Azidophosphazenes as functionalized intermediates

The synthesis of phosphazene cyclic trimers with azido side groups and aryl oxy, alkoxy, or dialkylamino cosubstituent groups was accomplished. The com pounds have the basic structure N3P3(R)(x)(N-3)(6-x), where R represents ph enoxy, trifluoroethoxy, dimethylamino, or diethylamino groups and x = 3-5. Experiments were also conducted to determine the ability of these materials to undergo a reaction unique to azido compounds known as nitrene insertion . The aryloxy derivative, N3P3(OC6H5)(5)(N-3), yielded a nitrene insertion product when heated with 1-phenylnonane at 280 degrees C. The alkoxy deriva tive, N3P3(OCH2CF3)(5)(N-3), produced a nitrene insertion product when ultr aviolet irradiated in an aliphatic solvent. The dialkylamino derivative, N3 P3(N(CH3)(2))(4)(N-3)(2), did not undergo nitrene insertion. The aryloxy an d alkoxy azido trimers reacted with various phosphorus(III) compounds to fo rm phosphinimines via the Staudinger reaction. Finally, sodium phenoxide di splaced azides from both the alkoxy- and aryloxyphosphazene trimers while n -butylamine displaced only the azide on the alkoxy trimer.