Organic fluoronitrogens. VI. Reduction of difluoramino compounds with iodide

Diazirines: Carbene Precursors Par Excellence

“…Phenylbromodiazirine or phenylchlorodiazirine were converted to phenylfluorodiazirine simply by stirring with “molten” tetrabutylammonium (TBA) fluoride at 25 °C, Table , entries 2 and 3. The new diazirine was a convenient photochemical source of phenylfluorocarbene (PhCF) . Similarly, phenoxychlorodiazirine was converted to phenoxyfluorodiazirine (Table , entry 4), progenitor of phenoxyfluorocarbene (PhOCF) .…”

“…Difluorodiazirine and chlorofluorodiazirine have been prepared from explosive or inconvenient precursors, − but can the diazirine exchange reaction be extended to the preparation of dihalodiazirines ? Monohalodiazirines are readily available from the Graham procedure (eq 1), so dihalodiazirines could be made by exchange if “R” were converted into a leaving group.…”

“…The new diazirine was a convenient photochemical source of phenylfluorocarbene (PhCF). 12 Similarly, phenoxychlorodiazirine was converted to phenoxyfluorodiazirine (Table 1, entry 4), progenitor of phenoxyfluorocarbene (PhOCF). 10 These were the first preparations of fluorodiazirines not involving dangerous or inconvenient manipulations of explosive perfluoroformamidine, 11 fluoroamine, 12 or difluorocyanamide 13 precursors.…”