新型氟虫酰胺、氯虫酰胺类似杀虫剂设计合成及生物活性的研究.pdf

摘要摘要近些年来,以鱼尼丁受体为作用靶标的杀虫剂的研发是杀虫剂发展史上又一重要突破。分别由日本农药公司和美国Dupont公司最先开发的邻苯二甲酰胺类和邻甲酰氨基苯甲酰胺类化合物,是最早发现的作用于鱼尼丁受体靶标的合成杀虫剂。这两类新型杀虫剂的作用机制独特,通过激活昆虫鱼尼丁受体,使钙离子从内源性钙离子库持续释放,最终导致昆虫死亡。因为这两类杀虫剂高效、低毒、结构与靶标新颖,对目标生物选择性高,与传统农药交互抗性低, 对人畜安全,因而成为现代杀虫剂研究的热点领域。本论文以在已有商品化杀虫剂氟虫酰胺(邻苯二甲酰胺类)和氯虫酰胺(邻甲酰氨基苯甲酰胺类)基本结构为基础,参考大量专利文献,利用活性片段拼接, 相似合成,生物等排等分子设计手段,设计合成了三个系列,共44个未见报道的新化合物。新化合物经核磁,元素分析或者是高分辨分析确认。在这三个系列中,有以氟虫酰胺为基本骨架,在邻苯二甲酸部分中的碘代基团置换为酰胺基团,形成类似于三酰胺结构的化合物;在苯胺部分,将七氟异丙基团置换为酰化的含氮杂环结构,并变化其位置;以氯虫酰胺为基本骨架,结合氟虫酰胺合成中重要中间体的邻苯二甲酰亚胺结构,并将其引入置换氯虫酰胺的苯甲酰胺结构。对合成的新化合物通过己建立的生测平台,进行了对东方粘虫的杀虫活性研究。结果表明:具有三酰胺结构的系列化合物中部分化合物具有良好的杀虫活性。可以对该类型的化合物做进一度的研究工作。关键词:鱼尼丁受体,邻苯二甲酰胺类,氟虫酰胺,氯虫酰胺,杀虫活性 Abstract Abstract Recently,firstly discovered by Nihon Nohyaku and Dupont respectively, phthalic aciddiamides and anthranilicdiamides which target theinsectryanodine receptor(RyR)were thelatestbreakthrough inthe R&D two classeschemicals showed special action on insects,which cause releasing ofthe endogenous calcium storeinuncontrolled manner andlead totwo classes ofsynthetic chemicals had novel mode ofaction,unique chemical structures, high larvicidal potency and low toxicity to non— novel structures have attractedmuch attentioninmodem insecticidalresearch. After reviewing thereported literaturesand patents related,based on the structures offlubendiamide(phthalic aciddiamides)and chloranthraniliprole (anthranilicdiamides),three seriesofnovel analogues ofryanodine receptor insecticidesincluding 42unreported pounds were designed andsynthesized through the approach of sub·structurelinkprinciple,analogue synthesis and pounds were characterized byNMR,elemental analysis or thethree pounds,referring to the structure of flubendiamide,various acylated amino were firstly introduced toreplace theiodine atom ofthephthalic acidmoiety;three kindsofacylatednitrogenheterocyclics were firstly introduced andtheposition toreplace theheptafluoroisopropyl group was tothestructu