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

Abstract

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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TANG Chu-Chi, ZHANG Mian-Ji, ZHANG Dian-Kun . Studies on Chiral Thiophosphoric Acids and Their Derivatives(Ⅸ)----Stereochemistry of Hydrolysis of O-Ethyl O-Phenyl Thiophosphoramides[J]. Chem. J. Chinese Universities, 1992, 13(11): 1406.

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

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