1-甲基葡萄糖的合成及其热裂解产物分析

Preparation and pyrolysis of 1-methyl-glucose

摘要:

以葡萄糖酸δ-内酯为原料，合成TMS保护的葡萄糖酸δ-内酯（Ⅰ），然后利用CH3Li加成，得到TMS保护的1-甲基葡萄糖（Ⅱ），将其溶于乙腈-水中，加入H+强阳离子交换树脂脱去TMS保护，得到1-甲基葡萄糖（Ⅲ）。目标产物结构经1HNMR、13CNMR、HRMS 确证，同时对其热裂解产物进行了测定。结果表明：以该方法合成的化合物为1-甲基-α-D-葡萄糖，在优化的条件下，3步反应总产率达到86%；1-甲基葡萄糖在醇溶液中经酸催化易转化为相应的糖苷；1-甲基葡萄糖热裂解后可释放出具有焦甜香气的物质2-乙酰基呋喃，5-甲基-2-乙酰基呋喃，5-羟甲基-2-乙酰基呋喃等，可用于食品、烟草等行业。

Abstract:

1-Methyl-glucose was obtained from δ-gluconolactone via three steps. δ-gluconolactone was protected by TMSCl firstly. Subsequently the addition reaction was employed to form TMS protected 1-methyl-glucose (Ⅱ), and then 1-methyl-glucose (Ⅲ) was obtained by hydrolysis of compound (Ⅱ) using acid cation exchange resin in acetonitrile solution. The target compound was confirmed by 1HNMR, 13CNMR and HRMS. The thermal pyrolysis behavior of 1-methyl-glucose was also investigated using on-line pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS).The results indicated that the compound (Ⅲ) synthesized was 1-methyl-α-D-glucose, and under these optimal conditions, the yield of compound (Ⅲ) was 86%. 1-Methyl-glucose could be transformed to corresponding glucoside easily in alcohol catalyzed by acid. The synthesized 1-methyl-glucose after pyrolysis could release 2-acetylfuran, 5-methyl-2-acetylfuran, 5-hydroxymethyl-2-acetylfuran and other aromatic components, which could be used in food, tobacco and other industries.