高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (07): 1631-1634.doi: 10.3969/j.issn.0251-0790.2012.07.047

• 高分子化学 • 上一篇    

位点可控的二乙氧磷酰化壳寡糖的合成

马力, 李克让, 李利民, 刘蒲   

  1. 郑州大学化学系, 郑州 450001
  • 收稿日期:2011-06-17 出版日期:2012-07-10 发布日期:2012-07-10
  • 通讯作者: 刘 蒲, 女, 博士, 教授, 主要从事功能高分子材料的研究. E-mail: liupu@zzu.edu.cn E-mail:liupu@zzu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20872134)资助.

Site-Controlled Synthesis and the Optimum Reaction Conditions of Diethoxy Phosphoryl Chitooligosaccharides

MA Li, LI Ke-Rang, LI Li-Min, LIU Pu   

  1. Department of Chemistry, Zhengzhou University, Zhengzhou 450001, China
  • Received:2011-06-17 Online:2012-07-10 Published:2012-07-10

摘要: 以壳寡糖(COS)为原料, 二乙基亚磷酸酯(DEPH)为磷酰化试剂, 通过改变反应体系中三乙胺(TEA)的用量控制二乙基磷酰基的进攻位点, 实现了2-N和3,6-O位点二乙基亚磷酰化壳寡糖衍生物的合成, 制备了N-二乙氧磷酰化壳寡糖及N,O,O-二乙氧磷酰化壳寡糖, 并采用单一变量法对合成条件进行了优化, 用31P NMR对产物进行了跟踪分析. 合成N-二乙氧磷酰化壳寡糖的最优反应条件为2 g COS, nCOSnTEA=1∶6, nCOSnDEPH=1∶3, 滴加DEPH和CCl4的时间为2 h, 低温反应2 h, 在该优化条件下产物的磷含量为1.50%(质量分数). 合成N,O,O-二乙氧磷酰化壳寡糖的最优反应条件为2 g COS, nCOSnTEA=1∶6, nCOSnDEPH=1∶5, 滴加DEPH和CCl4 的时间2 h, 低温反应4 h, 常温反应8 h, 在该优化条件下产物的磷含量为3.42%. 对合成反应的可能机理进行了推测.

关键词: 壳寡糖, 位点可控, 二乙氧磷酰化壳寡糖

Abstract: Using low molecular weight chitooligosaccharide and dialkyl phosphite as raw materials, the site-controlled diethoxy phosphoryl chitooligosaccharides were synthesized through varying the amount of triethlamine. Then, N-diethoxy phosphoryl chitooligosaccharide and N,O,O-diethoxy phosphoryl chitooligosaccharide were obtained. The optimal synthetic conditions were studied by the single factor variable method. And the optimum reaction conditions of N-diethoxy phosphoryl chitooligosaccharide were as follows: 2 g COS, nCOSnTEA=1∶6, nCOSnDEPH=1∶3, 2 h for the time of dropwise for the solution of DEPH in CCl4, 2 h for the time at the low temperature. The maximum phosphorus content achieves 1.50% under the optimum conditions. The optimum reaction conditions of N,O,O-diethoxy phosphoryl chitooligosaccharide were as follows: 2 g COS, nCOSnTEA=1∶6, nCOSnDEPH=1∶5, 2 h for the time of dropwise for the solution of DEPH in CCl4, 4 h for the time at the low temperature, 8 h for the reaction time at the room temperature. The maximum phosphorus content achieves 3.42% under the optimum conditions. Moreover, a possible reaction mechanism was proposed to explain the formation of diethoxy phosphoryl chitooligosaccharides.

Key words: Chitooligosaccharide, Locus control, Diethoxy phosphoryl chitooligosaccharide

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