Preparation, Spectroscopic and Structural Investigations of Spiro Derivatives of Hexachlorocyclotriphosphazatriene

Abstract

Mono-(N₃P₃Cl₄Y₂), bis-(N₃P₃Cl₂Y₄) and tris-spiro derivatives (N₃P₃Y₆) have been prepared with ethylene, 1, 3-propylene and 1,4-butylene glycols (Y₂ = glycol residue). The ¹H NMR spectra of mono- and tris-derivatives are relatively simple; those of the bis- very complex due to the intrinsic asymmetry of the methylene protons. This effect is made use of in studying the replacement pattern of N₃P₃Cl₄ [O (CH₂)₃O] with primary and secondary amines. Homonuclear ¹H decoupling simplifies the spectra and allows an unambiguous distinction to be made between the different isomeric possibilities of the bis amino derivatives N₃P₃Cl₂R₂ [O(CH₂)₃O] where R = amino residue. Primary amines give geminal, secondary amines nongeminal trans-derivatives. The trans-structure of the bis-pyrrolidino derivative has been confirmed by X-ray crystallography.