Chen Xiao-lan, Liao Xin-cheng, Lu Jian-sha, Guo Lei, Qu Ling-bo, Zhao Yu-fe
Chemistry Department, Zhengzhou University, Zhengzhou, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2004 Mar;24(3):379-80.
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.
阿特金森-托德反应已被广泛应用于磷酸盐和磷酰胺的合成。在阿特金森-托德反应条件下,亚磷酸二烷基酯可能转化为磷酰氯二烷基酯。我们曾尝试用阿特金森-托德反应合成水杨酸磷酸盐。但当水杨酸的-COOH未受保护时,产率相当低。发现-COOH可能参与了反应。水杨酸的-COOH和-OH之间可能存在竞争反应。为了了解详细机制,选择水杨酸乙酯进行磷酸化。最后,通过将DEPH和四氯化碳滴入水杨酸乙酯、三乙胺和二氧六环的混合溶液中,对经典的阿特金森-托德方法进行改进,成功地使水杨酸乙酯磷酸化,产率良好。通过核磁共振和电喷雾电离串联质谱数据对结构进行了阐明。