桃金娘烯醛基噻二唑-酰胺化合物的合成及性能

Synthesis and Properties of Myrtenal-Based Thiadiazole-amide Compounds

以α-蒎烯(Ⅰ)为原料,经选择性烯丙位甲基氧化反应制备了桃金娘烯醛(Ⅱ),Ⅱ再经缩合反应得到了桃金娘烯醛缩氨基硫脲(Ⅲ),进一步氧化环化得到了桃金娘烯醛基噻二唑(Ⅳ),然后与系列酰氯化合物进行N-酰化反应,以66%~81%的收率合成得到了11个桃金娘烯醛基噻二唑-酰胺化合物Ⅴa^k。采用FTIR、1HNMR、13CNMR和ESI-MS对目标化合物进行了结构表征,并测试了目标化合物的抑菌和除草活性。结果表明:在化合物Ⅴa^k的质量浓度为50 mg/L时,Ⅴa^k对测试的苹果轮纹病菌、黄瓜枯萎病菌、花生褐斑病菌、小麦赤霉病菌和番茄早疫病菌均显示不同程度的抑菌活性,其中桃金娘烯醛基噻二唑-乙酰胺(Ⅴa)、桃金娘烯醛基噻二唑-氯乙酰胺(Ⅴb)和桃金娘烯醛基噻二唑-正丙酰胺(Ⅴc)对苹果轮纹病菌的相对抑制率分别为93.0%、93.0%和98.2%,化合物Ⅴb对黄瓜枯萎病菌的相对抑制率为84.3%,表现出与阳性对照嘧菌酯(对苹果轮纹病菌和黄瓜枯萎病菌的相对抑制率分别为96.0%和87.5%)相当的抑菌活性。构效分析表明:脂肪族取代基衍生物表现出更好的抑菌活性。此外,在质量浓度为100 mg/L时,化合物Ⅴc对油菜胚根生长的相对抑制率为79.6%,显示出比阳性对照丙炔氟草胺(抑制率为63.0%)更好的除草活性。

Myrtenal （ Ⅱ ） was prepared by selective oxidation of allyl methyl using α-pinene （ Ⅰ ） as starting material. Then, myrtenal thiosemicarbazone （ Ⅲ ） was prepared by condensation reaction, followed by oxidative cyclization to afford myrtenal-based thiadiazole （Ⅳ）. Finally, eleven novel myrtenal-based thiadiazole-amide compounds V a - k were synthesized in 66% - 81% yields by N-acylation reaction of myrtenal-based thiadiazole with a series of acyl chlorides. All the target compounds were characterized by FTIR, 1HNMR, 13 CNMR, and ESI-MS. The antifungal and herbicidal activities were also evaluated in this study. The results showed that compounds V a - k displayed different antifungal activities against Physalospora piricola, Fusarium oxysporum f. sp. Cucumerinum, Cercospora arachidicola, Fusarium graminearum and Alternaria solani at 50 mg/L. Myrtenal-based thiadiazole-acetamide （ V a）, myrtenal-based thiadiazole-chloroacetamide （ V b）, and myrtenal-based thiadiazole-n-propionamide （ V c ） had inhibition rates of 93.0% , 93.0% and 98.2% against Physalospora piricola,respectively. Compound Vb had inhibition rate of 84. 3% against F. oxysporum f. sp. C , exhibiting fungicide azoxystrobin （positive and F. oxysporum f. sp. C comparable or even better antifungal activity than the commercial control, the inhibition rates of 96.0% and 87.5% against P. piricola , respectively）. The structure-activity relationship of synthesized compounds indicated that the aliphatic amide derivatives exhibited better antifungal activity than the others. In addition, at 100 mg/L, myrtenal-based thiadiazole-n-propionamide （V c） showed better growth inhibition activity against root of rape （ Brassica campestris） with the inhibition rate of 79.6% than the commercial herbicide flumioxazin with the inhibition rate of 63.0%.