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

Abstract

The reaction of the octachlorocyclotetraphosphazene N4P4Cl8 (1) in three stoichiometries (1 1 1 2 and 1 3) with the sodium derivative of the fluorinated chol 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 H-1 F-19 P-31 NMR spectroscopy and by X-ray crystallography where suitable single crystals were obtained the mono-spiro compound N4P4Cl6(OCH2CF2CF2CH2O) (3) its ansa isomer (4) as and trans bis-spiro derivatives N4P4Cl4(OCH2CF2CF2CH2O)(2) (5 and 6) tris-spiro compound N4P4Cl2(OCH2CF2CF2CH2O)(3) (7) its mono-spiro-bis ansa isomer (8) and tetrakis spiro compound N4P4(OCH2CF2CF2CH2O)(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 N3P3Cl6 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 N4P4F8 with the silyl derivative of the chol (2) (Me3SiOCH2CF2)(2) in a 1 0 4 mole ratio in THF (C) 2010 Elsevier Ltd All rights reserved