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Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: A comparison with butane-1,4-diol

Authors
Journal
Polyhedron
0277-5387
Publisher
Elsevier
Publication Date
Volume
25
Issue
4
Identifiers
DOI: 10.1016/j.poly.2005.10.027
Keywords
  • Cyclophosphazenes
  • Crystal Structure
  • Spiro
  • Ansa
  • Tetrafluorobutane-1
  • 4-Dioxy Derivatives

Abstract

Abstract Reaction of hexachlorocyclotriphosphazene, N 3P 3Cl 6 ( 1), in two stoichiometries (1:1.2 and 1:3) with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol ( 2), in THF solution at room temperature afforded six products, whose structures have been characterized by X-ray crystallography and 1H, 19F and 31P NMR spectroscopy: the mono-spiro compound, N 3P 3Cl 4(OCH 2CF 2CF 2CH 2O) ( 3), its ansa isomer ( 4), a di-spiro derivative N 3P 3Cl 2(OCH 2CF 2CF 2CH 2O) 2 ( 5), its spiro-ansa ( 6) and non-gem cis bis-ansa ( 7) isomers and a tri-spiro compound N 3P 3(OCH 2CF 2CF 2CH 2O) 3 ( 8). The tri-spiro derivative 8 was also formed in the reaction of the ansa compound 4 with diol ( 2) in a 1:3 ratio in THF at room temperature. The reactions of 1 with step-wise additions of 2 were also investigated at low temperature (−78 °C) to give the same range of products as at room temperature. The results of all reactions are compared with previous work on the reactions of 1 with butane-1,4-diol/pyridine mixtures and with the reaction of hexafluorocyclotriphosphazene, N 3P 3F 6 ( 9), with the silyl derivative of the diol ( 2), (Me 3SiOCH 2CF 2) 2, in a 1:0.4 mole ratio in the same solvent, THF.

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