含稠杂环结构的螺环丁烯内酯类化合物的合成及杀菌活性  

Synthesis and fungicidal activities of spirocyclic butenolide derivatives containing fused heterocyclic moiety

作　　者：李益豪 许磊川 张倩[1] 马好运 安鑫鲲 王明安[1] LI Yihao;XU Leichuan;ZHANG Qian;MA Haoyun;AN Xinkun;WANG Mingan(Innovation Center of Pesticide Research,Department of Applied Chemistry,China Agricutural Universiy,Beijing 100193,China)

机构地区：[1]中国农业大学应用化学系农药创新研究中心,北京100193

出　　处：《农药学学报》2022年第5期1152-1161,共10页Chinese Journal of Pesticide Science

基　　金：国家自然科学基金(21772229).

摘　　要：为了发现更高杀菌活性的螺环丁烯内酯类化合物并分析该类化合物的构效关系,设计并合成了一系列未见文献报道的含咪唑并噻唑、咪唑并噻嗪和咪唑并噻嗪酮等稠杂环结构的螺环丁烯内酯类化合物,其结构通过核磁共振氢谱(^(1)H NMR)、碳谱(^(13)C NMR)及高分辨质谱(HRMS)确证。离体杀菌活性测试结果表明,化合物5f和6f对油菜菌核病菌的EC_(50)值分别为33.2和29.8 mg/L,优于对照药剂咪唑菌酮(46.8 mg/L),化合物7b和7e对辣椒疫霉的EC_(50)值分别为45.8和43.5 mg/L,优于咪唑菌酮(50.7 mg/L),与先导化合物相比,其杀菌活性高于2-甲硫基衍生物,低于2-芳氨基衍生物,表明稠杂环的引入可以提高化合物的杀菌活性,而结构中的NH片段对杀菌活性具有关键作用。In order to find compounds with higher fungicidal activity and analyze the structure-activity relationship of spirocyclic butenolide compounds,a series of novel spirocyclic butenolide derivatives containing fused heterocyclic moiety such as imidazo[2,1-b]thiazol-5(6H)-one,imidazo[2,1-b][1,3]thiazin-3(2H)-one and imidazo[2,1-b][1,3]thiazine-3,6(2H,7H)-dione were designed and synthesized using spirocyclic butenolide as the orientation structure.Their structures were characterized by ^(1)H NMR,^(13)C NMR and HRMS spectral data.The in vitro fungicidal activity evaluation results showed that the EC_(50) values of compounds 5f and 6f against Sclerotinia sclerotiorum were 33.2 and 29.8 mg/L,respectively,which were better than that of the commercial fungicide fenamidone(46.8 mg/L).While the EC_(50) values of compounds 7b and 7e against Phytophthora capsici were 45.8 and 43.5 mg/L,which were also better than that of fenamidone(50.7 mg/L).Comparison with lead compounds,their fungicidal activities were higher than that of 2-methylthio analogues and lower than that of 2-arylamino analogues,which indicated that introduction of the fused heterocyclic moiety can improve the fungicidal activities,and the NH group in the structure play a key role in the fungicidal activity.

关 键 词：多样性导向合成 螺环丁烯内酯 稠杂环 合成 杀菌活性 

分 类 号：O626[理学—有机化学] TQ450.11[理学—化学]