高等学校化学学报

高等学校化学学报 ›› 1983, Vol. 4 ›› Issue (3): 317.

• 论文 • 上一篇    下一篇

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

唐除痴, 吴桂萍, 黄润秋, 柴有新   

  1. 南开大学元素有机化学研究所
  • 收稿日期:1981-12-05 出版日期:1983-06-24 发布日期:1983-06-24

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

Tang Chuchi, Wu Guiping, Huang Runqiu, Chai Yiuxin   

  1. Institute of Elemento-Organic Chemistry, Nankai University, Tianjin
  • Received:1981-12-05 Online:1983-06-24 Published:1983-06-24

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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。

Abstract: 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 Patom from the hydrolysis, alcoholysis and aminolysis of 5R, respec tively. Acid-catalysed hydrolysis and alcoholysis of 7Rformed 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 H2O2 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.

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