高等学校化学学报

高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (7): 940.

• 研究论文 • 上一篇    下一篇

O,O-二乙基亚磷酰基异氰酸酯与亚苄基苯胺的反应研究

杨华铮, 吕健斌   

  1. 南开大学元素有机化学研究所, 天津 300071
  • 收稿日期:1992-07-03 修回日期:1993-04-02 出版日期:1993-07-24 发布日期:1993-07-24
  • 通讯作者: 杨华铮.
  • 作者简介:第一作者:女, 57岁, 教授.
  • 基金资助:

    国家自然科学基金

Studies on the Reaction of Diethoxyisocyanatophosphine with Benzalanilines

YANG Hua-Zheng, LU Jian-Bin   

  1. Institute of Elemento-Organic Chemistry, , Nankai University, Tianjin, 300071
  • Received:1992-07-03 Revised:1993-04-02 Online:1993-07-24 Published:1993-07-24

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被引次数

1

摘要： O,O-二乙基亚磷酰基异氰酸酯与亚苄基苯胺反应,当亚苄基苯胺分子中苯环上具有邻位取代基时,产物不是稳定的1,3,4-二氮磷杂环戊烷衍生物,却是α-(O,O-二乙基)膦酰基苄基苯胺.这可能是由于邻位取代基的立体效应阻碍了环加成反应,且中间体水解之故.所得化合物均经元素分析、IR、H、N、AF及MS谱证实.

关键词: 环加成反应, 1, 3, 4-二氮磷杂环戊烷, 磷酰基异氰酸酯, 亚苄基苯胺

Abstract: Two kinds of compounds were synthesized by the reaction of diethoxyisocyanatophosphine with benzalanilines depending at the different positions of substituents attached to the benzene ring.When there was no substituent or the substituent was at m-, or p-position, the normal 1,3-dipolar cy-cloaddition took place to yield a stable compound 2, 1,3,4-diazaphospholidene, through a rearrangement of ethyl from Oatom to Natom.The effects of the reaction temperature and solvent were investigated and the diastereoisomers of compound 2 were separated by TLC.However, when the substituent was at o-position, compound 5, a-anilino phosphonate was obtained under the same experimental conditions.Aconclusion might be drawn that the steric hindrance effect of the ortho substituent block the cycloaddition and the intermediate was hydrolyzed by the moisture.Elementary analysis, 1H NMR, IRand MSspectra confirmed the structures of the compounds.

Key words: Cycloaddition reaction,1,3,4-Diazaphospholidene, Diethoxyisocyanatophosphine, Ben-zalaniline

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