Page 165 - 《精细化工》2022年第10期

第 39 卷第 10 期 精 细 化 工 Vol.39, No.10
2022 年 10 月 FINE CHEMICALS Oct. 2022

香料与香精
愈创木酚-β-D-葡萄糖苷的合成及其加香应用

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张改红 ，石栋栋 ，庞登红 ，白 冰 ，毛多斌 ，黄 龙
（1. 郑州轻工业大学 食品与生物工程学院，河南 郑州 450002；2. 湖北中烟工业有限责任公司，湖北 武
汉 430000）
摘要：以乙酰溴-α-D-葡萄糖（Ⅰ）和愈创木酚（Ⅱ）为原料，分别采用银盐法、相转移催化法和离子液体法，
合成了愈创木酚-2,3,4,6-四-O-乙酰基-β-D-葡萄糖苷（Ⅲ）；中间体Ⅲ脱去乙酰基得到了目标产物愈创木酚-β-D-
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葡萄糖苷（Ⅳ）。中间体及产物结构经 HNMR、 CNMR、FTIR 和 HRMS 确认。通过 TG-DSC 和感官评吸分别
考察了糖苷Ⅳ的热稳定性和加香效果。结果表明，3 种方法均可得到中间体Ⅲ，离子液体法优于相转移催化法
及银盐法。离子液体法的反应条件为：1-丁基-3-甲基咪唑四氟硼酸盐（[bmim]BF 4 ）为催化剂，无水 K 2 CO 3 为
缚酸剂，二氯甲烷为溶剂，n(Ⅱ)∶n(Ⅰ)∶n(催化剂)=1.0∶1.0∶0.3，室温反应 4 h，在该条件下糖苷Ⅲ的收率为
52.6%。糖苷Ⅲ在甲醇钠/甲醇体系中脱去乙酰基，得到目标糖苷Ⅳ，收率 77.4%。TG-DSC 结果表明，糖苷Ⅳ在
228.0 ℃以下具有较好的热稳定性。将糖苷Ⅳ添加于卷烟中能改善香气品质。
关键词：糖苷化；离子液体；愈创木酚-β-D-葡萄糖苷；热稳定性；加香
中图分类号：O629.13 文献标识码：A 文章编号：1003-5214 (2022) 10-2099-06

Synthesis of guaiacol-β-D-glucopyranoside and its flavoring application

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ZHANG Gaihong , SHI Dongdong , PANG Denghong , BAI Bing ,
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MAO Duobin , HUANG Long
（1. School of Food and Bioengineering, Zhengzhou University of Light Industry, Zhengzhou 450002, Henan, China;
2. China Tobacco Hubei Industrial Co., Ltd., Wuhan 430000, Hubei, China）
Abstract: The target product guaiacol-β-D-glucoside (Ⅳ) was obtained from deacetylation of intermediate
guaiacol-2,3,4,6-tetra-O-acetyl-β-D-glucoside(Ⅲ), which was synthesized from 2,3,4,6-tetra-O-acetyl-α-D-
glucopyranosyl bromide (Ⅰ) and guaiacol (Ⅱ) by silver salt method, phase transfer catalysis method and
ionic liquid method, respectively. The structures of intermediate Ⅲ and product Ⅳ obtained were firstly
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confirmed by HNMR, CNMR, FTIR and HRMS. Then, the thermal stability and flavoring effect of target
product Ⅳ were investigated by TG-DSC and sensory evaluation. The results showed that intermediate Ⅲ
could be synthesized by all of the three above-mentioned methods with ionic liquid method superior to
phase transfer catalysis and silver salt methods. The yield of intermediate Ⅲ produced by ionic liquid
method reached 52.6% under the reaction conditions: 1-Butyl-3-methylimidazole tetrafluoroborate
([bmim]BF 4 ) as catalyst, anhydrous potassium carbonate as acid binding agent, dichloromethane as solvent,
n(Ⅱ) : n(Ⅰ) : n(catalyst)=1.0 : 1.0 : 0.3, room temperature and reaction time of 4 h. The glycoside Ⅳ obtained
from acetyl group removal of intermediate Ⅲ in sodium methoxide/methanol system had a yield of 77.4%.
TG-DSC result demonstrated that the targeted compound had good thermal stability below 228.0 ℃.
Moreover, adding glycoside Ⅳ to cigarettes improved the aroma quality.
Key words: glycosylation; ionic liquids; guaiacol-β-D-glucoside; thermal stability; flavoring

糖苷键合态香料前体，又被称为潜香化合物， 本身性质稳定，不易挥发损失，不易氧化分解，但
是植物生长过程中形成的次级代谢产物，这类物质 在辐射、加热等条件下能够逐渐释放出特征香气物

收稿日期：2022-03-24; 定用日期：2022-06-06; DOI: 10.13550/j.jxhg.20220267
基金项目：河南省科技攻关计划项目（192102110212）
作者简介：张改红（1980—），女，副教授，博士，E-mail：50654048@qq.com。联系人：毛多斌（1962—），男，教授，E-mail: maoduobin@
sohu.com；黄 龙（1973—），男，研究员，E-mail：huanglonghbzy@163.com。