化学学报 ›› 1983, Vol. 41 ›› Issue (9): 834-842. 上一篇    下一篇

研究论文

有机磷化合物的研究 X:五价膦(磷)酸酯与卤代烷在卤化钠存在下的酯烷基交换反应

袁承业;叶伟贞;周国伟   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1983-09-15

Studies on organophosphorous compounds X: The ester alkyl exchange reaction of quinque-valent phosphorus esters with alkyl halide in the presence of sodium halide

YUAN CHENGYE;YE WEIZHEN;ZHOU GUOWEI   

  • Published:1983-09-15

关键词: 钠化合物, 反应机理, 卤化物, 有机磷化合物, 卤代烃, 磷酸酯类, 五价, 酯交换

A detailed study on the ester alkyl exchange reaction of various types of quinique-valent phosphorus esters with alkyl halide in the presence of sodium bromides was reported. This ester alkyl exchange reaction was evidently influenced by the structure of phosphorus esters and alkyl halides as well as by the nature of the halides of metal ions. In contrast with the reaction without sodium hadlide, the alkyl phosphinmate is more reactive than phosphonate and phosphate by treatment with alkyl halide in the presence of sodium halide. This is consistent with the high nucleophilicity of >P(CO)O- as leaving group. The reactivity of butyl halides was decreased in the following order: n-BuBr>i-BuBr=s-BuBr>t-BuBr. Alkyl iodide was proved to be more reactive than the corresponding bromide and chloride. However, the use of iodioe is limited by the formation of alkene resulted from the elimination of HI. These structural effects show the general characteristics of a nucleophilic substitution reaction. A reaction mechanism involving the formation of sodium salt intermecutiate was proposed based on the concept of HSAB principle. This reaction may, however, be used as a convenient method for the preparation of mixed esters of quinque-valent phosphorus acids.

Key words: SODIUM COMPOUNDS, REACTION MECHANISM, HALIDE, ORGANO PHOSPHORUS COMPOUNDS, HALOHYDROCARBON, PHOSPHORIC ACID ESTER, PENTAVALENCE, TRANSESTERIFICATION

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