有机化学 ›› 2011, Vol. 31 ›› Issue (9): 1475-1479. 上一篇    下一篇

研究简报

硫代硫酸钠脱除氨基酸铜络合物中铜的研究

张玲,郑友广,安琳,薛运生,牟杰,刘玲,刘毅*   

  1. (徐州医学院药学院 徐州 221004)
  • 收稿日期:2010-11-15 修回日期:2011-01-26 发布日期:2011-04-11
  • 通讯作者: 张玲 E-mail:zhamgling1999@163.com

A New Method for Removing Copper from Amino Acid-Copper Com-plexes by Sodium Thiosulfate

ZHANG Ling, ZHENG You-Guang, AN Lin, XUE Yun-Sheng, MOU Jie, LIU Ling, LIU Yi   

  1. (Faculty of Pharmacy, Xuzhou Medical College, Xuzhou 221004)
  • Received:2010-11-15 Revised:2011-01-26 Published:2011-04-11

报道了用硫代硫酸钠脱去侧链保护氨基酸铜络合物中铜离子的新方法, 该方法适用于合成Nδ-苄氧羰基鸟氨酸、Nδ-叔丁氧羰基鸟氨酸、Nδ-芴甲氧羰基鸟氨酸、Nδ-乙酰基鸟氨酸、Nδ-邻苯二甲酰基鸟氨酸、Nε-苄氧羰基赖氨酸、Nε-叔丁氧羰基赖氨酸、Nε-芴甲氧羰基赖氨酸、Nε-乙酰基赖氨酸、Nε-邻苯二甲酰基赖氨酸、γ-苄基谷氨酸、β-苄基天门冬氨酸. 产物用元素分析法与1H NMR法进行了表征. 探讨了反应温度、时间、投料比例、溶剂对脱铜反应的影响. 实验结果表明, 以硫代硫酸钠作为脱铜试剂, 侧链保护氨基酸铜络合物与硫代硫酸钠的物质的量比为1∶1或1∶2, 60 ℃反应1.5~2.0 h, 收率与产物纯度均较高. 该方法简便、高效、环境友好.

关键词: 硫代硫酸钠, 脱铜, 氨基酸铜络合物, 保护氨基酸

Sodium thiosulfate efficiently removed copper from amino acid-copper complexes. This new method was suitable for the synthesis of Nδ-benzyloxycarbonyl-L-ornithine, Nδ-tert-butyloxycarbonyl-L-ornithine, Nδ-fluorenylmethyloxycarbonyl-L-ornithine, Nδ-acetyl-L-ornithine, Nδ-phthalyl-L-ornithine, Nδ-benzyloxycarbonyl-L-lysine, Nδ-tert-butyloxycarbonyl-L-lysine, Nδ-fluorenylmethyloxycarbonyl-L-lysine, Nδ-acetyl-L-lysine, Nδ-phthalyl-L-lysine, γ-benzyl-glutamate, β-benzyl-aspartate and their molecular structures were confirmed by elemental analysis and 1H NMR. The effects of reaction remperature, time, materials propor-tion and solvent on copper-removing reaction were studied. It was shown that when Nδ-protective ornithine copper complexes and sodium thiosulfate were reacted with the molar ratio of 1∶1 or 1∶2 at 60 ℃ for 1.5~2.0 h, the product yield and purity were high. The method is rapid, convenient in operation and environment friendly.

Key words: sodium thiosulfate, copper removal, copper-amino acid complex, protected amino acid