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第 35 卷第 7 期 精 细 化 工 Vol.35, No.7
201 8 年 7 月 FINE CHEMICALS July 2018

精细化工中间体

ω-氯甲基长叶烯的合成及其抑菌活性

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蓝虹云，李庆永，黄道战 ，林 玲，李祖引，周 艳
（广西民族大学 化学化工学院；广西林产化学与工程重点实验室，广西 南宁 530008）

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摘要：以 ω-羟甲基长叶烯（Ⅰb）为原料，经过卤代反应，合成了 ω-氯甲基长叶烯（Ⅰc），产物经 FTIR、HNMR、
13 CNMR 和 HRMS 等进行了结构表征。考察了反应温度、反应物配比〔n(SOCl 2 )∶n(Ⅰb)〕和反应时间对卤代反
应的影响。结果表明：在较佳的反应条件〔反应温度 85 ℃，n(SOCl 2 )/n(Ⅰb)=1.10，反应时间 6 h〕下，Ⅰc 产率
达 94.2%。初步的抑菌活性实验结果表明：Ⅰc 对金黄色葡萄球菌、肺炎克雷伯氏菌和白色念珠菌的生长具有明
显的抑制作用，其最低抑菌质量浓度分别为 31.3、62.5 和 125 mg/L，且远小于长叶烯的最低抑菌质量浓度
（>500 mg/L）。运用密度泛函理论（DFT），采用 B3LYP/6-31G 方法对Ⅰc 和长叶烯进行几何结构优化，结果
表明，Ⅰc 抑菌活性高于长叶烯，与Ⅰc 的前线轨道能隙（0.063 a.u）比长叶烯（0.256 a.u）小有关。
关键词：长叶烯；ω-羟甲基长叶烯；卤代反应；ω-氯甲基长叶烯；抑菌活性；精细化工中间体
中图分类号：TQ35 文献标识码：A 文章编号：1003-5214 (2018) 07-1255-06

Synthesis and Antimicrobial Activity of ω-Chloromethyl Longifolene

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LAN Hong-yun, LI Qing-yong, HUANG Dao-zhan , LIN Ling, LI Zu-yin, Zhou Yan
（College of Chemistry and Chemical Engineering, Guangxi University for Nationalities,Guangxi Key Laboratory of
Chemistry and Engineering of Forest Products, Nanning 530008, Guangxi, China）

Abstract: ω-Chloromethyl longifolene (Ⅰc) was synthesized via halogenation of ω-hydroxymethyl
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longifolene (Ⅰb) and characterized by means of FTIR, HNMR, CNMR and HRMS. The factors affecting
the halogenation reaction such as reaction temperature, reaction time and material ratio were investigated.
Under the optimum reaction conditions, i.e., 85 ℃, 6 h, molar ratio of thionyl chloride to compound Ⅰb
1.10∶1.00, the yield of compound Ⅰc was up to 94.2%. The preliminary biological activity test showed
that compound Ⅰc could obviously inhibit the growth of two bacteria (staphylococcus aureus and Canidia
Albicans) and one fungus (Klebsiella pneumonia), the corresponding minimal inhibitory concentrations
were 31.3, 62.5, and 125 mg/L, respectively, far less than that of longifolene (500 mg/L). It was found that
the antimicrobial activity of compound Ⅰc was associated with its HOMO (highest occupied molecular
orbital)-LUMO (lowest unoccupied molecular orbital) energy gap (0.063 a.u), which was lower than that of
longifolene (0.256 a.u) calculated using the density function theory (DFT) at B3LYP/6-31G level.
Key words: longifolene; ω-hydroxymethyl longifolene; halogenation; ω-chloromethyl longifolene;
antimicrobial activity; fine chemical intermediate
Foundation items: National Natural Science Foundation of China (31460174); Natural Science Foundation
of Guangxi Zhuang Autonomous Region (2017GXNSFAA198027); Scientific Research Project of Guangxi
University for Nationalities (2014MDQD014); Graduate Education Innovation Project of Guangxi
University for Nationalities (gxun-chxzs2016118)

长叶烯(Ⅰ)是重质松节油的主要成分，具有独 身具有一定的抗菌、抑菌、消炎、抗癌、抑藻等生
[1]
特的分子结构和香气，主要用来合成香料 。其自 物活性 [2-7] ，在医药、农药等行业显示出良好的应用

收稿日期：2017-07-26; 定用日期：2017-11-28; DOI: 10.13550/j.jxhg.20170604
基金项目：国家自然科学基金（31460174）；广西自然科学基金（2017GXNSFAA198027）；广西民族大学科研项目 (2014MDQD014)；
广西民族大学研究生教育创新计划项目（gxun-chxzs2016118）
作者简介：蓝虹云（1969—），女，研究员，硕士生导师，E-mail：lanhongyun@gxun.edu.cn。联系人：黄道战（1968—），高级实验
师，博士，电话：0771-3267019，E-mail: huangdaozhan@gxun.edu.cn。