高等学校化学学报 ›› 1992, Vol. 13 ›› Issue (11): 1406.

• 论文 • 上一篇    下一篇

手性硫代磷酸及其衍生物的研究(Ⅸ)——O-乙基O-苯基硫代磷酰胺水解反应的立体化学

唐除痴, 张绵吉, 张殿坤   

  1. 南开大学元素有机化学研究所, 天津, 300071
  • 收稿日期:1992-01-27 修回日期:1992-05-15 出版日期:1992-11-24 发布日期:1992-11-24
  • 通讯作者: 唐除痴
  • 基金资助:

    国家教育委员会搏士点基金

Studies on Chiral Thiophosphoric Acids and Their Derivatives(Ⅸ)----Stereochemistry of Hydrolysis of O-Ethyl O-Phenyl Thiophosphoramides

TANG Chu-Chi, ZHANG Mian-Ji, ZHANG Dian-Kun   

  1. Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071
  • Received:1992-01-27 Revised:1992-05-15 Online:1992-11-24 Published:1992-11-24

摘要: 旋光活性O-乙基O-苯基硫代磷酰氯在碱存在下与伯胺、仲胺或氨反应,得到构型翻转的O-乙基O-苯基硫代磷酰胺.其酸性水解在6mol/L或9mol/L盐酸/二氧六环中进行,得P—N键断裂的构型翻转产物;碱性水解在1mol/L或3mol/LNaOH/二氧六环中进行,得到以OPh为离去基团的构型翻转产物.水解反应机理用三角双锥(TBP)中间体概念得到合理解释.

关键词: 硫代磷酰胺, 立体化学, 水解反应, 旋光活性, 绝对构型

Abstract: The reaction of optically active(+)-(S)-Oethyl O-phenyl thiophosphorochloride with various primary or secondary amines in the presence of base gave the optically active(-)-or(+)-(S)-O-ethyl O-Phenyl N,N,-dialkyl(or N-alkyl)thiophosphoramides 2 with the inversion of configuration at phosphorus atom.The acid hydrolysis of 2 was carried out in 6 mol/Lor 9 mol/L HCl/dioxane solution,and resulted in the cleavage of P-N bond,giving the products with the inversion of configuration.The alkaline hydrolysis of 2 occurred in 1 mol/Lor 3 mol/L NaOH/dioxane solution,and gave the products with the inversion of configuration with PhOas the leaving group.These hydrolysis mechanisms can be satisfactorily explained in the light of trigonal bipyramidal(TBP)intermediates concept.

Key words: Thiophosphoramide, Stereochemistry, Hydrolysis, Optical activity, Absolute configuration

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