Earnest Obed John

Oxadiazoles with NF2-containing substituents

Abstract Oxalyl chloride was reacted with sodium-5-(difluoroamino)- difluoromethyltetrazolate or sodium-5-pentafluoroethyltetrazolate to form [R f CNNC(O) ] 2 [R f z NF 2 CF 2 ( 7 )], and with F 2 NCF 2 C(NH 2 )NOH to give [F 2 NCF 2 C(NH 2 )NOC(O)] 2 ( 5 ) which may be dehydrated to the 1,2,4-oxadiazole ( 6 ). Both sodium salts can be reacted with perfluoroacyl acid chlorides to form 2,5-disubstituted 1,3,4-oxadiazoles, R f CNNC(R f ′)O where R f ′ = NF 2 CF 2 and R f = CF 3 ( 8 ), C 2 F 5 ( 9 ), or C 3 F 7 ( 10 ); R f ′ = C 2 F 5 and R f = CF 3 ( 11 ) or C 2 F 5 ( 12 ).

Highly fluorinated tetrazanes and other polynitrogen compounds

Abstract Highly fluorinated tetrazanes and cyclic, polycyclic and acyclic high nitrogen compounds are thermally and hydrolytically stable and, in general, shock insensitive materials. They are slightly volatile, colorless liquids which are only very slightly soluble in most solvents. Their synthetic routes are straighfforward but, as is typical of the chemistry of compounds which contain fluorine, there is always sufficient of the unexpected to tweak the imagination.

Some reactions of fluorinated azaalkenes, RfNCF2

Abstract More facile routes to fluorinated azaalkenes encourage further studies of the reactions of these compounds. Reactions of (CF3)2NCF2NCF2 with lithiated polyfluoroalkoxides give (CF3)2NCF2NCF2−x(ORf)x [X=1 or 2; RfCF3CH2, (CF3)2CH or (CF3)2C(CH3)]. Chlorine fluoride can be added to the nitrogen-carbon double bond of these mono- and bis-alkoxides with retention of the molecular backbone to give (CF3)2NCF2N(Cl)CF3−x(ORf)x [X=1 or 2; RfCF3CH2, (CF3)2CH or (CF3)2C(CH3)]. Photolysis of neat NF2CXFCF2NCl2, which results from chlorofluorination of F2NCXFCN (X=Cl or F), gives diazencs [F2NCXFCF2N]2. Thermolysis of F2NCF2CF2NCl2 in a 1:1 ratio with CF2CClF results in F2NCF2CF2N(Cl)CF2CCI2F. Upon photolysis of the latter, a new azaalkene, F2NCF2CF2NCF2 results. Following chlorofluorination of F2NCF2CF2NCF2, insertion of ClCN or F2NCF2CN into the resulting nitrogen-chlorine bond gives imines F2NCF2CF2N(CF3)NCCl2 and F2NCF2CF2N(CF3)NC(Cl)CF2NF2. Successive chlorofluorination of the latter compound with intramolecular elimination of chlorine, followed by photolysis, gives rise to a stable, non-volatile tetrazane (70%) that contains eight nitrogen atoms, F2NCF2CF2N(CF3)N(CF2CF2NF2)N(CF2CF2NF2)N(CF3)CF2CF2NF2.

Reactions of nitriles which contain the NF or NF2 functional group with boron halides

Abstract Dimeric insertion products [R f CXNBX 2 ] 2 (R f F 2 NCClF, F 2 NCF 2 , CF 3 C(NF), FC(NF); XCl, Br) are obtained when F 2 NCClFCN, F 2 NCF 2 CN, CF 3 C(NF)CN and FC(NF)CN are reacted with boron trichloride or boron tribromide, respectively. The structures of these water-sensitive materials is supported by infrared, 19 F and 11 B nuclear magnetic resonance and mass spectral data, and by elemental analyses.