1. Chemistry Deparment, Zhengzhou University, Zhengzhou 450052，China 2. The Key Laboratory for Biooganic Phosphorus Chemistry, Ministry of Education, School of Life Science and Engineering, Tsinghua University, Beijing 100084, China
Abstract：Atherton-Todd reaction has been extensively applied to the synthesis of phosphates and phosphoroamidates. Under Atherton-Todd reaction conditions, dialkyl phosphites were probably transformed into diakyl phosphorochloridates. We have tried to use Atherton-Todd reaction to synthesize phosphate of salicylic-acid. But when the —COOH of salicylic acid was under unprotected, the yield was quite low. It was found that the —COOH possibly participated in the reaction. The competitive reaction between the —COOH and —OH of salicylic acid probably existed. In order to understand the detail mechanism, ethyl-salicylate was selected to be phosphorylated. In the end, ethyl-salicylate successfully phosphorylated by modification of the classical Atherton-Todd procedure through dropping the DEPH and tetrachloromethane into the mixed solution of ethyl-salicylate, triethylamine and dioxane with good yields. The structures were elucidated by NMR and ESI/MS/MS data.
[1] CHEN Chang-mei，TONG Chun-yuan，FAN Chang et al. Journal of Tsinghua University(Science and Technology)(清华大学学报(自然科学版))，2001，41(7)S1：94. [2] LI Zheng-hua(李正化主编). Medicinal Chemistry(Third Edition)(药物化学(第三版)). Beijing: People's Medical Publishing House(北京：人民卫生出版社), 1993. 152. [3] Athion F R, Dpenshaw H T, Todd A R. J. Chem. Soc., 1945. 382.
