Synthesis of Biodegradable Polymer Having Saccharide Chai

在D-乳糖上，具有伯羟基的C-6和C-6‘被选择性地三苯甲基化，其余的仲羟基被乙酰化。在有害的苯甲基化过程中，乙酰化乳糖发生了酰基迁移，在C-6和C-4‘上有自由羟基。将得到的1，2，3，2‘，3’，6‘-六-ο-乙酰基-D-乳糖与对苯二甲酰氯缩聚，得到主链上含有乳糖的芳香族聚酯，然后对麦芽糖进行区域选择性取代，然后聚合得到可生物降解的聚合物。麦芽糖的两个伯羟基被对甲苯磺化，其余的仲羟基被乙酰化。对甲苯磺基被叠氮基取代。将叠氮麦芽糖衍生物与邻苯二甲酰氯反应生成酰胺类化合物，研究了b-环糊精的部分羧甲基化反应。B-环糊精在水溶液中用氯乙酸和氢氧化钠进行羧甲基化反应，很难得到产物。另一方面，以氢氧化钾为碱合成了二ο-羧甲基b-环糊精。用溴乙酸代替氯乙酸，可在较短的时间内得到二ο-羧甲基化的b-环糊精。在二甲基甲酰胺溶液中，b-环糊精与氯乙酸甲酯和氢化钠反应生成二ο-羧甲基b-环糊精。将二ο-羧甲基化的b-环糊精与六亚甲二胺缩合，得到了相对分子质量为104的聚酰胺。

On D-lactose, C-6 and C-6' which have the primary hydroxy groups were selectively triphenylmethylated and the remaining secondary hydroxy groups were acetylated. During detriphenylmethylation, acyl migration occurred to give acetylated lactose having free hydroxy groups on C-6 and C-4'. Polycondensation of the obtained 1,2,3,2',3',6'-hexa-ο-acetyl-D-lactose and terephthaloyl chloride gave the aromatic polyester having lactose in the main chain.Maltose was regioselectively substituted and the obtained derivative was polymerized in order to obtain a biodegradable polymer. Two primary hydroxyl groups of maltose were tosylated and the remaining secondary hydroxyl groups were acetylated. The tosyl group was replaced with azido group. The azidomaltose derivative was reacted with telephthaloyl chloride to give amide compound.Partial carboxymethylation of b-cyclodextrin was investigated. The carboxymethylation of b-cyclodextrin with chloroacetic acid and sodium hydroxide in water sokution was difficult to give the product. On the other hand, di-ο-carboxymethylated b-cyclodextrin was obtained by using potassium hydroxide as base. When bromoacetic acid was used instead of chloroacetic acid, di-ο-carboxymethylated b-cyclodextrin was obtained in shorter time. The reaction of b-cyclodextrin with methyl chloroacetate and sodium hydride in dimethylformamide solusion also gave di-ο-carboxymethylated b-cyclodextrin with the hydrolysis of methyl ester. Condensation reaction of di-ο-carboxymethylated b-cyclodextrin with hexamethylendiamine gave polyamide of which the molecular weight was 10^4.