莰烯醛肟及其烃基醚衍生物的合成与抑菌活性研究

由莰烯醛(1)与羟胺盐酸盐反应合成了莰烯醛肟(2),继而与卤代烃反应合成了5种莰烯醛肟烃基醚衍生物,分别为:莰烯醛肟乙基醚(3a)、莰烯醛肟正丙基醚(3b)、莰烯醛肟正丁基醚(3c)、莰烯醛肟正戊基醚(3d)和莰烯醛肟苄基醚(3e)。通过红外光谱、质谱和核磁共振等仪器分析手段对产物结构进行了确认。在此基础上,采用菌丝生长速率法,评价了莰烯醛肟及其烃基醚衍生物对12种植物病原真菌的生长抑制作用,结果表明:产物对12种植物病原真菌皆有一定抑制作用,其中莰烯醛肟的抑菌活性最优,并且对油茶炭疽病的抑制效果最好,EC 50为39.25 mg/L,对水稻纹枯病菌、猕猴桃果实拟茎点霉、玉米赤霉病菌和毛竹枯梢病病原菌的EC 50为40~50 mg/L;在质量浓度为500 mg/L时,莰烯醛肟对水稻纹枯病菌等9种植物病原真菌完全抑制,对松枯梢病菌和七叶树壳孢菌的抑制率达97%以上,当药液浓度降低时,莰烯醛肟对大部分病原菌的抑制率仍然超过百菌清500 mg/L时的抑制率。虽然莰烯醛肟烃基醚衍生物的抑菌活性较莰烯醛肟有所降低,但对毛竹枯梢病菌、梨链格孢菌和玉米赤霉病菌的抑制率皆高于(或等于)百菌清。

Synthesis and Antibacterial Activity of ω-formylcamphene Oxime and Its Hydrocarbyl Ethers Derivatives

ω-Formylcamphene oxime(2)was synthesized by the reaction of formylcamphene(1)with hydroxylamine hydrochloride.and then reacted with halohydrocarbon to synthesize five ω-formylcamphene oxime alkyl ether derivatives,such as ω-formylcamphene oxime ethyl ether(3a),ω-formylcamphene oxime propyl ether(3b),ω-formylcamphene oxime butyl ether(3c),ω-formylcamphene oxime n-pentyl ethers(3d),ω-formylcamphene oxime benzyl ethe(3e).Their structures were characterized by FI-IR,MS and NMR.The mycelium growth rate method was used to test the inhibitory effects ofω-formylcamphene oxime and its hydrocarbyl ethers on 12 kindsof plant pathogenic fungi.The results showed that the products had certain inhibitory effects on 12 kinds of plant pathogenic fungi,among which ω-formylcamphene oxime had the best activity and the best inhibitory against Colletotrichum gloeosporioides,EC50 was 39.25 mg/L.The EC50 values of Thanatephoruscu cumeris,Phomopsis sp.,Fusarium avenaceum and Ceratosphaeria phyllostachydis sp.nov.were 4050 mg/L.Under the concentration of 500 mg/L,ω-formylcamphene oxime completely inhibited 9 plant pathogenic fungi such as Thanatephorus cucumeris,and the inhibitory rates of ω-formylcamphene oxime against Sphaeropsi ssapinea and Fusicoccum aesuli were over 97%.When the medicament concentration of ω-formylcamphene oxime lowered,the inhibitory rates on most plant pathogenic fungi were still higher than that of chlorothalonil at 500 mg/L.Although the antibacteria activity of ω-formylcamphene oxime hydrocarbyl ethers was lower than that of ω-formylcamphene oxime,but the inhibitory rates of ω-formylcamphene oxime hydrocarbyl ethers against Ceratosphaeria phyllostachydis,Alternaria kikuchiana and Fusarium avenaceum were generally higher than that of chlorothalonil.