NEW DIOXYTETRAETHYLENEOXY MACROCYCLIC CYCLOPHOSPHAZENE DERIVATIVES

A series of macrocyclic cyclophosphazene containing derivatives of mon o-ansa, mono-spiro, spiro-ansa and bis-ansa structure together with po lymeric materials have been obtained by the reaction of hexachlorocycl otriphosphazene with tetraethylene glycol in the presence of sodium hy dride. 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. Cryst als 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 reflecti ons (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 dif ferent P atoms are coupled to an O(CH2CH2O)(4) chain, forming a 16-mem bered diphosphaza crown ether.