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  

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

作　　者：唐除痴[1] 张绵吉[1] 张殿坤[1] 

机构地区：[1]南开大学元素有机化学研究所,天津300071

出　　处：《高等学校化学学报》1992年第11期1406-1410,共5页Chemical Journal of Chinese Universities

基　　金：国家教育委员会搏士点基金

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6 mol/L或9 mol/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1 mol/L或3 mol/L NaOH/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.The reaction of optically active(+)-(S)-O ethyl 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/L or 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/L or 3 mol/L NaOH/dioxane solution,and gave the products with the inversion of configuration with PhO as the leaving group.These hydrolysis mechanisms can be satisfactorily explained in the light of trigonal bipyramidal(TBP)intermediates concept.

关 键 词：硫代磷酰胺 立体化学 水解反应 

分 类 号：O623.733[理学—有机化学]