酱油酮-β-D-葡萄糖苷的合成及热解转移率研究

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

摘要:

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)。合成糖苷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1HNMR、13CNMR、IR和HRMS确证。将糖苷Ⅳ加入卷烟中，测定其在卷烟主流烟气中的转移率。结果表明：两种方法均可得到糖苷Ⅲ，相转移催化法优于Koenigs -Knorr法。相转移催化法的反应条件为：四丁基溴化铵(TBAB)为催化剂，无水K2CO3为缚酸剂，二氯甲烷为溶剂，n(乙酰溴-α-D-葡萄糖): n(酱油酮)=1.2 : 1.0，室温反应8 h，糖苷Ⅲ的收率为44.5%。糖苷Ⅲ在甲醇钠/甲醇体系中脱去乙酰基，得到目标糖苷Ⅳ，收率88.0%。卷烟燃吸过程中，糖苷Ⅳ热裂解为酱油酮后，其在主流烟气中的转移率为3.1%。

Abstract:

Abstract: Soy sauce ketone -2,3,4,6-tetra-O-acetyl-β-D-glucoside (Ⅲ) and soy sauce ketone-β-D-glucoside (Ⅳ) was obtained by a glycosylation reaction between 2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl bromide (Ⅰ) and Soy sauce ketone (Ⅱ). The process of synthesizing glycoside Ⅲ was explored silver salt method and phase transfer catalysis method. The structures of the intermediates and products were confirmed by 1HNMR, 13CNMR, IR and HRMS. Glycoside Ⅳ was added into cigarettes to determine its transfer rate in cigarette mainstream smoke. The results show that both methods can obtain glycoside Ⅲ, and the phase transfer catalysis method is better than Koenigs-Knorr method. The reaction conditions of phase transfer catalysis were as follows: tetrabutylammonium bromide (TBAB) as catalyst, anhydrous potassium carbonate as acid binding agent, dichloromethane as solvent, n (acetyl bromide-α-D-glucose): n (soy sauce ketone) =1.2:1.0, reaction at room temperature for 8 hours, and the yield of glycoside Ⅲ was 44.5%. The acetyl group of glycoside Ⅲ was removed in the sodium methoxide/methanol system to obtain the target glycoside Ⅳ in 88.0% yield. Glucoside Ⅳwas added into cigarettes, the glucoside pyrolyzed into soy sauce ketone during smoking, and its transfer rate to mainstream cigarette smoke was 3.1%.