Phosphonitrilic derivatives. Part XIX. Dimethylaminofluorophosphonitriles and their reactions with hydrogen halides as a route to monosubstituted and non-geminal derivatives of the phosphonitrilic fluorides

Abstract

The dimethylamino-fluorophosphonitriles N_nP_nF_2n–x(NMe₂)_x(x= 1–3, n= 3–6) have been prepared by the reaction of the phosphonitrilic fluorides (NPF₂)_n with (a) dimethylaminotrimethylsilane at 100°(b) dimethylamine in diethyl ether at 0°. Except for n= 6, reaction (a) gives the higher yields of mono-substituted derivatives (x= 1). The ¹H and ¹⁹F n.m.r. spectra show that successive dimethylamination takes place non-geminally. The dimethylaminofluorophosphonitriles react with anhydrous hydrogen chloride or hydrogen bromide at 25°(n= 4–6) or at 100°(n= 3) to give the corresponding chlorides and bromides. The i.r. and ³¹P n.m.r. spectra of the dimethylaminofluorophosphonitriles and the ¹⁹F n.m.r. spectra of the monohalogenofluorophosphonitriles are discussed, and the preparation of the mono-isothiocyanato-derivatives of the phosphonitrilic fluorides described.