Wholly Substituted Cyclic Derivatives

Many reactions are known in which the halogen atoms of halophosphazenes can be wholly replaced by other atoms or groups. Thus replacement by hydroxyl can be effected by hydrolysis to give [PN(0H)2] , and by amine groups to give [PN(NH2)2] . Alkoxy and aryloxy derivatives can be 

Reaction (7.328) gives a white waxy product which has a high thermal stability and is soluble in many organic solvents. It is unaffected by boiling concentrated HNO3 or HCl, or by aqueous bases. 

Liquid ammonia will react under pressure with trimer and tetramer chloride to give fully ammo-niated products [PN(NH2)2l3 and [PN(NH2)2l4. These are white hygroscopic compounds which 

Cyclic halogenophosphazenes (phosphonitrUic halides) react with primary or secondary amines to give amine-substituted derivatives. Thushexakis(phenylamino) cyclotriphosphazene, [PN(NHPh)2l3 can be made by heating an aniline solution of the chloride at 100°C (7.329). Organoamine derivatives [PN(NHR)2] and [PN(NR2)2] (n = 3 or 4) are usuUy water stable in contrast to the aminophospha-zenes above. Thiol derivatives are obtained by reaction (7.330). 

Reaction with HE destroys the ring, however, and ammonium hexafluorophosphate (hexafluoro-phosphoride) is obtained in the unusual reaction (7.331). On the other hand, wholly substituted ring derivatives can be obtained by reactions such as (7.332) (in some cases a proportion of tetramer may also be obtained). 

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