含氟酰胺类农用杀菌剂的合成研究-应用化学专业论文.docxVIP

摘 要 20 世纪 80 年代以来，农药的研发进入一个新的时期，农药开始朝着高效、 低毒、环境友好的方向发展。杀菌剂作为现代农药的重要组成部分，在植物保护、 农作物增产等方面发挥着不可替代的作用。噻唑酰胺类化合物有着噻唑基和酰胺 基两种高活性的结构，往往具有高效、广谱的生物活性，在医药和农药领域有着 广泛的应用。其中尤以孟山都公司研制的 thifluzamide（噻氟菌胺）、组合化 学和 Ihara 化学工业公司联合开发的 tiadinil（苯噻菌胺）为代表。此外，通 过在噻唑环上或酰胺键后引入含氟取代基，使其药效得到进一步增强并表现出优 异高效低毒等特性，引起了人们广泛的关注和积极的研究。 本文以三氟乙酸乙酯和对三氟甲氧基苯胺为起始原料合成了农药噻氟菌胺。 三氟乙酰乙酸乙酯经氯化、环合、水解、酸化、酰化生成 2-甲基-4-三氟甲基噻 唑甲酸，再与 2,6-二溴-4-三氟甲氧基苯胺反应生成噻氟菌胺，总收率 36.55%， 最终产物纯度 98.6%。 为了寻找新型高效的噻唑酰胺类杀菌剂，本文结合噻氟菌胺的结构特点，根 据亚结构拼接原理，以 2-甲基-4-三氟甲基-5-噻唑甲酸为原料，与吡啶胺类、芳 胺类化合物连接得到了 7 个未经文献报道的噻唑酰胺类化合物，所有化合物结构 经过 1H NMR、HRMS、IR 和元素分析表征。对所合成化合物进行了室内抑菌活 性测试，初步生测结果表明，在 50μg/mL 浓度下，目标化合物对水稻纹枯病菌 等 8 种植物病菌均有一定的抑制效果，其中所有化合物对水稻纹枯病菌均表现出 较好抑制效果，3a 的抑制率达到 91.78%，3c 达到 87.67%，3d 达到 89.04%，3f 达到 86.30%。 关键词： 噻唑酰胺 合成 抑菌活性 ABSTRACT Since the 1980s, pesticide research and development have reached a full new stage, and the efficient, low toxicity, environment friendly pesticides have become the new trend. As an important part of modern pesticides, fungicides are playing an irreplaceable role in plant protection and crop production. Thiazole-amide derivatives are widely used in the field of medicine and pesticides, and often show high efficiency and broad-spectrum biological activity for its thiazole and amide structure. The pesticide thifluzamide launched by Monsanto, tiadinil launched by Combinatorial chemistry and Ihara chemical industry are the commercialized representatives. In addition, excellent efficacy was found with thiazole-amide derivatives after introducing the fluorine contained group into the molecules, which attracts widespread concern. 2-Methyl-4-trifluoromethyl-5-chlorocarbonyl thiazole was prepared from trifluoro-acetyl ethyl acetate by chlorination, cyclization, hydrolysis, acidification and acylation four steps. Thifluzamide was synthesized by reacting 2,6-dibromo-4-trifluoromethoxy aniline with 2-methyl-4-trifluoromethyl-5-chlorocarbonyl thiazole. The total yield is 36.55% and the purity was found as 98.6 %. In order to create new and