Reactions of (Difluoroamino)difluoroacetonitrile and (Difluoroamino)difluoroacetamidoxime

Abstract

(Difluoroamino)difluoroacetonitrile, NF2CF2CN, was reacted with ammonia, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, hydroxylamine and hydrazine to give the corresponding amidine, imidates, amidoxime, and diamidine. After being heated at 135 °C for 2 days, (difluoroamino)difluoroacetamidine undergoes cyclization to form 1-amino-3,5-bis[(difluoroamino)difluoromethyl] triazine. While the monosubstituted hydrazine F2NCF2C(═NH)NHNH2is only stable in solution, the bis(iminomethyl) hydrazine F2NCF2C(═NH)NHNHC(═NH)CF2NF2is a stable sublimable solid. (Difluoroamino)difluoroacetamidoxime, F2NCF2C(═NOH)NH2, is acylated with perfluoroacyl chlorides Rf[C(O)C1 (Rf= CF3, C2F5, C3F7) to form F2NCF2C(═NOC(O)Rf)NH2The latter are cyclized by dehydration with P4O1Oto give the respective 1,2,4-oxadiazoles, F2NCF2C═NOC(Rf)═N. With phosgene, F2NCF2C(═NOC(O)Cl)NH2is formed. Thermolysis of the latter at 100 °C results in loss of HCl giving F2NCF2C═NOC(O)NH. The acetamidoxime with perfluorosuccinic acid (1:1) gives (-CF2C═NC═N(CF2NF2)O)2in the presence of P4O1O. © 1988, American Chemical Society. All rights reserved.