高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (2): 229.

• 论文 • 上一篇    下一篇

O,O-二烷基硫代磷(膦)酸酯与三氯氧磷的异构化/氯化反应机理初探

唐除痴, 马缚鹏, 贺峥杰   

  1. 南开大学元素有机化学研究所, 天津, 300071
  • 收稿日期:1996-04-01 出版日期:1997-02-24 发布日期:1997-02-24
  • 通讯作者: 唐除痴, 男, 57岁, 教授
  • 作者简介:唐除痴, 男, 57岁, 教授
  • 基金资助:

    国家自然科学基金

Preliminary Research on Mechanism of the Isomerization/Chlorination of O, O-Dialkylthiophosphate (-onate)with Phosphorus Oxychloride

TANG Chu-Chi, MA Fu-Peng, HE Zheng-Jie   

  1. Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071
  • Received:1996-04-01 Online:1997-02-24 Published:1997-02-24

摘要: O,O-二烷基硫代磷(膦)酸酯(1)与三氯氧磷作用得到S-烷基硫代磷酰氯(2)和O-烷基磷酰二氯(3),此反应包含异构化和氧化两个过程.实验结果表明,1的预期氯化产物O-烷基硫代磷(膦)酰氯酯(5)与三氯氧磷不发生反应,而1的预期异构化产物O,S-二烷基硫代磷(膦)酸酯(6)与三氯氧磷能顺利反应得到2.由此推测,在1的异构化/氯化反应中,异构化很可能发生在氯化之前.根据此结果和三角双锥中间体(TBP)概念,提出了该反应初步的可能机理.

关键词: 硫代磷(膦)酸酯, 硫代磷(膦)酰氯酯, 异构化反应, 氯化反应, 反应机理

Abstract: In the previous papers, we reported that O,O-dialkylthiophosphate(-onate) 1 reacted with phosphorus oxychloride to give S-alkyl thiophosphoro (-on-)chloridate 2 and Oalkyl phosphorodichloridate 3.Obviously both of isomerization and chlorination occurred in this reaction.The recent experimental results show that phosphorus oxychloride doesn' t react with O-alkyl thiophosphoro(-no)chlorldate 5 which is a desired chlorination product of 1,while it can smoothly react with O,S-dialkythiophosphate(-onate) 6 which is a desired isomerization product of 1 to give 2- Based on this fact we suggest that the isomerization may occur ahead of the chlorination in the isomerization/chlorination of 1.In the light of the above results and trigonal bipyramid (TBP) intermediate concept, the mechanism 0f the isomerization /chlorination of 1 is discussed.

Key words: Thiophosphate (-onate), Thiophosphoro(-no)chloridate, Isomerization, Chlorination, Reaction mechanism

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