Richter Alexander, Wagenknecht Wolfgang
Fraunhofer Institute of Applied Polymer Science, Geiselbergstr. 69, D-14476, Golm, Germany.
Carbohydr Res. 2003 Jun 23;338(13):1397-401. doi: 10.1016/s0008-6215(03)00179-4.
Amylose triacetate (ATA) dissolved in DMSO was partially deacetylated by 1,6-hexamethylendiamine, 1,8-octamethylendiamine, 1,12-dodecylmethylendiamine and 1,2-cyclohexyldiamine (mixture of cis and trans isomers) at 80 degrees C. The reaction kinetics of the deacetylation were studied. Differences were found in the course of the reaction depending on the type of alkylene diamine (linear or cyclic). The isolated amylose acetates were dissolved in DMF and subsequently sulfated with sulfamic acid. In the course of the sulfation, the acetyl groups acted as protective groups and were completely cleaved after reaction. The amylose acetates and sulfates obtained were studied by 13C NMR spectroscopy and elemental analysis. It could be shown, that the deacetylation of ATA with the described alkylene diamines as well as the subsequent sulfation are highly regioselective. By proceeding this reaction scheme it is possible to synthesize 6-amyloseacetate, 2,6-di-amyloseacetate and 2-amylosesulfate with a high structural uniformity.
将溶解于二甲基亚砜（DMSO）中的直链淀粉三乙酸酯（ATA）在80℃下用1,6 - 己二胺、1,8 - 辛二胺、1,12 - 十二烷二胺和1,2 - 环己二胺（顺式和反式异构体混合物）进行部分脱乙酰化反应。研究了脱乙酰化反应的动力学。根据亚烷基二胺的类型（直链或环状），在反应过程中发现了差异。将分离得到的直链淀粉乙酸酯溶解于N,N - 二甲基甲酰胺（DMF）中，随后用氨基磺酸进行硫酸化。在硫酸化过程中，乙酰基起到保护基团的作用，反应后被完全裂解。通过13C核磁共振光谱法和元素分析对得到的直链淀粉乙酸酯和硫酸盐进行了研究。结果表明，ATA与所述亚烷基二胺的脱乙酰化反应以及随后的硫酸化反应具有高度的区域选择性。通过采用该反应方案，可以合成具有高度结构均匀性的6 - 直链淀粉乙酸酯、2,6 - 二直链淀粉乙酸酯和2 - 直链淀粉硫酸盐。
