酱油酮-β-D-葡萄糖苷的合成及热解转移率  

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

作　　者：张改红 石栋栋 李童 杨靖 黄申 毛多斌 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)

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》2023年第3期621-626,共6页Fine Chemicals

基　　金：河南省科技攻关计划项目(192102110212)。

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法和相转移催化法。中间体及产物结构经^(1)HNMR、^(13)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%。4-Hydroxyl-2-ethyl-5-methyl-3(2H)-furanone-2,3,4,6-tetra-O-acetyl-β-D-glucoside(Ⅲ)and2-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 prepared were confirmed by ^(1)HNMR,^(13)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,productⅣwith 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.

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 

分 类 号：TS411[农业科学—烟草工业] O629.13[理学—有机化学]