高等学校化学学报

高等学校化学学报 ›› 1983, Vol. 4 ›› Issue (1): 87.

• 论文 • 上一篇    下一篇

手征性硫代磷酸及其衍生物的研究(Ⅱ)——旋光活性的O-乙基O-苯基硫代磷酸及其硫(醇)代酯的绝对构型

唐除痴, 吴桂萍   

  1. 南开大学元素有机化学研究所
  • 收稿日期:1981-09-12 出版日期:1983-02-24 发布日期:1983-02-24

STUDIES ON CHIRAL THIOPHOSPHORIC ACIDS AND THEIR DERIVATIVES (Ⅱ) -ABSOLUTE CONFIGURATIONS OF THE OPTICAL ACTIVE O-ETHYL O-PHENYL PHOSPHOROTHIOIC ACID AND ITS THIOL-ESTERS

Tang Chuchi, Wu Guiping   

  1. Institute of Elemento-Organic Chemistry, Nankai University, Tianjin
  • Received:1981-09-12 Online:1983-02-24 Published:1983-02-24

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摘要： O一乙基-O-苯基硫代磷酸(1)及其硫(醇)代酯(2)的绝对构型可由以下两步反应确定(见图1)。即,(-)-(2)的氯化和(-)-O-乙基-O-苯基磷酰氯(3)的酯化反应。由(-)-(2)→(-)-(3)氯化反应的立体化学过程已a.R′=CH3 b.R′=n-pr c.R′=CH2CH2OC2H5经证明,不管是使用氯气还是使用SO2Cl2为氯化剂,均为磷原子构型保留,由(-)-(3)生成(-)-O-乙基-O-甲基O-苯基磷酸酯(4)的反应则使构型翻转。同时(-)-(4)构型已知为(R)-(+)-(4)、(S)-(-)-(4),所以(+)-(1)和(-)-(2)的绝对构型可确定为:(R)-(+)-(1)和(R)-(-)-(2)。这一结果与X-射线衍射法所得结果完全一致。

Abstract: The absolute configurations of O-ethyl O-phenyl phosphorothioic acid ( 1) and its thiol-esters (2) were established by the following reactions (Scheme l.):the chlorination of (-)-(2)and esterification of (-)-O-ethyl O-phenyl phosphorochloride; (3) It has been confirmed that the chlorination of (-)-(2) either with Cl2 or SO2 Cl2 proceeds with retention of the configuration, and the esterification of(-)-(3) forms (-)-O-ethyl O-methyl O-phenyl phosphate; (4) proceeding with complete inversion of its configuration..a.R′=CH3 b.R′=n-pr c.R′=C2H2OET Since the absolute configurations of (-)-(4) are kno wn as: (S)-(-)-(4), (R)-( + )-(4), the absolute configurations of ( + )-(1) and (-)-(2 ) should be (R)-( + )-(l) and (R)-(-)-(2),respectively. This result consists with that one obtained by X-ray diffraction method.

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