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

The reaction of the octachlorocyclotetraphosphazene, N4P4Cl8 (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, N4P4Cl6(OCH2CF2CF2CH2O) (3), its ansa isomer (4), cis- 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 diol (2), (Me3SiOCH2CF2)2, in a 1:0.4 mole ratio in THF.

Geometrical isomers (cis- and trans-bis-spiro) and novel spiro-ansa compound (mono-spiro-bis-ansa) were obtained from the reaction of cyclotetraphosphazene with fluorinated butanediol.Figure optionsDownload as PowerPoint slide