The preparation of polyfluoroalkyl phosphonitrilates and N-(perfluoracyl) phosphoramidic dichlorides

Abstract The phosphonitrilic fluorides can be made to react readily with sodium polyfluoroalkyl alcoholates, CHF 2 (CF 2 ) n CH 2 ONa, to give high yields of the corresponding phosphonitrilic esters, viscous, high boiling liquids, which are soluble in a variety of organic and fluorocarbon solvents, but insoluble in water. The end product of reactions between fluorocarbon amides and PCl 5 are N-(perfluoroacyl)-phosphoramidic dichlorides, R f CONHPOCl 2 , where R f is a perfluoroalkyl radical. The structure of this type of compound was confirmed by their reactions with fluoroalcohols and hydrazine. Reactions of phosphonitrilic chloride trimer, (NPCl 2 ) 3 , with fluorocarbon amides, and imide and the barium salt of trifluoroacetic acid were studied. Amides undergo the same chemistry as benzamide, the salt acts similarly to sodium benzoate, while perfluoroglutarimide was converted to the acid-amide adduct of pyridine when pyridine was used as a solvent.