THE ALCOHOLYSIS OF TRIALKYLALKOXYSILANES. PART II. THE PREPARATION AND CHEMISTRY OF METHYL 2,3,4-TRI-O-TRI-METHYLSILYL-ALPHA-DGLUCOPYRANOSIDE,
THE ALCOHOLYSIS OF TRIALKYLALKOXYSILANES. PART II. THE PREPARATION AND CHEMISTRY OF METHYL 2,3,4-TRI-O-TRI-METHYLSILYL-ALPHA-DGLUCOPYRANOSIDE,
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三烷基烷氧基硅烷的醇解。
DOI：
10.1139/v65-269
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发表时间：
1965
影响因子：
1.1
通讯作者：
A. Mcinnes
中科院分区：
文献类型：
--
作者：
D. T. Hurst;A. Mcinnes
摘要：甲基2，3，4，6-四-O-三甲基甲硅烷基-α-D-吡喃葡萄糖苷的6-位上的三甲基甲硅烷基优先通过甲醇分解除去，使用碱性或酸性催化剂，以高产率（>80%）得到甲基2，3，4-三-O-三甲基甲硅烷基-α-D-吡喃葡萄糖苷。后者与乙酸酐、苯甲酰氯或异氰酸苯酯反应，以定量产率产生相应的6-取代衍生物。来自后一种化合物的三甲基甲硅烷基残基被50%甲醇水溶液水解，同时以优异的产率形成甲基α-D-吡喃葡萄糖苷的6-O-乙酰基、6-O-苯甲酰基或6-氨基甲酸酯衍生物。化学和质子磁共振（p.m.r.）研究确定了甲基2，3，4-三-O-三甲基甲硅烷基-α-D-吡喃葡萄糖苷和由该化合物制备的后续衍生物的结构。红外和p.m.r.提供了证据来支持关于在这些化合物中的一些中连接到葡糖苷残基的C6和C5上的基团或原子的构象的结论。（作者）
Abstract : The trimethylsilyl group on the 6-position of methyl 2,3,4,6-tetra-O-trimethylsilyl-alpha-D-glucopyranoside is preferentially removed by methanolysis, using basic or acidic catalysts, giving methyl 2,3,4-tri-O-trimethylsilyl-alpha-D-glucopyranoside in high yield (>80%). Reaction of the latter with acetic anhydride, benzoyl chloride, or phenyl isocyanate produces the corresponding 6-substituted derivatives in quantitative yield. The trimethylsilyl residues from the latter compounds are hydrolyzed by 50% aqueous methanol with the concomitant formation of 6-O-acetyl, 6-O-benzoyl, or 6-carbanilate derivatives of methyl alpha-D-glucopyranoside in excellent yield. Chemical and proton magnetic resonance (p.m.r.) studies established the structure of methyl 2,3,4-tri-O-trimethylsilyl-alpha-D-glucopyranoside, and of subsequent derivatives prepared from this compound. Infrared and p.m.r. evidence is offered to support conclusions regarding the conformation of the groups or atoms attached to C6 and C5 of the glucoside residue in some of these compounds. (Author)