以D-葡萄糖为原料，分别合成了2,3,4,6-四-O-乙酰基-α-D-溴代吡喃葡糖苷（2，溴代葡萄糖法）和2,3,4,6-四-O-乙酰基-α-D-葡萄糖基三氯乙酰亚胺酯（4，三氯乙腈法），2和4再分别与甲基环戊烯醇酮（MCP）进行偶联反应，然后脱乙酰基制备了结构不同的MCP-β-D-葡糖苷[3-甲基-1-氧代环戊-2-烯基-β-D-吡喃葡糖苷（1）和5-甲基-1-氧代环戊-2-烯基-β-D-吡喃葡糖苷（1′）]；用1H NMR和HRMS技术对中间体和产物的结构进行了表征；并研究了糖苷1和1′的热裂解。结果表明：①两种合成方法所得到的产物都是目标产物，溴代葡萄糖法优于三氯乙腈法；②溴代葡萄糖法的最佳反应条件为甲基环戊烯醇酮与化合物2的摩尔比为1∶1.2，温度35℃，反应时间5 h，目标产物的产率82.0%，反应总产率59.6%；③卷烟燃吸过程中，糖苷1和1′热裂解为甲基环戊烯醇酮后，其在主流烟气中的转移率分别为16.13%和16.40%。%Taking D-glucose as material, 2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl bromide(Compound 2) and 2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl trichloroacetimidate (Compound 4′) were synthesized byα-D-acetobromoglucose method (Method A) and trichloroacetonitrile method (Method B), respectively. Compounds 2 and 4′ were coupled with methylcyclopentenolone(MCP), then deacetylated to form MCP-β-D-glucopyranosides [3-methyl-1-oxocyclopenta-2-en-2-yl-β-D-glucopyranoside (Compound 1) and 5-methyl-1-oxocyclopenta-2-en-2-yl-β-D-glucopyranoside (Compound 1′), respectively. The molecular structures of intermediates and final products were characterized by 1H NMR and HRMS. The thermal pyrolysis of glucosides 1 and 1′ was also studied, and the results indicated that: 1) The compounds synthesized by the two methods were target products, Method A was better than Method B. 2)The optimal conditions of Method A were the molar ratio of MCP to compound 2 1∶1.2 and reacting at 35 ℃ for 5 hours, the yield of target product reached 82.0% and the total yield of reaction was 59.6%. 3)Glucosides 1 and 1′were added into cigarettes separately, the glucosides pyrolyzed into MCP during smoking, and their transfer rates to mainstream cigarette smoke were 16.13% and 16.40%, respectively.
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