NEW DIOXYTETRAETHYLENEOXY MACROCYCLIC CYCLOPHOSPHAZENE DERIVATIVES

A series of macrocyclic cyclophosphazene containing derivatives of mono-ansa, mono-spiro, spiro-ansa and bis-ansa structure together with polymeric materials have been obtained by the reaction of hexachlorocyclotriphosphazene with tetraethylene glycol in the presence of sodium hydride. Structure determination was based on mass and P-31 NMR spectral analysis. The formation of macrocyclic compounds points to a template effect being operative during substitution. The structure of the mono-ansa compound has been confirmed by an X-ray diffraction study. Crystals are triclinic, P (1) over bar, a=7.797(1), b=10.705(1), c=12.336(1) Angstrom, alpha=88.74(1), beta=72.404(7), gamma=72.15(1)degrees Z=2 at 130 K. The refinement converged to R=0.034 for 3434 unique reflections (I greater than or equal to 2.5 sigma(I)) and 273 parameters. The basic structure consists of an N3P3 six-membered ring in which two different P atoms are coupled to an O(CH2CH2O)(4) chain, forming a 16-membered diphosphaza crown ether.