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高等学校化学研究 ›› 2003, Vol. 19 ›› Issue (1): 32-36.

• Articles • 上一篇    下一篇

Syntheses of 10-Hydroxy-5,10-dihydrophenophosphazine 10-Oxide and Its Methyl Derivatives

YIN Zhi-gang1,2, ZHAO De-feng1   

  1. 1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, P. R. China;
    2. Chemical Engineering Department, Zhengzhou Institute of Light Industry, Zhengzhou 450002, P. R. China
  • 收稿日期:2001-11-29 出版日期:2003-01-24 发布日期:2011-08-06
  • 基金资助:

    Supported by National Natural Science Foundation of China(No.29972006).

Syntheses of 10-Hydroxy-5,10-dihydrophenophosphazine 10-Oxide and Its Methyl Derivatives

YIN Zhi-gang1,2, ZHAO De-feng1   

  1. 1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, P. R. China;
    2. Chemical Engineering Department, Zhengzhou Institute of Light Industry, Zhengzhou 450002, P. R. China
  • Received:2001-11-29 Online:2003-01-24 Published:2011-08-06
  • Supported by:

    Supported by National Natural Science Foundation of China(No.29972006).

PDF (PC)

摘要： Ph2NH and PCl3 interacted at a molar ratio of 1∶1.05 and slow-elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H2O to produce a very hard brown solid believed to be a mixture of 5,10-dihydrophenophosphazine 10-oxide(1a) and 10,10'(5H,5H')-spirobipenophosphazinium chloride(1b). This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10-hydroxy-5,10-dihydropheno-phosphazine 10-oxide(2) with a higher yield(45%) than that of the literature(27%). When treated with excess SOCl2, compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10-methoxy-5,10-dihydrophenophosphazine 10-oxide in 70% as treated with NaOMe in methanol. Compound 2 could also be converted to a bisanion when treated with NaH in DMF. The resulted bisanion reacted with MeI to give 5-methyl-10-hydroxy-5,10-dihydrophenophosphazine 10-oxide in a 73% yield which would be converted to 5-methyl-10-methoxy-5,10-dihydrophenophosphazine 10-oxide in a 56% yield by the same way of synthesizing 10-methoxy-5,10-dihydrophenophosphazine 10-oxide. All these compounds obtained were identified by surveying their melting points, and spectra and elemental analysis.

关键词: Synthesis, 5, 10-Dihydrophenophosphazine, Derivative, Structure identification

Abstract: Ph2NH and PCl3 interacted at a molar ratio of 1∶1.05 and slow-elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H2O to produce a very hard brown solid believed to be a mixture of 5,10-dihydrophenophosphazine 10-oxide(1a) and 10,10'(5H,5H')-spirobipenophosphazinium chloride(1b). This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10-hydroxy-5,10-dihydropheno-phosphazine 10-oxide(2) with a higher yield(45%) than that of the literature(27%). When treated with excess SOCl2, compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10-methoxy-5,10-dihydrophenophosphazine 10-oxide in 70% as treated with NaOMe in methanol. Compound 2 could also be converted to a bisanion when treated with NaH in DMF. The resulted bisanion reacted with MeI to give 5-methyl-10-hydroxy-5,10-dihydrophenophosphazine 10-oxide in a 73% yield which would be converted to 5-methyl-10-methoxy-5,10-dihydrophenophosphazine 10-oxide in a 56% yield by the same way of synthesizing 10-methoxy-5,10-dihydrophenophosphazine 10-oxide. All these compounds obtained were identified by surveying their melting points, and spectra and elemental analysis.

Key words: Synthesis, 5,10-Dihydrophenophosphazine, Derivative, Structure identification