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第 36 卷第 2 期 精 细 化 工 Vol.36, No.2
201 9 年 2 月 FINE CHEMICALS Feb. 2019

香料与香精
5-甲基糠醇-β-D-葡萄糖苷的合成及热裂解

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张改红，白 冰 ，杨 静，程传玲，张月丽，毛多斌
（郑州轻工业学院 食品与生物工程学院，河南 郑州 450002）

摘要：为了开发新型糖苷类香料，首先以 D-葡萄糖为原料，合成了溴代四乙酰葡萄糖(Ⅲ)，再以 5-甲基糠醛（Ⅰ）
为原料，经还原制备了 5-甲基糠醇（Ⅱ），化合物Ⅱ与Ⅲ进行糖苷化反应，分别采用 Koenigs-Knorr 法和相转移
催化法，合成了 5-甲基糠醇-2, 3, 4, 6-四-O-乙酰基-β-D-葡萄糖苷（Ⅳ）；最后，将化合物Ⅳ水解，得到目标产物
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5-甲基糠醇-β-D-葡萄糖苷（Ⅴ）。中间体和产物结构经 HNMR、 CNMR、IR、HRMS 确证，并对糖苷Ⅴ的热
裂解性能进行了测定。结果表明：两种糖苷化方法所得到的产物均为糖苷Ⅳ，Koenigs-Knorr 法更优。Koenigs-Knorr
法的最佳反应条件为：n(5-甲基糠醇) : n(溴代四乙酰葡萄糖)=1 : 1.6，n(5-甲基糠醇) : n(Ag 2 CO 3 )=1 : 1.5，回流
反应 4 h，化合物Ⅳ的产率为 42.9%。目标糖苷Ⅴ热裂解后能够释放出 5-甲基糠醛、5-甲基糠醇等香味成分，可
用于食品、烟草等行业。
关键词：糖苷化；5-甲基糠醇-β-D-葡萄糖苷；热裂解；香料与香精
中图分类号：O629.13 文献标识码：A 文章编号：1003-5214 (2019) 02-0271-06

Synthesis and Pyrolysis of 5-Methyl Furfuryl Alcohol-β-D-Glucopyranoside

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ZHANG Gai-hong, BAI Bing , YANG Jing, CHENG Chuan-ling, ZHANG Yue-li, MAO Duo-bin
（School of Food and Bioengineering, Zhengzhou University of Light Industry, Zhengzhou 450002, Henan, China）

Abstract: To develop a new type of glycoside flavor, firstly, 2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl
bromide (Ⅲ) was synthesized from D-glucose. Then, 5-methyl furfuryl alcohol (Ⅱ) was prepared by a
reduction reaction of 5-methylfurfural (Ⅰ). Subsequently, a glycosylation reaction between compounds Ⅲ
and Ⅱ led to 5-methyl furfuryl alcohol-2, 3, 4, 6-tetra-O-acetyl-β-D-glucoside (Ⅳ) by Koenigs-Knorr
method and phase transfer catalysis method, respectively. Finally, the target compound 5-methyl furfuryl
alcohol-β-D-glucoside (Ⅴ) was obtained by hydrolysis of compound Ⅳ. These compounds were
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confirmed by HNMR, CNMR, IR and HRMS. The thermal pyrolysis of glucoside (Ⅴ) was also studied.
The results indicated that the compound Ⅳ synthesized by the two above-mentioned methods was target
product, the Koenigs-Knorr method was better than phase transfer catalysis method. The optimal conditions
for the preparation of compound Ⅳ by Koenigs-Knorr method were as follows : n(5-methyl furfuryl
alcohol) : n (2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl bromide)=1 : 1.6, n(5-methyl furfuryl
alcohol) : n(silver carbonate)=1 : 1.5, refluxing time for 4 h. Under these optimal conditions, the yield of
compound Ⅳ reached 42.9%. The synthesized 5-methyl furfuryl alcohol-β-D-glucoside after pyrolysis
could release 5-methyl furfural, 5-methyl furfuryl alcohol and other aromatic components, which could be
used in food, tobacco and other industries.
Key words:glycosylation;5-methyl furfuryl alcohol-β-D-glucoside;pyrolysis;perfumes and essences
Foundation item: Science and Technology Project of Henan Province (172102210068)

糖苷是许多天然香味成分的前体物质，常温下 糖苷键断裂后释放出香味成分，从而可以大大提高
性质稳定，不易挥发损失，但在加热或酶解条件下， 天然香味成分的稳定性，因此，在食品、烟草等领

收稿日期：2018-06-22; 定用日期：2018-11-09; DOI: 10.13550/j.jxhg.20180456
基金项目：河南省科技攻关计划项目（172102210068）
作者简介：张改红（1980—），女，博士，副教授。联系人：白 冰（1982—），男，博士，E-mail：baibingzzuli@126.com。