磷酸苯基二乙基酯的合成及波谱检测  

Study on the Phosphorylaions Reaction between Ethyl Salicylate and DEPH

作　　者：陈晓岚[1] 廖新成[1] 卢建莎[1] 郭蕾[1] 屈凌波[1] 赵玉芬[1] 

机构地区：[1]郑州大学化学系,河南郑州450052

出　　处：《光谱学与光谱分析》2004年第3期379-380,共2页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金 (39870 4 1 5);2001河南省拨院士基金

摘　　要：作为有机磷小分子化合物 ,磷酰胺及其酯类衍生物大多具有广泛的生物活性。磷作为生命的重要元素 ,在生命体系中处于一种重要的地位 ,研究磷参与的生命过程的化学本质 ,对于更好地认识生命体及人类自身都具有重要意义。从化学意义上讲 ,磷参与的绝大部分生命过程 ,其化学本质都是磷酰基转移反应 ,对于这样一类生物体普遍存在的磷酰基转移反应 ,亦可应用到医药和农药上 ,对一些官能团进行结构改造 ,以改变其活性及仿生作用。Atherton Todd反应是合成此类物质极有价值的方法。为了进一步改善和提高水杨酸类药物的仿生作用 ,作者曾采用Atherton Todd反应合成了水杨酸羟基磷酸酯 ,但产率偏低。因此怀疑是水杨酸中羧基和羟基与磷酰化试剂发生竞争反应时羧基更具反应活性 ,为进一步探讨原因 ,文章选择了不含羧基的酯化过的水杨酸乙酯作为磷酰化反应的对象。结果首次采用改造后的Atherton Todd反应成功地制备出o [邻乙氧甲酰 (基 )苯基 ]磷酸二乙酯 ,并具较高产率。文章进一步详细给出了o [邻乙氧甲酰 (基 )苯基 ]磷酸二乙酯NMR谱数据 ,首次探讨了其ESI MS质谱裂解规律 。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.

关 键 词：磷酸苯基二乙基酯 合成 波谱检测 水杨酸类药物 Atherton-Todd反应 核磁共振 

分 类 号：TQ463[化学工程—制药化工]