Controlled hydrolysis of hexachlorocyclotriphosphazene and related, sulphur-containing ring systems

Abstract

Reactions of the ring systems (NPCl₂)₃, (NPCl₂)₂NSOX, and NPCl₂(NSOX)₂(X = Cl or Ph) with water in acetonitrile in the presence of AsPh₄Cl or KCl–C₁₂H₂₄O₆(1,4,7,10,13,16-hexaoxacyclooctadecane) afford salts derived from hydroxy derivatives of these rings. In all compounds the introduced oxygen ligands are exclusively attached to phosphorus atoms. In addition to monosubstituted derivatives some disubstituted ones can also be isolated. For (NPCl₂)₃ a non-geminal structure for the two isomeric disubstituted derivatives was established, whereas the derivative of (NPCl₂)₂NSOCl appears to have a geminal structure. The difference in reaction behaviour of these two ring systems is rationalized in terms of the different base strengths of the rings. The ³¹P n.m.r. spectra of the salts are briefly discussed.