Page 147 - 《精细化工》2020年第5期

第 37 卷第 5 期 精 细 化 工 Vol.37, No.5
202 0 年 5 月 FINE CHEMICALS May 2020

香料与香精
麦芽酚-β-D-葡萄糖苷的便捷合成及其加香应用

张改红，徐改改，白 冰，杨 静，黄备备，毛多斌

（郑州轻工业大学 食品与生物工程学院，河南 郑州 450002）

摘要：为了改进糖苷化反应的合成工艺，以 D-葡萄糖为原料，合成了溴代四乙酰葡萄糖（Ⅱ），化合物Ⅱ与麦
芽酚（Ⅰ）分别经相转移催化和 Koenigs-Knorr 糖苷化反应合成了麦芽酚-2,3,4,6-四-O-乙酰基-β-D-葡萄糖苷（Ⅲ），
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化合物Ⅲ脱乙酰基得到目标产物麦芽酚-β-D-葡萄糖苷（Ⅳ）。产物结构经 HNMR、 CNMR、IR、HRMS 确证。
考察了糖苷Ⅳ的热裂解和加香评吸效果。结果表明，对于糖苷化反应，相转移催化法优于 Koenigs-Knorr 法。相
转移催化法的反应条件为：丙酮为溶剂，无水 K 2 CO 3 为缚酸剂，四丁基溴化铵（TBAB）为相转移催化剂，n（麦
芽酚）∶n（溴代四乙酰葡萄糖）=1.0∶1.2，室温反应 4 h，化合物Ⅲ的产率为 75.6%。化合物Ⅲ在甲醇钠/甲醇体
系进行水解得到化合物Ⅳ。糖苷Ⅳ受热裂解能释放出麦芽酚等特征香味成分，将其添加于卷烟中能够改善香气品质。
关键词：糖苷化；麦芽酚-β-D-葡萄糖苷；相转移催化；热裂解；卷烟；香味成分
中图分类号：O629.13 文献标识码：A 文章编号：1003-5214 (2020) 05-0997-05

Facile preparation of maltol alcohol-β-D-glucopyranoside and
its flavoring application

ZHANG Gaihong, XU Gaigai, BAI Bing, YANG Jing, HUANG Beibei, MAO Duobin
（School of Food and Bioengineering, Zhengzhou University of Light Industry, Zhengzhou 450002, Henan, China）

Abstract: To improve the synthesis of glycoside reaction, 2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl
bromide (Ⅱ) was synthesized from D-glucose. A glycosylation reaction between compound Ⅱ and maltol
(Ⅰ) led to maltol-2,3,4,6-tetra-O-acetyl-β-D-glucoside (Ⅲ) by phase transfer catalysis and Koenigs- Knorr
method, respectively. Subsequently, the target compound maltol-β-D-glucoside (Ⅳ) was obtained by
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hydrolysis of compound Ⅲ. These compounds were characterized by HNMR, CNMR, IR and HRMS.
The effects of pyrolysis and aroma evaluation of glycoside Ⅳ were studied. The results indicated that
compound Ⅲ synthesized by two above-mentioned methods was target product, phase transfer catalysis
was better than Koenigs-Knorr method. The optimal conditions for the preparation of compound Ⅲ by
phase transfer catalysis were as follows: acetone as solvent, anhydrous potassium carbonate as acid binding
agent, and tetrabutyl ammonium bromide (TBAB) as phase transfer catalyst, n(maltol) ∶ n(2,3,4,
6-tetra-O-acetyl-α-D-glucopyranosyl bromide)=1.0∶1.2, reaction at room temperature for 4 h. Under these
conditions, the yield of compound Ⅲ reached 75.6%. Compound Ⅲ was hydrolyzed in sodium
methoxide/methanol system to obtain compound Ⅳ. Glycoside Ⅳ could release characteristic flavor
components such as maltol by pyrolysis, which can be added to cigarettes to improve aroma quality.
Key words: glycosylation; maltol-β-D-glucoside; phase transfer catalysis; pyrolysis; cigarette; flavor
component

糖苷是许多天然香味成分的前体物质，常温下 此，糖苷是一类耐高温的香料前体。烟草中某些挥
性质稳定，但在加热、酶解等条件下，糖苷键断裂 发性香味物质是以糖苷的形式存在，且在加工、储
释放出香味成分，从而达到缓释香气的效果 [1-6] ，因 存过程中能够保持稳定。具有焦甜香的环戊烯醇酮

收稿日期：2019-12-10; 定用日期：2020-02-20; DOI: 10.13550/j.jxhg.20191157
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。