有机化学 ›› 2017, Vol. 37 ›› Issue (9): 2369-2376.DOI: 10.6023/cjoc201702016 上一篇    下一篇

研究论文

α-氨基亚甲基膦酸酯构建偕二胺衍生物

黄晓丽, 任林静, 蒲家志, 贺春阳, 姚秋丽   

  1. 遵义医学院药学院 遵义 563000
  • 收稿日期:2017-02-15 修回日期:2017-05-04 出版日期:2017-09-25 发布日期:2017-05-04
  • 通讯作者: 姚秋丽 E-mail:yaoqiuli@zmc.edu.cn
  • 基金资助:

    国家自然科学基金基金(No.21462056)、贵州省联合基金(No.[2014]7542)及贵州省大学生创新(No.201610661006)资助项目

An Access to the gem-Diamine Derivatives from α-Carbamatemethylphosphonate

Huang Xiaoli, Ren Linjing, Pu Jiazhi, He Chunyang, Yao Qiuli   

  1. School of Pharmacy, Zunyi Medical University, Zunyi, 563000
  • Received:2017-02-15 Revised:2017-05-04 Online:2017-09-25 Published:2017-05-04
  • Contact: 10.6023/cjoc201702016 E-mail:yaoqiuli@zmc.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21462056), the Science and Technology Foundation of Guizhou Province (No.[2014]7542) and the Education Department of Guizhou Province (No. 201610661006).

报道了由α-氨基亚甲基膦酸酯构建膦酸酯的偕二胺衍生物的研究.在前期的研究中,磺砜与磷酸二乙酯的反应主要生成产物α-氨基亚甲基膦酸酯;当降低磷酸二乙酯的用量时,检测到另一副产物——α-氨基亚甲基膦酸酯的偕二胺衍生物.研究表明这一类独特的化学结构具有潜在的抗癌活性,但关于其合成的研究报道很少,针对这一背景,进一步研究了这一类型化合物的合成方法学.以石油醚作为溶剂,在氢氧化锂碱性条件下,α-磺酰烷氨基甲酸酯与α-烷氧酰胺亚甲基膦酸酯反应,能以良好至优秀的产率顺利地合成α-氨基亚甲基膦酸酯的偕二胺衍生物.该方法操作简便,条件温和,底物适用性广.

关键词: α-氨基亚甲基膦酸酯, 偕二胺衍生物, 磺砜

The preparation of gem-diamine derivatives of phosphonates from α-carbamatemethylphosphonates is reported. In our earlier work, the reaction of sulfone with dialkylphosphonate gave α-carbamatemethylphosphonate as the major product. However, gem-diamine derivative of phosphonate was unexpectedly formed as a side product when decreasing the amount of dialkylphosphonate. Although few reports exist on the synthesis of this unique structure, gem-diamine derivatives have shown potential biological activity as an anti-cancer reagent. After optimization, a methodology for the synthesis of gem-diamine derivatives of α-carbamatemethylphosphonate is provided. The reaction of α-carbamatemethylsulfone with α-carbamatemethylphosphonate using LiOH as a base and commercial petroleum ether as solvent provided gem-diamine derivatives in good to excellent yields. This simple protocol runs under very mild conditions, and has a broad substrate scope.

Key words: α-carbamatemethylphosphonate, gem-diamine derivatives, sulfone