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林业科学 ›› 2017, Vol. 53 ›› Issue (12): 93-101.doi: 10.11707/j.1001-7488.20171210

• 论文与研究报告 • 上一篇    下一篇

桃金娘烯醛基噻唑-腙类化合物的合成及抑菌活性

陈智聪1, 段文贵1, 林桂汕1, 张瑞1, 罗梦香1, 杨章旗2   

  1. 1. 广西大学 南宁 530004;
    2. 广西林业科学研究院 南宁 530002
  • 收稿日期:2016-09-05 修回日期:2016-11-03 出版日期:2017-12-25 发布日期:2018-01-13
  • 基金资助:
    国家自然科学基金项目"新型桃金娘烯醛基生物活性化合物的合成及构效关系研究"(31460173);八桂学者专项"松树资源培育及产业化关键技术创新"。

Synthesis and Antifungal Activity of Novel Myrtenal-Based Thiazole-hydrazone Compounds

Chen Zhicong1, Duan Wengui1, Lin Guishan1, Zhang Rui1, Luo Mengxiang1, Yang Zhangqi2   

  1. 1. Guangxi University Nanning 530004;
    2. Guangxi Academy of Forestry Nanning 530002
  • Received:2016-09-05 Revised:2016-11-03 Online:2017-12-25 Published:2018-01-13

摘要: [目的]桃金娘烯醛可由可再生的α-蒎烯选择性氧化而得到,且本身具有多种生物活性。另外,含噻唑或腙亚结构化合物具有广泛的生物活性,常用于构建生物活性分子的砌块。本研究将噻唑和腙2类活性基团引入到桃金娘烯醛骨架中,合成得到系列新型桃金娘烯醛基噻唑-腙类生物活性化合物,为我国的天然优势林产资源α-蒎烯的改性和高值化利用提供新的途径。[方法]α-蒎烯经选择性烯丙位氧化得到桃金娘烯醛,然后与氨基硫脲缩合制备桃金娘烯醛缩氨基硫脲,再与一系列取代的α-溴代苯乙酮反应,合成得到16个桃金娘烯醛基噻唑-腙类化合物。通过FT-IR、1H-NMR、13C-NMR和ESI-MS等技术手段确认目标化合物的结构,并用琼脂稀释法测定对所合成的目标产物的抑菌活性。[结果]合成得到16个新型桃金娘烯醛基噻唑-腙类目标化合物4a-4p。测试4a-4p抑菌活性,在50 mg·L-1质量浓度下,目标化合物对水稻纹枯病菌、黄瓜枯萎病菌、花生褐斑病菌、玉米小斑病菌、苹果轮纹病菌、西瓜炭疽病菌、番茄早疫病菌和小麦赤霉病菌均具有一定的抑制活性。总体上,目标化合物对苹果轮纹病菌的抑制效果最好,有12个化合物的抑菌率大于60%,尤其是化合物4n(R=4-NO2),其抑菌率高达90.6%(活性级别为A级)。[结论]合成得到系列新型桃金娘烯醛基噻唑-腙类化合物。这些化合物均具有一定的抑菌活性,其中化合物4n(R=4-NO2)是值得进一步研究的先导化合物。

关键词: α-蒎烯, 桃金娘烯醛, 噻唑-腙, 合成, 抑菌活性

Abstract: [Objective] Myrtenal can be derived by selective oxidation of α-pinene, which is renewable and abundant in China.Myrtenal has been found to exhibit various biological activities. The compounds containing thiazole orhydrazone moieties have been found to show a wide range of biological activities, and have been widely used as blocks for designing bioactive molecules. Therefore,a series of novel myrtenal-based thiazole-hydrazone bioactive compounds can be synthesized by incorporating both thiazole and hydrazone active blocks into the myrtenal skeleton with an attempt to provide a new pathway for the modification and high-value utilization of α-pinene which is a natural and preponderant forest resource in China.[Method] Myrtenal was prepared by the selectively allylic oxidation of α-pinene. Then, myrtenal-based thiosemicarbazone was prepared by the condensation reaction of myrtenal with thiosemicarbazide, followed by the reaction of myrtenal-based thiosemicarbazone with a series of substituted α-bromoacetophenones to yield sixteen myrtenal-based thiazole-hydrazone compounds 4a-4p which have not been reported in the literature. The molecular structures of the target compounds were confirmed by FT-IR,1H-NMR,13C-NMR, and ESI-MS, and antifungal activity of the target products was evaluated by agar dilution method.[Result] Sixteen novel myrtenal-based thiazole-hydrazone target compounds were synthesized.At 50 mg·L-1, the antifungal activity test showed that all the target compounds exhibited to certain degree antifungal activity against Rhizoctonia solani,Fusarium oxysporum f. sp. cucumerinum,Cercospora arachidicola,Helminthosporium maydis, Physalospora piricola,Colleetotrichum lagenarium,Alternaria solani, and Gibberella zeae. In total, the target compounds displayed the best antifungal activity against P.piricola,and there were twelve compounds with an inhibition rate of more than 60%, in particular, compound 4n (R=4-NO2)presented the best inhibition rate of 90.6% (A-class activity level).[Conclusion] A series of novel myrtenal-based thiazole-hydrazone compounds were synthesized. These compounds exhibited to certain degree antifungal activity, and among them compound 4n (R=4-NO2) was a leading compound worthy of deep research.

Key words: α-pinene, myrtenal, thiazole-hydrazone, synthesis, antifungal activity

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