高等学校化学学报

高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (12): 1682.

• 研究论文 • 上一篇    下一篇

手性硫代磷酸及其衍生物的研究(Ⅹ)——O-乙基-O-苯基硫代磷酰胺酯甲醇解反应的立体化学

唐除痴, 张绵吉   

  1. 南开大学元素有机化学研究所, 天津 300071
  • 收稿日期:1992-12-04 修回日期:1993-07-05 出版日期:1993-12-24 发布日期:1993-12-24
  • 通讯作者: 唐除痴, 男, 55岁, 教授.
  • 作者简介:唐除痴, 男, 55岁, 教授.
  • 基金资助:

    国家教委博士学科点专项科研基金

Studies on Chiral Thiophosphoric Acids and Their Derivatives (Ⅹ) ——Stereochemistry of Methanolysis of O-Ethyl-O-Phenyl Thiophosphoramidates

TANG Chu-Chi, ZHANG Mian-Ji   

  1. Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071
  • Received:1992-12-04 Revised:1993-07-05 Online:1993-12-24 Published:1993-12-24

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摘要： 旋光活性O-乙基-O-苯基硫代磷酰胺酯在4.7mol/LHCl-MeOH溶液中进行酸性甲醇解时得到P—N键断裂的构型翻转产物,与MeONa-MeOH的碱性甲醇解得到以PhO基为离去基的构型翻转产物.两种甲醇解反应的机理均可用三角双锥(TBP)中间体概念完满地解释.

关键词: 硫代磷酰胺酯, 甲醇解, 绝对构型, 立体化学

Abstract: Optically active (+)-or(--)-(R)-0-ethyl-O-phenyl thiophosphoramidates 2 were obtained with the inversion of configuration at phosphorus atom by the reaction of optically active (--)-(R)-O-ethyl-O-phenyl thiophosphorochloridate 1 with various primary or secondary amines, or ammonia in the presence of base.The acid methanolysis of 2 was carried out in 4.7 mol/L HCl-MeOHsolution, and resulted in cleavage of P-Nbond to give the products with the inversion of configuration.The alkaline methanolysis of 2 occurred in MeONa-MeOHsolution, and gave the products with the inversion of configuration with PhOas a leaving group.These results can be satisfactorily interpreted in the light of trigonal bipyramidal(TBP) intermediates concepts.

Key words: Thiophosphoramidate, Methanolysis, Absolute configuration, Stereochemistry

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