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手征性硫代磷酸及其衍生物的研究(Ⅲ)——旋光活性O-乙基O-苯基硫代磷酸及其衍生物的某些反应的立体化学 总被引:1,自引:1,他引:0
本文报导了(+)-O-乙基O-苯基硫代磷酸(1R)与五氯化磷反应得到构型翻转的产物(-)-O-乙基O-苯基硫代磷酰氯(5R);5R经水解、醇解及胺解,均发生了构型翻转,并讨论了这些产物某些反应的立体化学过程。 相似文献
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The reaction of optically active O-ethyl O-phenyl phosphorochloride 1 with alcohol, phenol,amine, mercaptan or thiophenol, respectively, in the presence of an alkali obtained optically activeO-ethyl O-phenyl phosphorothioic derivatives 2 with inversion of configuration. The hydrolysis of 2was carried out in 1 N NaOH-dioxane solution. The hydrolysis of 2a and 2h predominantly gaveproducts with inversion of configuration with OPh as leaving group, but also gave products withretention of configuration with OMe or SPr as leaving group. Exclusive products with inversion ofconfiguration with OPh as leaving group were only obtained from the hydrolysis of 2b, 2f and 2g.The hydrolysis of 2c gave product with inversion of configuration with OC_6H_4NO_2-p as leavinggroup. From 2d, 2e and 2i, products with retention of configuration were formed with OC (Me)-CHCO_2 Et(Z), OC(Me)-CHCO_2Et(E) and SPh as leaving group, respectively. All the above resultscan be satisfactorily interpreted in the light of trigonal bipyram 相似文献
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旋光活性的O-乙基O-苯基硫代磷酰氯1在碱存在下与醇、酚、胺、硫醇或硫酚反应得到构型翻转的O-乙基O-苯基硫代磷酸衍生物2。2的水解在1N NaOH液-二氧六环中进行。2a及2h的水解主要得到以OPh作为离去基的构型翻转的产物,部分得到以OMe或SPr作为离去基的构型保留的产物。2b,2f和2g的水解唯一地得到以OPh作为离去基的构型翻转产物。从2c得到的却是OC_6H_4NO_2-P作为离去基的构型翻转产物。从2d,2e及2i分别得到以OC(Me)=CHCO_2Et(Z),OC(Me)=CHCO_2Et(E)及SPh作为离去基的构型保留产物。这些结果均能用三角双锥(TBP)中间体概念和假旋转(BPR)概念来完满地解释。 相似文献