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化学学报
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化学学报 ›› 1991, Vol. 49 ›› Issue (3): 272-277. 上一篇    下一篇

研究论文

有机磷化合物的研究XXXIX. 溶剂性质对烷基膦酸-O, O-1,3-丙二酯及-O,O-1,4-丁二酯的碱性水解动力学的影响

袁承业;李树森;廖秀高   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1991-03-15

Studies on organophosphorus compounds XXXIX. Solvent effect on the alkaline hydrolysis of 2-alkyl-2-oxo-1, 3-dioxaphosphorinane and-phosphepane

YUAN CHENGYE;LI SHUSEN;LIA XIUGAO   

  • Published:1991-03-15

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本文报道烷基膦酸-O, O-1,3-丙二酯及O, O-1,4-丁二酯于50%二甲亚砜水溶液中的水解动力学, 考察了取代基结构对膦酸酯水解速率常数的影响。通过它们在50%的二甲亚砜水溶液和50%的二氧六环水溶液中碱性水解速率常数的比较, 说明在这些混合溶液中, 烷基的空间结构对水解速率常数的影响是近似平行的。同时, 正丙基膦酸-O, O-1,3-丙二酯于不同混合溶剂中碱性水解时, 溶剂分子的给质子接受质子的能力对水解反应过程有重要影响。

关键词: 溶剂, 亚砜, 反应动力学, 水解, 有机磷化合物, 膦酸酯类, 反应速度常数, 取代基, 烷基

The kinetic behavior of alkaline hydrolysis of 2-alkyl-2-oxo-1,3-dioxaphosphorinane and phosphepane in various solvents was investigated. In 50% aqueous DMSO, alkaline hydrolysis of these two cyclic esters of alkylphosphonates behaves as a second order reaction. Multiple regression analyses involving log k with s* and DDE gave very good results. It showed that the alkyl substituents effect on the rate of hydrolysis of these two alkylphosphonates is very similar. Log k for alkaline hydrolysis in various solvents do not relate either with the dielec. constant or with the solvent parameter ET. However, the strength of proton-donor and acceptor solvents showed significant influence on the alkaline hydrolysis of the title compounds

Key words: SOLVENTS, SULFOXIDE, REACTION KINETICS, HYDROLYSIS, ORGANO PHOSPHORUS COMPOUNDS, PHOSPHONIC ACID ESTER, REACTION RATE CONSTANT, SUBSTITUENT GROUP, ALKYL

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