Basic study for acyl chitosan isothiocyanates synthesis by model experiments using glucosamine derivatives
Basic study for acyl chitosan isothiocyanates synthesis by model experiments using glucosamine derivatives
复制标题
氨基葡萄糖衍生物模型实验合成酰基壳聚糖异硫氰酸酯的基础研究
DOI：
10.1016/j.ijbiomac.2019.03.114
复制
发表时间：
2019
影响因子：
8.2
通讯作者：
Toshiyuki Takano
中科院分区：
文献类型：
--
作者：
Shouko Nishida;Masaya Shibano;Hiroshi Kamitakahara;Toshiyuki Takano
以辛基2-氨基-2-脱氧-β-D-葡萄糖苷为模型化合物，研究了N-苯硫代氨甲酰化和酰化反应合成酰基壳聚糖异硫氰酸酯的影响因素。N-苯硫氨甲酰基氨基葡萄糖衍生物与乙酸酐/吡啶的乙酰化反应发现，氨基葡萄糖异硫氰酸酯是通过N，N-（乙酰基）苯硫氨甲酰基氨基葡萄糖衍生物生成的，而N，N-（乙酰基）苯硫氨甲酰基氨基葡萄糖衍生物向氨基葡萄糖异硫氰酸酯的转化主要是通过N，N-（乙酰基）苯硫氨甲酰基的热降解进行的。反应温度是影响异硫氰酸酯合成的重要因素。另一方面，从N-乙基硫代氨基甲酰基衍生物（或N-烯丙基硫代氨基甲酰基衍生物）与乙酸酐/吡啶的乙酰化反应中发现，氨基葡萄糖异硫氰酸酯也由N-乙基硫代氨基葡萄糖胺衍生物（或N-烯丙基硫代氨基葡萄糖胺衍生物）制备，但N-苯基硫代氨基甲酰基化比N-乙基硫代氨基甲酰基化和N-烯丙基硫代氨基甲酰基化更优选用于异硫氰酸酯的合成。然后，可以通过反应温度和反应体系控制N-苯硫代氨基甲酰基壳聚糖的酰化产物（N，N-（己酰基）苯硫代氨基甲酰基壳聚糖己酸酯或己酰基壳聚糖异硫氰酸酯）。
Affecting factors to the acyl chitosan isothiocyanate synthesis byN-phenylthiocarbamoylation and the following acylation was investigated using octyl 2-amino-2-deoxy-β-D-glucopyranoside as a model compound. It was found from the acetylation ofN-phenylthiocarbamoyl glucosamine derivative with acetic anhydride/pyridine that the glucosamine isothiocyanate was formed viaN,N-(acetyl)phenylthiocarbamoyl glucosamine derivative and the conversion ofN,N-(acetyl)phenylthiocarbamoyl glucosamine derivative to the glucosamine isothiocyanate proceeded mainly by thermal degradation ofN,N-(acetyl)phenylthiocarbamoyl groups. The reaction temperature was an important factor to the isothiocyanate synthesis. On the other hand, it was found from the acetylation ofN-ethylthiocarbamoyl derivative (orN-allylthiocarbamoyl derivative) with acetic anhydride/pyridine that the glucosamine isothiocyanate was also prepared fromN-ethylthiocarbamoyl glucoamine derivative (orN-allylthiocarbamoyl glucosamine derivative), but thatN-phenylthiocarbamoylation was more preferable to the isothiocyanate synthesis thanN-ethylthiocarbamoylation andN-allylthiocarbamoylation. Then, acylation products ofN-phenylthiocarbamoyl chitosan (N,N-(hexanoyl)phenylthiocarbamoyl chitosan hexanoate or hexanoyl chitosan isothiocynate) could be controlled by the reaction temperature and reaction system.