Preparation and Reactions of 2-Chloroethyl 1-Thio-β-D-glycopyranosides Derived from D-Galactose, D-Glucose, and 2-Acetamido-2-deoxy-D-glucose
Preparation and Reactions of 2-Chloroethyl 1-Thio-β-D-glycopyranosides Derived from D-Galactose, D-Glucose, and 2-Acetamido-2-deoxy-D-glucose
复制标题
D-半乳糖、D-葡萄糖和 2-乙酰氨基-2-脱氧-D-葡萄糖衍生的 2-氯乙基 1-硫代-β-D-吡喃葡萄糖苷的制备和反应
DOI：
10.1135/cccc19961489
复制
发表时间：
1996
影响因子：
--
通讯作者：
M. Buděšínský
中科院分区：
文献类型：
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作者：
M. Černý;T. Trnka;M. Buděšínský
用1-溴-2-氯乙烷将相应的1-硫-β- d -己基吡喃糖3a-3c与1-溴-2-氯乙烷烷基化，然后去乙酰化，制备了d -半乳糖和d -葡萄糖构型5a-5c的氯乙基1-硫-β- d -甘黄苷。用异硫脲盐从乙酰化的甘氨酰卤化物中得到起始的1-硫-β- d -六吡喃糖。证明了氯乙基硫甙5a-5c在水溶液中水解得到2-羟乙基硫甙6a-6c和还原性己糖，这种水解是通过异磺盐进行的。通过1H和13C核磁共振谱监测水解过程。在含有苯酚或苯胺的1%碳酸钠水溶液中，巯基糖苷5a-5c除提供上述水解产物外，还分别提供苯氧乙基和苯胺乙基巯基糖苷9a、10a和9b、10b。
Chloroethyl 1-thio-β-D-glycopyranosides of the D-galacto and D-gluco configurations 5a-5c were prepared by alkylation of the corresponding 1-thio-β-D-hexopyranoses 3a-3c with 1-bromo-2-chloroethane followed by deacetylation. The starting 1-thio-β-D-hexopyranoses were obtained from the acetylated glycopyranosyl halides via isothiouronium salts. It was demonstrated that the chloroethyl thioglycosides 5a-5c undergo hydrolysis in aqueous solutions to give the 2-hydroxyethyl thioglycosides 6a-6c and reducing hexoses and that this hydrolysis proceeds via episulfonium salts. The hydrolysis was monitored by 1H and 13C NMR spectroscopy. In 1% aqueous solutions of sodium carbonate containing phenol or aniline, the thioglycosides 5a-5c provide, in addition to the above hydrolysis products, also the phenoxyethyl and phenylaminoethyl thioglycosides 9a, 10a and 9b, 10b, respectively.