Synthesis of stereoregular head,tail hydroxylated nylons derived from D-glucose
Synthesis of stereoregular head,tail hydroxylated nylons derived from D-glucose
复制标题
DOI：
10.1021/jo960201e
复制
发表时间：
1996-08-23
影响因子：
3.6
通讯作者：
Kiely, DE
中科院分区：
文献类型：
--
作者：
Chen, L;Kiely, DE
介绍了一种由D-葡萄糖酸和烷二胺衍生的立体规则聚羟基聚酰胺，即头、尾羟基尼龙的简单制备方法。以D-葡萄糖酸单钾为原料，经D-葡萄糖-6，3-内酯两步反应制得D-葡萄糖酸钠6，3-内酯。将偶数C-2至C-12脂肪族二胺的甲醇溶液与不溶的D-葡萄糖酸钠-6，3-内酯回流，方便地合成了6-[N-(氨基烷基)]-D-葡萄糖胺钠盐的甲醇不溶前驱体。得到的每一种盐在C-1端用盐酸/甲醇进行酯化/内酯化，产物经碱性处理得到相应的游离碱氨基酸酯/内酯混合物。后者自发地进行自我聚合，得到目标聚酰胺。从手性D-葡萄糖酸制备立体规则聚酰胺的这一一般过程的一个重要特征是，它不需要任何碳水化合物羟基保护/去保护步骤。
A simple procedure for the preparation of stereoregular polyhydroxypolyamides, i.e., head,tail hydroxylated nylons, derived from D-glucaric acid and alkylenediamines is described. Sodium D-glucarate 6,3-lactone was made in two steps from monopotassium D-glucarate by way of D-glucaro-6,3-lactone. Methanol insoluble salt of sodium 6-[N-(aminoalkyl)]-D-glucaramide monomer precursors were conveniently prepared by refluxing methanol solutions of even-numbered C-2 to C-12 aliphatic diamines with insoluble sodium D-glucarate-6,3-lactone. Each of the resulting salts was esterified/lactonized at the C-1 carboxylate terminus with HCl/methanol, and the products were made basic to give the corresponding free base amino acid ester/lactone mixture. The latter spontaneously underwent self-polymerization to give the target polyamides. An important feature of this general procedure for stereoregular polyamides from chiral D-glucaric acid is that it does not require any carbohydrate hydroxyl group protection/deprotection steps.