摘要
以前期合成的6/7/8-羟基-3-香豆素甲酸乙酯为原料,使其与卤代烃发生Williamson反应制得化合物1~6;以2,4-二羟基苯甲醛为原料,使其与季鏻盐发生Wittig反应得到中间体化合物7;以取代间苯二酚为原料,使其与乙酰乙酸乙酯发生Pechmann缩合得到化合物8~10;在TBAB催化下,化合物7~10与相应的卤代烃发生Williamson反应制得化合物11~17;通过1H NMR、13C NMR和ESI-MS等波谱技术确定了所有目标化合物的结构。在50μg·mL-1时,以醚菌酯或多菌灵为阳性对照,测定了所有化合物对12种常见植物病原真菌的抑制作用,发现它们均具有不同程度的抗菌活性。其中,4、5、7和13对苹果腐烂菌、苹果炭疽菌、白菜黑斑、水稻稻瘟、烟草赤星、苹果轮纹等6种植物病原菌的抑制活性高于阳性对照醚菌酯或多菌灵。由此可见,化合物4、5、7和13具有开发成新型农用抗菌剂的潜力,这为后续香豆素类抗菌剂的研发奠定了理论基础。
Compounds 1~6 were synthesized by Williamson reaction of 6/7/8-hydroxylcoumarin-3-formates with the corresponding alkyl halides.Intermediate 7 was prepared through Witting reaction using 2,4-dihydroxybenzaldehyde as starting material,and intermediates 8~10 were synthesized via Pechmann condensation reaction of substituted resorcinol with ethyl 3-oxobutanoate.Seven compounds,11~17,were afforded by Williamson reaction of intermediates 7~10 with corresponding alkyl halides.The structures of these compounds were identified by 1H NMR,13C NMR and ESI-MS spectrum.At the concentration of 50μg·mL-1,using kresoxim-methyl or carbendazol as positive control,the antifungal activity of these compounds against 12 types of phytopathogens was then tested by the linear growth rate method.All the compounds displayed the antifungal activity in varying degrees.The antifungal activities of compounds 4,5,7,and 13 against Valsa mali,Colletotrichum gloeosporioides,Alternaria brassicae,Pyricularia oryza,Alternaria alternate and Botryosphaeria dothidea were higher than those of the positive control pesticides.Therefore,the compounds 4,5,7,and 13 had great potentials for further research and development,which provided theoretical basis for further research on coumarin antifungal agents.
作者
张丽霞
史晨燕
刘睿媛
耿会玲
ZHANG Li-xia;SHI Chen-yan;LIU Rui-yuan;GENG Hui-ling(College of Chemistry and Pharmacy,Northwest A&F University,Yangling 712100,China)
出处
《化学研究与应用》
CAS
CSCD
北大核心
2020年第7期1214-1226,共13页
Chemical Research and Application
基金
国家自然科学基金项目(31572038)资助
陕西农业攻关项目(2016NY-130)资助
陕西博士后科学基金项目(2014-03)资助。
关键词
香豆素类化合物
化学合成
抗菌活性
构效关系
coumarin′s compounds
chemical synthesis
antifungal activity
structure-activity relationship
