PERFLUOROVINYLAMINES - REACTIONS OF THE PERFLUOROVINYL GROUP WITH NUCLEOPHILES AND ELECTROPHILES

The chemistry of acyclic and heterocyclic perfluoro-N-vinylamines has been investigated extensively for the first time. The reaction of these compounds with electrophiles is equally facile when compared to those with nucleophiles even under very mild conditions. With nitrogen based nucleophiles such as ammonia, methylamine, and 2,2,2-trifluoroethylamine, R(f)CHFCN and R(f)CHFCF=NR [R(f) = CF2CF2CF2CF2N or CF2CF2OCF2CF2N and R = CH3 or CH2CF3] are obtained, respectively. Formation of beta-substituted perfluorovinylamines i.e. R(f)CF = CFR [R(f) = CF2CF2CF2CF2N or CF2CF2OCF2CF2N and R = CH3, n-C4H9 or N(CH3)2] is achieved using alkyllithium or (dimethylamino)trimethylsilane reagents. Some of these derivatives have good potential as monomers for the little known perfluorovinylamine copolymers. Reaction with electrophilic reagents such as ClOSO2F, ClF, and SF5OCl results in bidirectional addition to form isomers of the type R(f)CFXCF2Cl (I) and R(f)CFClCF2X (II) [R(f) = CF2CF2CF2CF2N, CF2CF2OCF2CF2N, CF2CF2CF2CF2CF2N or (CF3)2N; X = F, OSO2F or OSF5]. However, in some cases only isomer I is obtained, e.g., CF2CF2CF2CF2CF2NCF(OSO2F)CF2Cl, from the reaction with ClOSO2F as an addition product. When CF3OF is added across these perfluorovinylamines, a single addition isomer R(f)-CF2CF2OCF3 is formed. With (CF3)3COCl, complete reversal of addition is observed on reaction with perfluorovinylpyrrolidine vis-a-vis perfluorovinylmorpholine. Although no reaction is observed thermally, photolytic reactions with SF5Cl and (CF3)2NCl give R(f)NCFXCF2Cl [R(f) = CF2CF2CF2CF2N or CF2CF2OCF2CF2N; X = N(CF3)2 or SF5]. These derivatives are characterized by IR, NMR, and mass spectra and elemental analyses.