Design,Synthesis And Insecticidal Activity Studies Of Chlorantraniliprole Derivatives

Chlorantraniliprole is the most important diamide insecticide,accounting for the largest market share.It is a new chemical pesticide developed by DuPont and has a novel diamide chemical structure,targeting at insecticide ryanodine receptors(RyRs),without cross-resistance to other pesticides on the market.Moreover,it has a prominent effect on the Lepidoptera pests,while easy to degrade in the environment and non-toxic or less toxic to non-target insects and mammals.However,the emergence of resistance presents a new challenge for the application of chlorantraniliprole.In this paper,chlorantraniliprole and its active metabolite quinazolinone were used as lead compounds.Three series of chlorantraniliprole derivatives were synthesized by introducing a silicon atom fragment with the synergistic effect of pesticide,"mixed" halogen atoms,and pharmaceutically active molecule dihydroquinazolone.The three series of chlorantraniliprole derivatives were tested for Lepidoptera pests in Guangxi Pastoral Biochemical Co.Ltd.The derivative,Z-30 had prominent activity against the Mythimna separata,and the derivative,Z-18 had prominent activity against the chilo suppressalis and the activities exceeded that of the control drug chlorantraniliprole.My thesis consists of the following parts:Part I: We detailedly summarized the synthesis and research progress of natural products of ryanodine,ryanodine receptor,ryanodine receptor insecticides.Part II: Design,synthesis and bioactivity test of pyrazole 3-position silyl ether substituted chlorantraniliprole derivatives.Silicone molecules are widely used as potentiators of pesticides because of their unique properties.They have the advantages of improving the solubility and permeability of pesticides,slowing the metabolic rate of pesticide preparations in pests and improving the virulence and efficacy of pesticides.In this experiment,a series of derivatives were successfully synthesized by the introduction of the silicon atom into the chlorantraniliprole pyrazole C-3.Part Ⅲ: Design,synthesis and bioactivity activity studies of halogen-substituted chlorantraniliprole derivatives.Due to the high prevalence of chemical pesticides,the number of halogen-containing pesticides increased year by year.The research and development of halogen-containing pesticides have been increasing rapidly.In order to realize the high efficiency and environmental safety of modern pesticides,the introduction of halogens into the original product with excellent activity is commonly used by researchers.The chemical structure of many products on the market even appears "mixed" halogens.In this experiment,with chlorantraniliprole as the leading molecule,a series of compounds were synthesized by introducing "mixed" halogens on pyridine,pyrazole and benzene rings.All of synthesized compounds were evaluated for their biological activities mainly against Lepidoptera pests,including Chilo suppressalis,Pyrausta nubilalis,Mythimna separata,Spodoptera litura and some showed better biological activities than the chlorantraniliprole.Part IV: Synthesis of tetrahydroquinoline derivatives based on chlorantraniliprole metabolitesInspired by DuPont Crops Company’s research on the chlorantraniliprole metabolites,we used chlorantraniliprole quinazolinone as a lead compound and synthesized a series of compounds by introducing tetrahydroquinoline structures as a amine bridge for anthranilic benzamides.