高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (S1): 403.

• Physical Organic Chemistry • 上一篇    下一篇

Substituent Effects And Structure-Reactivity Relationship of Organophosphorus Compounds

Wenxiang HU1,2, Chengye YUAN1, Shushen LI1, Jianying WANG1,2   

  1. 1. The Centre of Research and Development of Medicine and Pharmaceuticals, Commission of Science & Technology and Industry for National Denfence, Beijing 100101;
    2. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • 出版日期:1998-12-31 发布日期:1998-12-31

Substituent Effects And Structure-Reactivity Relationship of Organophosphorus Compounds

Wenxiang HU1,2, Chengye YUAN1, Shushen LI1, Jianying WANG1,2   

  1. 1. The Centre of Research and Development of Medicine and Pharmaceuticals, Commission of Science & Technology and Industry for National Denfence, Beijing 100101;
    2. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Online:1998-12-31 Published:1998-12-31

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摘要： To evaluate the substituent effect in organophosphorus compounds, a series of model compounds, namely 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2] octane-1-oxides, alkyl hydrogen p-substituted phenyl-phosphonates, dialkyl p-substituted phenylphosphonates, as well as alkyl hydrogen alkylphosphonates, were synthesized and studied. Since in these compounds the substituents are located far away from reaction centre and the contribution of the steric effect of substituents can thus be eliminated, the substituent polar effect was evaluated based on 31P NMR, pKa and charge density of phosphoryl oxygen of these compounds calculated by the quantum mechanies MNDO method. The results showed that the polar effects of substituent in carboxylic and organophosphorus esters are similar, and the variation in polar effect among the alkyl groups is not significant. In the meantime, some steric parameters Esp of substituents were suggested for organophosphorus compounds, which are different from the Taft's Es and Charton's υ parameters[1,2].

Abstract: To evaluate the substituent effect in organophosphorus compounds, a series of model compounds, namely 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2] octane-1-oxides, alkyl hydrogen p-substituted phenyl-phosphonates, dialkyl p-substituted phenylphosphonates, as well as alkyl hydrogen alkylphosphonates, were synthesized and studied. Since in these compounds the substituents are located far away from reaction centre and the contribution of the steric effect of substituents can thus be eliminated, the substituent polar effect was evaluated based on 31P NMR, pKa and charge density of phosphoryl oxygen of these compounds calculated by the quantum mechanies MNDO method. The results showed that the polar effects of substituent in carboxylic and organophosphorus esters are similar, and the variation in polar effect among the alkyl groups is not significant. In the meantime, some steric parameters Esp of substituents were suggested for organophosphorus compounds, which are different from the Taft's Es and Charton's υ parameters[1,2].

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