氢氧化铯催化O,O-二烷基-Se-芳基磷酸酯的合成有机化学.pdfVIP

DOI: 10.6023/cjoc201304024 研究简报 有机化学 Chinese Journal of Organic Chemistry NOTE 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* (湖南大学化学化工学院 长沙 410082) 摘要 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) P－(O)Cs＋, (RO) P－(O)Cs＋亲核进攻 ArSeSeAr 生 2 2 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 Synthesis of O,O-Dialkyl-Se-aryl Phosphoroselenoates Catalyzed by Cesium Hydroxide Li, Yuanyuan Chen, Sihai Su, Liu Li, Jianhua Xu, Xinhua* (College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082) Abstract 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) P－(O)Cs＋, which underwent nucleophilic 2 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. Keywords cesium hydroxide; diaryl diselenide; O,O-dialkyl-Se-arylphosphoroselenoates 磷酸硒酯