Reactions of Bi(cyclophosphazenes) with Sodium Alkoxides or Aryl Oxides

Harry R. Allcock, Mark S. Connolly, Paul J. Harris

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Bi(cyclophosphazenes) (2) react with nucleophiles such as sodium trifluoroethoxide or sodium phenoxide by two alternative pathways—(a) with cleavage of the PP ring linkage unit and cleavage of PCl bonds to yield organocyclotriphosphazenes (3) or (b) by cleavage of PCl bonds without rupture of PP bonds to give organobi(cyclophosphazenes) (6). These latter species eventually undergo PP bond scission with alkoxides or aryl oxides under more forcing reaction conditions. Cleavage of the bi(cyclophosphazenes) 2 or 6 also yields phosphazene anions (4), which react with alcohols to form hydridocyclotriphosphazenes (5). Treatment of these with chlorine brings about the conversion of the PH to PCl units. The phosphazene anions (4) also react with allyl bromide with attachment of the allyl residue to the ring and with carbon tetrachloride to abstract Cl+ and generate neutral chloroorganocyclotriphosphazene species (9). These interconnected processes were monitored by both product isolation and NMR spectroscopy. Appendices A and B (supplementary material) outline the interpretation of the more complex 1H and 31P NMR coupling patterns observed.

Original languageEnglish (US)
Pages (from-to)2482-2490
Number of pages9
JournalJournal of the American Chemical Society
Volume104
Issue number9
DOIs
StatePublished - Jan 1 1982

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Oxides
Anions
Negative ions
Sodium
Nucleophiles
Carbon tetrachloride
Carbon Tetrachloride
Chlorine
Nuclear magnetic resonance spectroscopy
Byproducts
Rupture
Alcohols
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
allyl bromide
Proton Magnetic Resonance Spectroscopy

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Allcock, Harry R. ; Connolly, Mark S. ; Harris, Paul J. / Reactions of Bi(cyclophosphazenes) with Sodium Alkoxides or Aryl Oxides. In: Journal of the American Chemical Society. 1982 ; Vol. 104, No. 9. pp. 2482-2490.
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Reactions of Bi(cyclophosphazenes) with Sodium Alkoxides or Aryl Oxides. / Allcock, Harry R.; Connolly, Mark S.; Harris, Paul J.

In: Journal of the American Chemical Society, Vol. 104, No. 9, 01.01.1982, p. 2482-2490.

Research output: Contribution to journalArticle

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AB - Bi(cyclophosphazenes) (2) react with nucleophiles such as sodium trifluoroethoxide or sodium phenoxide by two alternative pathways—(a) with cleavage of the PP ring linkage unit and cleavage of PCl bonds to yield organocyclotriphosphazenes (3) or (b) by cleavage of PCl bonds without rupture of PP bonds to give organobi(cyclophosphazenes) (6). These latter species eventually undergo PP bond scission with alkoxides or aryl oxides under more forcing reaction conditions. Cleavage of the bi(cyclophosphazenes) 2 or 6 also yields phosphazene anions (4), which react with alcohols to form hydridocyclotriphosphazenes (5). Treatment of these with chlorine brings about the conversion of the PH to PCl units. The phosphazene anions (4) also react with allyl bromide with attachment of the allyl residue to the ring and with carbon tetrachloride to abstract Cl+ and generate neutral chloroorganocyclotriphosphazene species (9). These interconnected processes were monitored by both product isolation and NMR spectroscopy. Appendices A and B (supplementary material) outline the interpretation of the more complex 1H and 31P NMR coupling patterns observed.

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