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  

STUDIES ON CHIRAL THIOPHOSPHORIC ACIDS AND THEIR DERIVATIVES (Ⅲ)——STEREOCHEMISTRY OF SOME REACTIONS IN O-ETHYL O-PHENYL PHOSPHOROTHIOIC ACID AND ITS DERIVATIVES

作　　者：唐除痴[1] 吴桂萍[1] 黄润秋[1] 柴有新[1] Tang Chuchi;Wu Guiping;Huang Runqiu;Chai Yiuxin(Institute of Elemento-Organic Chemistry,Nankai University,Tianjin)

机构地区：[1]南开大学元素有机化学研究所

出　　处：《高等学校化学学报》1983年第3期317-322,共6页Chemical Journal of Chinese Universities

摘　　要：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。The chlorination of ( + )-O-ethyl O-phenyl phosphorothioic acid (1R) with PC15 gave (-)-O-ethyl O-phenyl phosphorothiochloride (5R) and proceeded with inversion of configuration. lR, (-)-O-ethyl O-phenyl O-methyl phosphorothionate (6R) and ( + )- or (-)-O-ethyl O-phenyl N-ethyl(or N, N-diethyl) phosphorothioamide (7R) were obtained with inversion of configuration at P atom from the hydrolysis, alcoholysis and aminolysis of 5R, respec tively. Acid-catalysed hydrolysis and alcoholysis of 7R formed to (-)-O-ethyl O-phenyl phosphorothioic acid (lS) and (+)-O-ethyl O-phenyl O-methyl phosphorothionate(6S) respectively were realized, while both reactions proceeded with inversion. The oxidation of 6R with either H_(2)O_(2) or m-chloroperoxybenzoic acid resulted in (-)-O-ethyl O-methyl O-phenyl phosphoronate (4S) in the same stereochemi-cal course with retention of configuration at P atom, but it was discovered that, by using dimethyl sulphoxide-iodine,6R was isomerized to (-) -O-ethyl O-phenyl S-methyl phosphorothiolate(2R), instead of oxidation to 4S.

关 键 词：立体化学 构型翻转 硫代磷酸 (Ⅲ) 五氯化磷 旋光活性 硫代磷酰氯 手征性 

分 类 号：O62[理学—有机化学]