麦芽酚-β-D-葡萄糖苷的便捷合成及其加香应用  

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

作　　者：张改红 徐改改 白冰 杨静 黄备备 毛多斌 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)

机构地区：[1]郑州轻工业大学食品与生物工程学院,河南郑州450002

出　　处：《精细化工》2020年第5期997-1001,共5页Fine Chemicals

基　　金：河南省科技攻关计划项目(192102110212)。

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),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1HNMR、13CNMR、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K2CO3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4h,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。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 hydrolysis of compound Ⅲ. These compounds were characterized by 1 HNMR, 13 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.

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 

分 类 号：O629.13[理学—有机化学]