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脱氢松香基1,2,4-三唑-3-硫酮衍生物的合成及抑菌活性探究
Synthesis and Antifungal Activities of Dehydroabietyl 1,2,4-Triazole-3-thione Derivatives
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摘要: 为拓展松香资源的高值化利用并筛选具有植物病原菌体外抑制活性的先导化合物,以脱氢松香胺为原料,经与二硫化碳和N,N-二环己基碳二亚胺反应制得脱氢松香基异硫氰酸酯2,再与16种取代酰肼反应得到脱氢松香基酰基硫脲3a~3p,随后在质量分数为5%的NaOH水溶液中环化,合成16种脱氢松香基1,2,4-三唑-3-硫酮衍生物4a~4p,分离产率为50.9%~65.0%。采用FTIR、1H NMR、13C NMR和HRMS进行综合表征,菌丝生长速率法测定目标化合物在200 μg/mL质量浓度下对苹果腐烂病菌、辣椒疫霉菌和尖孢镰刀菌西瓜专化型的体外抑制活性。结果表明:不同目标化合物对3种供试植物病原菌的抑制作用存在明显差异。4f和4e对苹果腐烂病菌的抑制率分别为57.69%和56.92%;4a和4d对辣椒疫霉菌的抑制率均为23.89%;4a对尖孢镰刀菌西瓜专化型的抑制率为28.57%。仅部分化合物对苹果腐烂病菌表现出中等水平的抑制活性,而该系列化合物对辣椒疫霉菌和尖孢镰刀菌西瓜专化型的整体活性较弱。Abstract: To expand the high-value utilization of rosin resources and identify lead compounds with in vitro inhibitory activity against phytopathogens, a series of dehydroabietyl 1,2,4-triazole-3-thione derivatives were synthesized and evaluated. Dehydroabietyl isothiocyanate was first prepared from dehydroabietylamine via reaction with carbon disulfide and N,N-dicyclohexylcarbodiimide, and was subsequently reacted with 16 substituted hydrazides to afford the corresponding dehydroabietyl acylthiosemicarbazides 3a-3p. Cyclization of these intermediates in 5% NaOH aqueous solution yielded 16 dehydroabietyl 1,2,4-triazole-3-thione derivatives 4a-4p in isolated yields of 50.9%-65.0%. The combined FTIR, 1H NMR, 13C NMR, and HRMS data supported the proposed structures of the target compounds. Their in vitro inhibitory activities against Valsa mali, Phytophthora capsici, and Fusarium oxysporum f. sp. niveum were evaluated at 200 μg/mL using the mycelial growth rate method. The compounds exhibited markedly different inhibitory activities against the three tested phytopathogens. Compounds 4f and 4e showed inhibition rates of 57.69% and 56.92%, respectively, against V. mali, whereas 4a and 4d each inhibited P. capsici by 23.89%. Compound 4a showed an inhibition rate of 28.57% against F. oxysporum f. sp. niveum. Overall, only selected compounds exhibited moderate inhibitory activity against V. mali, while the series showed generally weak activity against P. capsici and F. oxysporum f. sp. niveum.
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