【目的】为了及时了解我国主要稻区二化螟对氯虫苯甲酰胺和氟苯虫酰胺的抗药性发展情况,同时明确对氯虫苯甲酰胺原药和制剂的抗性水平是否存在差异及二化螟对新研发的双酰胺类杀虫剂溴氰虫酰胺、四氯虫酰胺及氯氟氰虫酰胺与氯虫苯甲酰胺、氟苯虫酰胺间是否存在交互抗性。【方法】采用稻苗浸渍法测定了2015年我国7省19地二化螟田间种群对氯虫苯甲酰胺和氟苯虫酰胺的抗药性,同时测定了浙江余姚和象山两个抗性种群对97.3%氯虫苯甲酰胺原药、20%氯虫苯甲酰胺悬浮剂制剂的抗药性及其对溴氰虫酰胺、四氯虫酰胺及氯氟氰虫酰胺与氯虫苯甲酰胺和氟苯虫酰胺间的交互抗性。【结果】浙江余姚和苍南种群对氯虫苯甲酰胺已达141.1倍和135.0倍的高水平抗性,象山种群为87.9倍的中等水平抗性;这三个种群对氟苯虫酰胺均表现为中等水平抗性(15.0~58.7倍)。二化螟对97.3%氯虫苯甲酰胺原药和20%氯虫苯甲酰胺悬浮剂制剂存在抗性差异,浙江余姚和象山种群对制剂的抗性更高。交互抗性研究结果显示,对氟苯虫酰胺和氯虫苯甲酰胺均产生了中到高水平抗性(27.6~133.6倍)的象山、余姚种群,对溴氰虫酰胺、四氯虫酰胺和氯氟氰虫酰胺同样也产生了中到高水平抗性(30.3~127.0倍)。【结论】各二化螟地理种群之间对氯虫苯甲酰胺和氟苯虫酰胺抗药性差异较大,分别表现出117.6倍和146.8倍的差异,浙江余姚和象山二化螟种群对20%氯虫苯甲酰胺悬浮剂制剂抗药性更高且三种新双酰胺类杀虫剂与氯虫苯甲酰胺和氟苯虫酰胺之间存在交互抗性。     

The story of a new insecticidal chemistry class: the diamides

This paper describes the story of the invention of the diamides, a novel chemical class of insecticides. It starts with the pioneering work by Nihon Nohyaku researchers, who developed a herbicide lead with weak insecticidal activity to flubendiamide, a highly potent lepidoptericide. The journey continues with Nissan's isoxazolines and the invention of the anthranilamides by DuPont, culminating in the discovery of the blockbuster chlorantraniliprole and its analogue cyantraniliprole. The next steps are Syngenta's sulfoximines and bicyclic anthranilamides, Ishihara Sangyo Kaisha's cyclopropylamides, Sumitomo's hydrazides, Bayer's pyrazoles and tetrazoles, BASF's sulfoximines and more recent contributions from Chinese agrochemical companies and academic institutions. The diamides affect calcium homeostasis by binding to ryanodine receptors and releasing calcium from the intracellular stores. Investigations at Nihon Nohyaku, DuPont and Bayer on the action of the diamides on ryanodine receptors will be briefly reported.     

含嘧啶氧基和一氟甲氧基的吡唑邻甲酰氨基苯甲酰胺的合成及杀虫活性

以取代邻氨基苯甲酸和取代吡啶基吡唑羧酸为原料,合成了10个结构新颖的含嘧啶基和一氟甲氧基的吡唑邻甲酰氨基苯甲酰胺类化合物,其结构通过1H NMR和MS表征。盆栽法试验表明,在500 mg/L 质量浓度下,部分化合物对小菜蛾 Plutella xylostella 和苜蓿蚜 Aphis medicaginis的相对防效达100%。