α-D-甲基葡萄糖苷的伯羟基选择性保护及工艺改进

The Selective Protections at Primary Hydroxy of Methyl-α-D-glucopyranoside and improvement in their Procession

以α D 甲基葡萄糖苷为原料 ,采用常用的 3种方法选择性保护伯羟基 ,改进了工艺 ,得到 3种重要的衍生物 :①用对甲苯磺酰氯将 6位羟基对甲苯磺酰化 ,再直接加入乙酸酐乙酰化 ,得到 6 OTs 2 ,3,4 三 O 乙酰基 α D 甲基葡萄苷 (Ts :对甲苯磺酰基 ) ,收率达 5 6 % ;②用三苯基膦和四氯化碳将 6位羟基氯化 ,除去三苯基膦氧 ,乙酸酐乙酰化 ,得到 6 Cl 2 ,3,4 三 O 乙酰基 α D 甲基葡萄糖苷 ,收率为 4 8% ;③用三苯氯甲烷将 6位羟基苯甲基化 ,乙酸酐乙酰化 ,得到 6 OTr 2 ,3,4 三 O 乙酰基 α D 甲基萄萄糖苷 (Tr :三苯甲基 ) ,收率为 80 %。

Three methods were used to protect the primary hydroxy group of methylα-D-glucopyranoside. Three important derivatives were prepared with the improved methods: ① p-toluenesulfonyl chloride was used to protect the 6th position hydroxy, acetic anhydride was added to protect other hydroxyl directly ,and methyl -2,3,4-tri-O-acetyl-6-OTs-α-D-glucopyranoside(Ts:p-tolysulfonyl )was prepared with the yield 56%;② Triphenylphosphine and tetrachloromethane was applied to chloridate the 6th positionhydroxy, and methyl 2,3,4-tri-O-acetyl-6-chloro-6-deoxy-α-D-glucopyranoside was prepared with the yeild 48% after acethylation and purification; ③ chlorotriphenylmethane was used to protect the 6 position hydroxy, methyl 2,3,4-tri-O-acetyl-6-OTr-α-D-glucopyranoside (Tr:trityl)was prepared to after acetylation with acetic anhydride, and the yield was elevated to 80%.