Alkylation of Cyclic and High Polymeric Phosphazenes via Reactions between Aluminum Alkyls and Aminophosphazenes

Harry R. Allcock, James L. Desorcie, J. Steven Rutt

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5 Scopus citations


(Dimethylamino)chlorophosphazenes react with (CH3)3A1, (C2H5)2A1C1, or (C2H5)3A1 to replace chlorine atoms geminal to the amino groups by alkyl units. Subsequent treatment of these products with hydrogen chloride brings about replacement of the dimethylamino groups by chlorine. These reactions have been investigated for cyclic phosphazene trimers that bear one, two, or three dimethylamino units, for cyclic phosphazene tetramers that bear two or four dimethylamino units, and for a mixed-substituent high polymeric phosphazene substrate. Chlorine replacement by aluminum alkyls is promoted by the electron-supplying character of the amino side groups, and three plausible mechanisms are presented. Alkylation is accompanied by phosphorus-nitrogen bond cleavage during reactions that involve the high polymer. The new cyclophosphazenes were characterized by elemental analysis, mass spectrometry, and 31P and 1H NMR analysis. The high polymeric derivatives were also examined by gel permeation chromatography and differential scanning calorinaetry.

Original languageEnglish (US)
Pages (from-to)612-619
Number of pages8
Issue number3
StatePublished - Mar 1988

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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