3-香豆素甲酸衍生物的合成与抗真菌活性

Synthesis and Antifungal Activity of the Derivatives of Coumarin-3-formic Acid

[目的]寻找有较高抗菌活性的3-香豆素甲酸衍生物。[方法]在哌啶催化下,取代水杨醛与丙二酸二乙酯发生Knoevenagel反应,生成3-香豆素甲酸乙酯类化合物,经碱性水解后得到目标化合物。采用~1H NMR、^(13)C NMR和ESI-MS对其结构进行表征。[结果]18个目标化合物在50 mg/L时对12种植物病原真菌均有不同程度的抑制活性,其中B3、B4、B6、B7、B16、B18对苹果腐烂、玉米弯孢、苹果轮纹、马铃薯干腐病菌抑制活性较高;B16对苹果腐烂、苹果轮纹病原菌的活性最高,EC_(50)值分别为8.7、19.4 mg/L。[结论]为香豆素类抗菌剂的研发提供了理论依据和技术支撑,B3、B6、B16和B18有进一步研究与开发价值。

[Aims] The aims were to explore several derivatives of coumarin-3-formic acid with ideal antifungal activity. [Methods] Ethyl coumarin-3-formates were prepared through piperidine-catalyzed Knoevenagel reaction of substituted salicylaldehyde with diethyl malonate. The derivatives of coumarin-3-formic acid were obtained by the hydrolysis of those esters with sodium hydroxide solution. The structural characterization of all the compounds was conducted by IH NMR, 1,3C NMR and ESI-MS. [Results] Most of the compounds displayed the antifungal activity in varying degrees at 50 mg/L. Compounds B3, B4, B6, B7, B16 and BI8 exhibited higher activity against Valsa mali, Curvularia lunata, Botryosphaeria dothidea, and Fusarium solani. Compound B16 showed the highest activity for V. ma/i and B. dothidea and the EC50 values were 8.7 and 19.4 mg/L, respectively. [Conclusions] Theoretical basis and technical support for the development of the antimicrobial agent containing coumarin backbone was provided. Compounds B3, B6, B16 and B18 have great potentials for further research and development.