氯虫酰胺衍生物的设计、合成与杀虫活性研究

发布时间：2018-06-03 18:32

本文选题：氯虫酰胺 + 硅原子　；参考：《兰州大学》2017年硕士论文

【摘要】：氯虫酰胺(Chlorantraniliprole)是杜邦公司开发的最重要的,占市场份额最大的一种双酰胺类杀虫剂,因其作用于独特的鱼尼丁受体,与市场上其他的杀虫剂无交互抗性,对鳞翅目害虫有突出的防效,对有益昆虫和哺乳动物无害而备受关注。近年来氯虫酰胺对害虫抗药性问题日益严重对其应用提出了新的挑战。本论文以氯虫酰胺及其喹唑啉酮活性代谢物为先导化合物,引入具有农药增效作用的硅原子片段,“混合”卤素原子,活性二氢喹唑啉酮结构片段合成三个系列的氯虫酰胺衍生物,并对这三个系列的衍生物做了鳞翅目害虫毒杀活性测试,其中衍生物Z-30对粘虫有较为突出的毒杀活性,衍生物Z-18对二化螟有较为突出的毒杀活性,活性均超过了氯虫酰胺。全文由四部分构成:1、对天然产物鱼尼丁碱、鱼尼丁受体、鱼尼丁受体杀虫剂的合成及研究进展进行了概述。2、吡唑3位硅醚取代氯虫酰胺衍生物的设计合成及生物活性测定。有机硅分子因其独特的性质被广泛用作农药的增效剂,具有提高农药的溶解性,渗透性,减慢农药制剂在害虫体内的代谢速度,提高农药的毒力和药效等作用。本实验以氯虫酰胺为先导分子,将硅原子引入氯虫酰胺吡唑C-3位合成了一系列衍生物。3、卤素取代的氯虫酰胺衍生物的合成及生物活性测定。化学农药盛行以来,含卤素农药的数量逐年增加,含卤素农药的研究和开发得到快速发展,为了实现现代农药的高效性,环境安全性等,将卤素引入原本就有优异活性的产品是研究者常用的优化手段,市场上许多产品的化学结构甚至出现“混合”卤素。本实验以氯虫酰胺为母体化合物分子,在吡啶,吡唑,苯环上引入“混合”卤素合成一系列化合物,并对目标化合物进行了生物活性测试,主要针对鳞翅目害虫,包括二化螟(Chilo suppressalis),玉米螟(Pyrausta nubilalis),粘虫(Mythimna separata),斜纹夜蛾(Spodoptera litura)。其中部分衍生物活性高于氯虫酰胺。4、基于氯虫酰胺代谢产物途径设计合成四氢喹啉衍生物。杜邦作物公司对氯虫酰胺代谢产物的研究给了我们灵感,据此,我们把氯虫酰胺喹唑啉酮作为先导结构,引入四氢喹啉结构作为邻氨基苯甲酰胺类化合物的胺桥部分设计合成了一系列化合物。
[Abstract]:Chlorantraniliproleis is one of the most important and most marketable bisamide insecticides developed by DuPont because it acts on unique fish nitine receptors and is not cross-resistant to other pesticides on the market. Lepidoptera pests have a prominent control effect, beneficial insects and mammals harmless and has attracted much attention. In recent years, the problem of chloramides resistance to insect pests is becoming more and more serious, which poses a new challenge to its application. In this paper, chloramides and their active metabolites of quinazolone were used as lead compounds, and silicon atoms with synergistic effect of pesticides were introduced to "mix" halogen atoms. Three series of chloramides derivatives were synthesized from the structure fragments of active dihydroquinazolinone, and the toxic activity of these three series derivatives were tested by Lepidoptera pests. Derivative Z-18 has outstanding toxic activity against Chilo suppressalis, and its activity is higher than that of chloramides. This paper is composed of four parts: 1. The synthesis and research progress of the natural products of fish nidine and fish nipple receptor insecticides are summarized. The design, synthesis and bioactivity determination of the 3-position silicoether substituted chloramides derivatives with pyrazole are reviewed in this paper. Silicone molecules are widely used as synergists for pesticides because of their unique properties. They can improve the solubility and permeability of pesticides, slow down the metabolism of pesticide formulations in insect pests, and improve the virulence and efficacy of pesticides. In this experiment, a series of derivatives .3were synthesized by introducing silicon atom into the C-3 position of chloramide-pyrazole. Halogen-substituted chloramides derivatives were synthesized and their biological activities were determined. Since the prevalence of chemical pesticides, the number of halogen containing pesticides has increased year by year, and the research and development of halogen pesticides have been developed rapidly. In order to achieve the high efficiency and environmental safety of modern pesticides, The introduction of halogen into products with excellent activity is a common optimization method for researchers, and many products even have "mixed" halogens in the market. A series of compounds were synthesized by introducing "mixed" halogens on pyridine, pyrazole and benzene rings with chloramides as parent compounds. The biological activity of the target compounds was tested, mainly for Lepidoptera pests. These include Chilo suppressalis, Pyrausta nubilis, Mythimna separa, Spodoptera litura. Some of the derivatives were more active than chloramides. 4. The tetrahydroquinoline derivatives were designed and synthesized based on the chloramide-metabolite pathway. We were inspired by DuPont crop's research on chloramide-metabolites, and we used chloramide-quinazolinone as the lead structure. A series of compounds were synthesized by introducing tetrahydroquinoline structure as the amine bridge part of o-aminobenzoamide compounds.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：R914;R96

【参考文献】