Page 220 - 《精细化工》2021年第3期

第 38 卷第 3 期 精 细 化 工 Vol.38, No.3
202 1 年 3 月 FINE CHEMICALS Mar. 2021

精细化工中间体
柠檬醛基 1,2,3-三唑类化合物的合成及其抑菌活性

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何 云 ，王 秀 ，段文贵 ，林桂汕 ，岑 波 ，雷福厚
（1. 广西大学 化学化工学院，广西 南宁 530004；2. 广西林产化学与工程重点实验室，广西 南宁
530008）
摘要：分别将橙花醇和香叶醇（Ⅰ）（柠檬醛两个立体异构体的前体）氧化为相应的醛（Ⅱ），进一步氧化为酸
（Ⅲ），然后与溴丙炔发生亲核取代反应得到末端炔酯（Ⅳ），最后与系列取代叠氮化合物发生 Husigen 环加成
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反应，得到 26 个(Z)-、(E)-柠檬醛基 1,2,3-三唑类化合物（Ⅴa~m）。采用 FTIR、 HNMR、 CNMR 和 ESI-MS
对目标化合物结构进行了表征，并测试了目标化合物的抑菌活性。结果表明：在目标化合物质量浓度为 50 mg/L
时，对西瓜炭疽病菌、黄瓜枯萎病菌、花生褐斑病菌、苹果轮纹病菌、小麦赤霉病菌、番茄早疫病菌、玉米小
斑病菌和水稻纹枯病菌 8 种植物病原菌均显示出一定的抑菌活性，其中，(E)-柠檬醛基对-溴苄基 1,2,3-三唑〔(E)-
Ⅴm〕、(E)-柠檬醛基邻-甲基苄基 1,2,3-三唑〔(E)-Ⅴb〕和(Z)-柠檬醛基间-甲基苄基 1,2,3-三唑〔(Z)-Ⅴc〕对西
瓜炭疽病菌的相对抑制率分别为 95.2%（A 级活性水平，优于阳性对照百菌清）、81.0%（B 级活性水平）和 81.0%
（B 级活性水平）。此外，目标化合物(E)-Ⅴm 对玉米小斑病菌的抑制率高达 95.2%（A 级活性水平，优于阳性
对照百菌清）。因此，化合物(E)-Ⅴm 有望成为新的候选抑菌剂。
关键词：柠檬醛；1,2,3-三唑；合成；抑菌活性；精细化工中间体
中图分类号：O626 文献标识码：A 文章编号：1003-5214 (2021) 03-0640-09

Synthesis and antifungal activity of citral-based 1,2,3-triazole compounds

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HE Yun , WANG Xiu , DUAN Wengui , LIN Guishan , CEN Bo , LEI Fuhou
（1. School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China; 2. Guangxi
Key Laboratory of Chemistry and Engineering of Forest Products, Nanning 530008, Guangxi, China）
Abstract: Nerol and geraniol (Ⅰ) (precursors of two stereoisomers of citral) were oxidized into their
corresponding aldehydes (Ⅱ), respectively. Subsequently, the aldehydes were further oxidized into their
corresponding acids (Ⅲ). Then, terminal alkynyl esters (Ⅳ) were prepared by nucleophilic substitution
reaction of acids (Ⅲ) with propargyl bromide, followed by Husigen cycloaddition reaction of the terminal
alkynyl esters (Ⅳ) with a series of substituted azide compounds to yield twenty-six (Z)- and (E)-citral-based
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1,2,3-triazole compounds (Ⅴa~m). All the target compounds were characterized by FTIR, HNMR,
13 CNMR and ESI-MS. Their antifungal activity was also evaluated. It was found that the target compounds
Ⅴa~m (mass concentration 50 mg/L) showed certain antifungal activity against eight tested plant pathogens,
including Colletotrichum lagenarium, Fusarium oxysporum f.sp. cucumerinum, Cercospora arachidicola,
Physalospora piricola, Gibberella zeae, Alternaria solani, Helminthosporium maydis, and Rhizoctonia
solani. Among them, (E)-citral-based p-bromobenzyl 1,2,3-triazole [(E)- Ⅴ m], (E)-citral-based
o-methylbenzyl 1,2,3-triazole [(E)-Ⅴb], and (Z)-citral-based m-methylbenzyl 1,2,3-triazole [(Z)-Ⅴc] had
inhibition rates of 95.2% (A-class activity level, better than that of the positive control chlorothalonil),
81.0% (B-class activity level), and 81.0% (B-class activity level), respectively, against Colletotrichum
lagenarium. Besides, compound (E)-Ⅴm had inhibition rate of up to 95.2% against Helminthosporium
maydis (A-class activity level, better than that of the positive control chlorothalonil). Therefore, compound
(E)-Ⅴm is expected to become a new candidate antifungal agent.

收稿日期：2020-08-09; 定用日期：2020-09-17; DOI: 10.13550/j.jxhg.20200738
基金项目：国家自然科学基金（31870556）；广西林产化学与工程重点实验室开放基金（GXFC17-18-01）
作者简介：何 云（1994–），女，硕士生。联系人：段文贵（1964–），男，教授，博士生导师，E-mail：wgduan@gxu.edu.cn。