The first synthesis and X-ray structures of polyfluorinated 1,2-, 2,3- and 2,4a-dihydro-1,3-diazafluorenes

Acetic acid-catalyzed condensation of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)-1,1,4,5,6,7-hexafluoroindene (1b) with acetone and cyclopentanone gives 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene (2a) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3a) together with small amounts of 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene (2b) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3b), respectively. When acted upon by (CH3)2SO4 compounds 2, 3 were converted into corresponding fluorine-containing 1-methyl-1,2-dihydro-1,3-diazafluorenes 6, 7. 4a-Chloro-5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,4a-dihydro-1,3-diazafluorene (8) has been synthesized by the interaction of compound 2 with SOCl2. Solution of compound 2 as well as 8 in CF3SO3H-CD2Cl2 generated 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2,3,4-tetrahydro-1,3-diazafluorene-4-yl cation (2c). The structures of compounds 2, 3, 6–8 have been determined by single crystal X-ray diffraction.