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、1HNMR、（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。
ω-Chloromethyl longifolene（Ⅰc） was synthesized via halogenation of ω-hydroxymethyl longifolene（Ⅰb） and characterized by means of FTIR, 1 HNMR, 13 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 B3 LYP/6-31 G level.
作者
蓝虹云
李庆永
黄道战
林玲
李祖引
周艳
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, Chin)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2018年第7期1255-1260,共6页
Fine Chemicals
基金
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)~~
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
longifolene
co-hydroxymethyl longifolene
halogenation
co-chloromethyl longifolene
antimicrobial activity
fine chemical intermediate
