化学学报 ›› 1980, Vol. 38 ›› Issue (4): 339-350. 上一篇    下一篇

论文

有机磷化合物的研究 Ⅶ.二丁基膦酸酯的合成及其碱性水解反应

袁承业, 袁群   

  1. 中国科学院上海有机化学研究所
  • 投稿日期:1978-06-20 发布日期:2013-06-03

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS Ⅶ. SYNTHESIS AND ALKALINE HYDROLYSIS OF THE ESTERS OF DIBUTYLPHOSPHINIC ACID

YUAN CHENG-YE, YUAN QUN   

  1. Shanghai Institute of Organic Chemistry, Academia Sinica
  • Received:1978-06-20 Published:2013-06-03

提供一个由氧化二丁基膦在四氯化碳存在下与碱、醇或酚反应,合成二丁基瞵酸及其酯的方法。研究二丁基瞵酸对位取代苯酯的取代基性质与超加折射值、纸上层析比移值与紫外光谱的关系。取代基团的σ值与红外光谱特征频率及Lewis碱性参数间均有良好的线性关系。应用电导法测得二丁基瞵酸对位取代苯酯的等浓度碱性水解速度常数,计算了相应的活化能。这些常数与取代基的σ值均存在线性关系,并在此基础上讨论了碱性水解反应机理。为探讨磷-氧键的dπ-pπ键特性,比较了相应羧酸的水解行为。

A new method ha.s beon reported for the preparation of dibutylphosphinic acid and its esters based on the reaction of dibutylphosphine oxide with water or alcohols and a base in the presence of carbon tetrachloride.As dialkylphosphonate and monoal-kylphosphonate, dialkylphosphi.nc; oxide can also effect oxidative phosphinylation of hydroxy compounds though the yield is rather poor.It is in consequence of the enhancement of the electron density of phosphorus atom by the inductive effect of alkyl groups.It is thus proposed that the reaction operates by an ionic process rather than a radical mechanism.Dibutylphosphinic acid obtained in this way is proved to be identical with that synthesized by classical methods in its behaviour in paper chromatography, paper electrophoresis, potentiometric titration and infrared spectra.With dicyclohegylamin), quinine as well as S-bonzylisothiouronium chloride dibutylphosphinic acid forms crystalline salts with sharp melting pointy.