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【目的】提高百里香酚的热稳定性，对其进行糖苷化反应研究。【方法】将乙酰溴-α-D-葡萄糖(I)和百里香酚(Ⅱ)在离子液体催化下进行反应，合成百里香酚-2, 3, 4, 6-四-O-乙酰基-β-D-葡萄糖苷(Ⅲ)，化合物Ⅲ脱去乙酰基得到百里香酚-β-D-葡萄糖苷(Ⅳ)。通过TG-DTG考察化合物Ⅳ的热稳定性，通过Py-GC-MS考察了化合物Ⅳ的热裂解行为，并通过GC-MS对化合物Ⅱ和Ⅳ在主流烟气粒相中的热解转移率及转移率随时间的变化进行研究。【结果】离子液体催化合成化合物Ⅲ的反应条件为：氢氧化钠水溶液为缚酸剂，1-丁基-3-甲基-溴化咪唑鎓为催化剂，二氯甲烷为溶剂，n(I):n(NaOH)=1:2,n(I):n(1-丁基-3-甲基-溴化咪唑鎓)=1:1,n(Ⅰ)∶n(Ⅱ)=1:1，反应时间4 h，化合物Ⅲ收率55.1%。化合物Ⅲ在甲醇钠作用下脱去乙酰基，得到目标糖苷Ⅳ，收率80.6%。产物结构经1HNMR、13CNMR、IR和HRMS确证。化合物Ⅳ的热稳定性优于化合物Ⅱ，化合物Ⅳ在不同温度下的主要裂解产物均为化合物Ⅱ，化合物Ⅳ的释香稳定性优于化合物Ⅱ。【结论】百里香酚-β-D-葡萄糖苷可以改善百里香酚的缺点，可作为一种热稳定及释香稳定的烟用香料前体。
Abstract：[Background] This study aim to improve the thermal stability of thymol by conducting glycosylation research. [Methods]Acetyl bromide-α-D-glucose(Ⅰ) and thymol(Ⅱ) were reacted under ionic liquid catalysis to synthesize thymol-2, 3, 4, 6-tetra-O-acetyl-β-D-glucoside(Ⅲ), and compound Ⅲ was deacetylated to obtain thymol-β-D-glucoside(Ⅳ). The thermal stability of compound Ⅳ was investigated through TG-DTG, its pyrolysis behavior was studied through Py-GC-MS, and the pyrolytic transfer rate of compounds Ⅱ and Ⅳ in the particulate phase of mainstream smoke, as well as the change in transfer rate over time, was researched through GC-MS. [Results]The reaction conditions for the catalytic synthesis of compound Ⅲ using ionic liquids were as follows: sodium hydroxide aqueous solution as acid binding agent, 1-butyl-3-methyl-bromimidazolium as catalyst, dichloromethane as solvent, n(Ⅰ): n(NaOH)=1:2, n(I): n(1-butyl-3-methyl-bromimidazolium)=1:1, n(I): n(Ⅱ)=1:1, reaction time 4 hours, with a yield of 55.1% for compound Ⅲ. Under the action of sodium methoxide, compound Ⅲ was deacetylated to obtain the target glucoside Ⅳ, with a yield of 80.6%. The structure of the product was confirmed by 1HNMR, 13CNMR, IR, and HRMS. The thermal stability of compound Ⅳ was superior to that of compound Ⅱ,and the main pyrolysis products of compound Ⅳ at different temperatures were compound Ⅱ, indicating that the fragrance stability of compound Ⅳ was superior to that of compound Ⅱ. [Conclusion] Thymol-β-D-glucoside can improve the drawbacks of thymol and can be used as a thermally stable and fragrance-stable precursor for tobacco flavoring.
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基本信息:
DOI：10.16472/j.chinatobacco.2023.123
中图分类号:TS264.3
引用信息:
[1]张改红,石栋栋,杜帅等.百里香酚-β-D-葡萄糖苷的合成及转移率研究[J].中国烟草学报,2024,30(04):1-9.DOI:10.16472/j.chinatobacco.2023.123.
基金信息:
中国烟草总公司重大科技项目“香味前体物液相色谱-质谱数据库构建及应用研究”(110202201053(SJ-03))