Spiro, ansa-derivatives of cyclotetraphosphazenes with a tetrafluorobutane-1,4-diol

Abstract

The reaction of the octachlorocyclotetraphosphazene, N 4P 4Cl 8 ( 1), in three stoichiometries (1:1, 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 produced seven products, whose structures have been characterized by elemental analysis, mass spectrometry, 1H, 19F, 31P NMR spectroscopy and by X-ray crystallography, where suitable single crystals were obtained: the mono-spiro compound, N 4P 4Cl 6(OCH 2CF 2CF 2CH 2O) ( 3), its ansa isomer ( 4), cis- and trans-bis-spiro derivatives N 4P 4Cl 4(OCH 2CF 2CF 2CH 2O) 2 ( 5 and 6), tris-spiro compound N 4P 4Cl 2(OCH 2CF 2CF 2CH 2O) 3 ( 7), its mono-spiro-bis-ansa isomer ( 8) and tetrakis-spiro compound N 4P 4(OCH 2CF 2CF 2CH 2O) 4, ( 9). X-ray crystallographic studies confirmed that the structure of the mono-spiro-bis-ansa isomer ( 8) has been reported as a first example in the literature. The results of all reactions were compared with previous work on the reaction of hexachlorocyclotriphosphazene, N 3P 3Cl 6 with the sodium derivative of the diol ( 2), in a 1:1.2 mole ratio in the in the same solvent, THF, and with the reaction of octafluorocyclotetraphosphazene, N 4P 4F 8, with the silyl derivative of the diol ( 2), (Me 3SiOCH 2CF 2) 2, in a 1:0.4 mole ratio in THF.