Phosphorus-Nitrogen Compounds. I. Reactions of Cl₂P(O).N[dbnd]PCl₃ with an Excess of Pyrrolidine: Isolation of an Acycylic Phosphazene, (H₈C₄N)₂P(O).N[dbnd]P(NC₄H₈)₃, Bis (Pyriolidinophosphinoyl)Amine, [H₈C₄N)₂P(O)]₂NH and Amidinium Salt, [CH₃(H₈C₄N)C[dbnd]NH]. HCl

Abstract

Reactions of 1-(dichlorophosphinyl)-2,2,2-trichlorophosphazene, Cl₂P(O).N[dbnd]PCl₃, with an excess of pyrrolidine led to the isolation of the acyclic pyrro-lidino-derivative, (H₈C₄N)₂P(O).N[dbnd]P(NC₄H₈)₃, and bis(pyrrolodinophosphinoyl) ∼ amine, [(H₈C₄N)₂P(O)]₂NH. N',N'-tetramethyleneacetamidiniumchloride, [CH₃ ∼ (H₈C₄N)C[dbnd]NH]. HCl, was formed from CH₃CN, pyrrolodine and HCl evolved during the reactions in CH₃CN. The reactions of N₃P₃Cl₆, N₄P₄Cl₈, and N₄P₄(NHEt)₂Cl₆ with an excess of pyrrolidine in CH₃CN gave the above mentioned amidinium salt and some known phosphazene derivatives. The phosphazene compounds promote the formation of the amidinium salt. The reaction of N₃P₃(NH₂)₂Cl₄ with an excess of dimethylamine gives the free base, N₃P₃(NH₂)₂(NMe₂)₄, and its salt, N₃P₃(NH₂)₂(NMe₂). HCl, but no amidinum salt, [Me(Me₂N)C[dbnd]NH]. HCl could be separated as a stable product. The basicities of these phosphazene derivatives in nitrobenzene solution are reported. Possible reaction mechanisms for the formation of the new phosphazenes and the amidinium salt are considered.