有机化学 ›› 2013, Vol. 33 ›› Issue (9): 1999-2003.DOI: 10.6023/cjoc201304024 上一篇    下一篇

研究简报

氢氧化铯催化O,O-二烷基-Se-芳基磷酸酯的合成

李媛媛, 陈四海, 苏柳, 李建华, 许新华   

  1. 湖南大学化学化工学院 长沙 410082
  • 收稿日期:2013-04-17 修回日期:2013-04-28 发布日期:2013-05-13
  • 通讯作者: 许新华 E-mail:xhx1581@hnu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 21273068, 21172061, J1210040, J1103312)资助项目

Synthesis of O,O-Dialkyl-Se-aryl Phosphoroselenoates Catalyzed by Cesium Hydroxide

Li Yuanyuan, Chen Sihai, Su Liu, Li Jianhua, Xu Xinhua   

  1. College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082
  • Received:2013-04-17 Revised:2013-04-28 Published:2013-05-13
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21273068, 21172061, J1210040, J1103312)

在催化量氢氧化铯存在下, O,O-二烷基膦酸酯与二芳基二硒醚在DMSO中、室温、空气氛中反应, 高收率得到磷酸硒酯. 反应机理为氢氧化铯与O,O-二烷基膦酸酯反应生成的(RO)2P-(O)Cs+, (RO)2P-(O)Cs+亲核进攻ArSeSeAr生成磷酸硒酯和ArSe-Cs+, 后者在水存在下, 被氧化得到ArSeSeAr和氢氧化铯. 这方法为合成磷酸硒酯提供了一条简便有效的路径.

关键词: 氢氧化铯, 二芳基二硒醚, O,O-二烷基-Se-苯基膦酸酯

In the presence of cesium hydroxide, using dimethyl sulfoxide (DMSO) as solvent, dialkyl phosphites reacted with diaryldiselenides at room temperature to afford the corresponding Se-aryl phosphoroselenoates in high yields. The reaction mechanism is that dialkyl phosphites reacted with cesium hydroxide to give (RO)2P-(O)Cs+, which underwent nucleophilic attack on ArSeSeAr to give product Se-aryl phosphoroselenoates and ArSe-Cs+, the latter was oxidized in the presence of water to form diaryldiselenides and catalyst cesium hydroxide. The method could provide a new and expedient way for the Se-aryl phosphoroselenoates.

Key words: cesium hydroxide, diaryl diselenide, O,O-dialkyl-Se-arylphosphoroselenoates