SYNTHESIS OF TRANSANNULAR-SUBSTITUTED AND SPIRO-SUBSTITUTED CYCLOTRIPHOSPHAZENES - X-RAY CRYSTAL-STRUCTURES OF 1,1-[N3P3(OCH2CF3)4(O2C12H8)], 1,3-[N3P3(OCH2CF3)4(O2C12H8)], 1,1-[N3P3(OCH2CF3)4(O2C10H6)], AND 1,3-[N3P3(OCH2CF3)4(O2C10H6)]

A cyclic triphosphazene with four trifluoroethoxy side groups and two nongeminal chlorine atoms, 1,3-[N3P3(OCH2-CF3)4Cl2], reacts with difunctional alcohols or amines to give transannular derivatives. Examples of the difunctional reagents used include catechol, 2,2'-biphenol, 1,8-dihydroxynaphthalene, 1,8-diaminonaphthalene, 1,3-propanediol, 1,3-diaminopropane, and 2,2'-dilithiobiphenyl. These are the first examples of transannular-bridged structures derived from aromatic diols or diamines. The analogous spirocyclic derivatives were prepared directly from hexachlorocyclotriphosphazene via a simple two-step reaction pathway using the same difunctional reagents. The solid-state structures of 1, 1- and 1,3- [N3P3(OCH2CF3)4(O2C12H8)] and 1, 1- and 1,3-[N3P3(OCH2CF3)4(O2C10H6)] were determined by X-ray diffraction, and the effects of transannular versus spiro substitution on the planarity of the phosphazene ring and (by implication) on the phosphazene ring strain were studied. These compounds are starting materials for phosphazene ring-expansion or ring-opening polymerization reactions.