Page 165 - 《精细化工》2023年第3期

第 40 卷第 3 期 精 细 化 工 Vol.40, No.3
20 23 年 3 月 FINE CHEMICALS Mar. 2023

香精与香料
酱油酮-β-D-葡萄糖苷的合成及热解转移率

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张改红，石栋栋，李 童，杨 靖，黄 申，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：以乙酰溴-α-D-葡萄糖（Ⅰ）为糖基供体和酱油酮（Ⅱ）进行反应，分别合成了酱油酮-2,3,4,6-四-O-乙酰
基-β-D-葡萄糖苷（Ⅲ）和酱油酮-β-D-葡萄糖苷（Ⅳ）。在合成中间体Ⅲ的过程中探索了 Koenigs-Knorr 法和相转
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移催化法。中间体及产物结构经 HNMR、 CNMR、FTIR 和 HRMS 确证。将产物Ⅳ加入卷烟中，测定了其在
主流烟气粒相中的转移率。结果表明，两种方法均可得到中间体Ⅲ，相转移催化法优于 Koenigs-Knorr 法。最优
的相转移催化法的反应条件为：0.10 g 四丁基溴化铵为催化剂、10 mL 二氯甲烷为溶剂、n(Ⅰ)=1.2 mmol、1.60 g
无水 K 2 CO 3 为缚酸剂、n(Ⅰ)∶n(Ⅱ)=1.2∶1.0，室温反应 8 h。在上述条件下中间体Ⅲ的收率为 44.5%。中间体
Ⅲ在甲醇钠/甲醇体系中脱去乙酰基，得到目标产物Ⅳ，收率 88.0%。卷烟燃吸过程中，产物Ⅳ热裂解为酱油酮
后，其在主流烟气粒相中的转移率为 3.11%。
关键词：糖苷化；相转移催化；酱油酮-β-D-葡萄糖苷；热解转移率；香精与香料
中图分类号：TS411；O629.13 文献标识码：A 文章编号：1003-5214 (2023) 03-0621-06

Synthesis and pyrolysis transfer rate of 2-ethyl-5-methyl-3(2H)-
furanone-4-O-β-D-glucopyranoside

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ZHANG Gaihong, SHI Dongdong, LI Tong, YANG Jing, HUANG Shen, MAO Duobin
（School of Food and Bioengineering, Zhengzhou University of Light Industry, Zhengzhou 450002, Henan, China）

Abstract: 4-Hydroxyl-2-ethyl-5-methyl-3(2H)-furanone-2,3,4,6-tetra-O-acetyl-β-D-glucoside ( Ⅲ ) and
2-ethyl-5-methyl-3(2H)-furanone-4-O-β-D-glucopyranoside ( Ⅳ ) were obtained, respectively, from
glycosylation reaction of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide ( Ⅰ) and 4-hydroxyl-2-
ethyl-5-methyl-3(2H)-furanone (Ⅱ), and the Koenigs-Knorr method as well as phase transfer catalysis
method were explored in the synthesis of intermediate Ⅲ. The structures of intermediate and product
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prepared were confirmed by HNMR, CNMR, FTIR and HRMS. Product Ⅳ was then added into
cigarettes and its transfer rate in mainstream tobacco smoke was analyzed. The results showed that, though
intermediate Ⅲ could be synthesized via both methods, phase transfer catalysis method was superior to
Koenigs-Knorr method. The optimized reaction conditions of phase transfer catalysis, under which the yield
of intermediate Ⅲ reached 44.5%, were as follows: 0.10 g tetrabutylammonium bromide (TBAB) as
catalyst, 10 mL dichloromethane as solvent, n(Ⅰ)=1.2 mmol, 1.60 g anhydrous potassium carbonate as acid
binding agent, n(Ⅰ)∶n(Ⅱ)=1.2∶1.0, reaction at room temperature for 8 h. Meanwhile, product Ⅳ with
a yield of 88.0% was obtained by deacetylation of intermediate Ⅲ in sodium methoxide/methanol system.
Moreover, product Ⅳ was pyrolyzed into 4-hydroxyl-2-ethyl-5-methyl-3(2H)-furanone during cigarette
combustion with a transfer rate of 3.11% in mainstream flue gas.
Key words: glycosidation; phase transfer catalysis; 2-ethyl-5-methyl-3(2H)-furanone-4-O-β-D-glucopyranoside;
pyrolysis transfer rate; perfume and essence

收稿日期：2022-06-16; 定用日期：2022-08-29; DOI: 10.13550/j.jxhg.20220560
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，E-mail：50654048@qq.com。联系人：毛多斌（1962—），男，教授，E-mail：maoduobin@
sohu.com。