导　　师： 杨光富

学科专业： I0403

授予学位： 博士

作　　者： ;

机构地区： 华中师范大学

摘　　要： strobilurins类杀菌剂是人们以天然产物为先导化合物设计合成的一类新型高效、广谱、安全性高的杀菌剂，现已成为当今世界杀菌剂市场最活跃、最有发展潜力的新一代杀菌剂。由于长期施用，该类杀菌剂也产生了抗性。因此针对抗性的产生，要求不断改造更新杀菌剂品种的骨架结构。 为了寻求高活性的结构骨架或先导结构，本文采用电子等排原理、活性亚结构拼接方法，对strobilurins类杀菌剂的侧链进行了结构改造和修饰，设计合成了四种结构类型十个系列共155个未见文献报道的化合物。并研究了所合成化合物的生物活性、构效关系及波谱性质，寻找到一批具有优良杀菌活性的新型化合物。具体研究内容如下： 1、系统总结了具有杀菌活性的strobilurins衍生物的分类、合成方法、作用机制及其抗性等方面的研究进展。 2、设计合成了四大类十个系列共155个新型strobilurins衍生物。所有合成化合物都采用1h nmr、ms、元素分析进行了结构表征，同时也获得了部分代表性化合物的晶体，进一步确证了化合物的结构。 3、按照《农药生物活性测定标准操作规范(sop)》，采用活体盆栽法，测试了所有化合物的除草、杀虫和杀菌活性(部分化合物的生物活性测试正在进行中)。发现了一批具有优良杀菌活性的化合物，其中化合物iv1k已成功申请国内专利和国际pct专利保护，其开发工作正在进行中。这将为我国开发具有自主知识产权的新型农药做出贡献。 杀菌活性方面：在200 mg．l-1浓度下，测定了所有化合物对黄瓜霜霉病、黄瓜自粉病、黄瓜灰霉病、水稻纹枯病的杀菌活性。发现了一批具有优良杀菌活性的化合物，其中化合物Ⅰ1a、Ⅰ1c、Ⅰ1m、Ⅰ1w、Ⅰ1x、Ⅰ3j、Ⅰ3l、Ⅳ1b、Ⅱ1a、Ⅱ1g、Ⅱ1i、Ⅱ1j、Ⅱ1k、Ⅱ1l、Ⅱ1p、Ⅱ1q、Ⅱ1r、Ⅱ3b、Ⅱ3c、Ⅱ The strobilurins are an outstanding new class of agricultural fungicides,and this class of fungicides is based on a group of natural lead derivatives of/(E/)-methylβ-methoxyacrylate,such as strobilurin A,oudemansin A and myxothiazol A.With their broad spectrum of activity,high activity at low rates of application and outstanding environmental tolerability,the strobilurins have been one of the most important classes of agricultural fungicides and might in the near future assume the number one position in the market.However,as we all know that the resistance appeared after the long term use of fungicides,new frame construction are needed to be found to keep or improve the biological activity. In order to search for novel strobilurin derivatives with high activities,according to the bioisosterism and the connecting principle of actively biological groups,nineteen series and seven kinds of two hundred and twenty-nine strobilurin derivatives were designed and synthesized in good to excellent yields.Their bioactivities,structure-activity relationship and spectral properties were studied,and many of them were found to show excellent fungicidal activities.This dissertation may be summarized as follows: The strobilurin derivatives are summarized in the paper,and the review describes in detail their main categorizationp,synthesis methods,biochemical mode of action and resistance risk. Two hundred and twenty-nine strobilurin derivatives were designed and synthesized by a multiple step synthetic procedures.Their structures were characterized by ~ⅠH NMR,MS spectroscopies, element quantitative analysis and X-Ray analysis.The results of bioactivity assay indicated that many compounds displayed excellent fungicidal activity against tested fungi at the concentration of 200 mg.L~/(-1/),such asⅠ1a,Ⅰ1c,Ⅰ1m,Ⅰ1w,Ⅰ1x,Ⅰ3j,Ⅰ3l,Ⅳ1b,Ⅱ1a,Ⅱ1g,Ⅱ1i,Ⅱ1j,Ⅱ1k,Ⅱ1l,Ⅱ1p,Ⅱ1q,Ⅱ1r,Ⅱ3b,Ⅱ3c,Ⅱ3d,Ⅲ1a,Ⅲ1d,Ⅲ2d,Ⅲ2f,Ⅲ3a,Ⅲ3b,Ⅲ3c,Ⅲ3d,Ⅲ3e,Ⅲ3h,Ⅲ3j,Ⅲ3k,Ⅳ1f,Ⅳ1g,Ⅳ1k,Ⅳ1l,Ⅳ2g th

关 键 词： 杀菌剂 苯并噻唑 生物活性 分子设计 分子合成

领　　域： [化学工程]