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

Chem. J. Chinese Universities ›› 1993, Vol. 14 ›› Issue (12): 1682.

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

TANG Chu-Chi, ZHANG Mian-Ji

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

Abstract

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

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