Reaction of aromatic or heterocyclic amines and perfluoro-2-methylpent-2-ene to give fused pyridines, ketenimines, or enamines

Exceptional Products of the Desulfurization ofN,2-Diaryl-5-(arylimino)- 2,5-dihydro-4-nitroisothiazol-3-amines

“…A mechanism similar to that proposed for the formation of the nitroquinolinediamines 7 (Scheme 5) has been reported by Flowers et al [41] for the synthesis of Narylquinolin-4-amines from perfluoro-2-methylpent-2-ene and 2-unsubstituted primary arylamines. The products were formed via an intramolecular electrophilic aromatic substitution of an arylimino group by the electrophilic C-atom of a ketene imine.…”

Preparations and reactions of 2-trifluoromethylketenimines

“…The orange oil of 2-(2-nitrophenyl)sulfenyl-2-trifluoromethylketenimine (9) (0.265 g, 0.72 mmol, 35%) was obtained. 19 F NMR d 104.3 (s, 3F) ppm; 1 H NMR d 3.84 (s, 3H), 6.93 (d,J = 9 Hz,2H),7.28 (d,J = 9 Hz,2H),7.36 (ddd,J = 2,7,8 Hz,1H),7.69 (ddd,J = 2,7,8 Hz,1H),7.81 (d,J = 8 Hz,1H),8.29 (dd,J = 2,8 Hz,1H) ppm; IR (neat) 2050 cm À1 ; MS m/z (DI) 368 (M + , trace), 230 (22), 149 (100), 138 (36), 77 (88), 69 (67); elemental analysis: Calcd for C 16 H 11 F 3 N 2 O 3 S: C, 52. 17;H,3.01;N,7.61.…”

“…Bis(trifluoromethyl)ketenimines have been prepared by perfluoroisobutene or its analogs [5]. More complicated ketenimine has been prepared by the reaction of perfluoro(3,4-dimethylhex-3-en-2-one) with tert-butylamine [6], the reaction of perfluoro(2-methyl-2-pentene) with amines [7], and the reaction of 3,4-dicyano-1,1,1,4,4,4-hexafluoro-2-butene with thiadiazoline [8]. These ketenimines react with nucleophiles to give aldimines [9], heterocyclic compounds [5b, 6,10], and metal complex [11].…”

Synthesis of partly-fluorinated heterocycles: reaction of perfluoro-2-methyl-2-pentene or perfluoro-5-aza-4-nonene with aniline or its derivatives

“…Moreover, perfluoro-2-methylpent-2-ene is known to react with ferf-butylamine, iso-pqylamine and n-propylamine to yeld azetine derivatives [12,14-161. On the other hand, reaction of internal perfluoroolefin with aniline has been noticed to provide quinoline derivatives [ 10,17,18]. Thus, treament of aniline with 2H-heptafluorobut-2-ene produced the phenyl-(2-tnfluoromethyl-quinoline-4-yl)amine [ 131 and reaction of aniline with tetrafluoroethylene trimer provided 2-trifluoromethyl-3(1-N-phenylimino-2,2,2-~fluoroethyl)-4-(N-phenylamino)quinoline [lo].…”

“…The presence of electron-donating substituents in aromatic amines is supposed to facilitate the formation of quinoline derivatives. As a matter of fact, reaction of perfluoro-2-methylpent-2-ene with 2,4dimethoxyaniline gave 4(2,4dimethoxyanilino)-6,8-dimethoxy-2-pentafluoroethyl-3-trifluoromethylquinoline [17]. However, that kind question remains unclear yet since reaction of aniline with octafluoro- -159 -intemal perfluoro-olefins, we have investigated in detail the reactions of perfluoro-2-methylpent-2-ene (1) and perfluoro-5-azanon-4-ene (2) with aniline and its derivatives: 4-fluoroaniline, 2,6-dimethylaNline, 2,6-dichloroaniline, 4-methoxyaniline, 2-and 4-nitroaniline and pentafluoroaniline.…”