Fluorocarbon Nitrogen Compounds. VII.¹ The Indirect Fluorination of Some Fluorocarbon Nitrogen Derivatives²

The Mechanism of the Reaction of Carbonatopentaamminecobalt(III) witn Divalent Ions

“…where CO2 adds to one coordinated oxygen and subsequently one coordinated water is lost. 4 The fact that C02 rather than C032-is removed from the carbonato complex is consistent with the speed of the reactions with Hg2+ and Pb2+. Substitution at Co (III) in the ammine complexes is usually slow and thus Co-0 bond fission in the present reaction might be expected to be slow.…”

Preparation and Properties of Imido Intermediates (Imidogens)

“…It was argued that if bond formation were significantly involved in the transition state, * would probably have been negative. The intermediacy of an acylimidogen in the Curtius reaction has also been argued on the basis of a study of the indirect fluorination of trifluoroacetic acid imide (341). The above discussion indicates that the question of the detailed mechanism of these rearrangements is far from settled and that much more work is necessary to clarify the situation.…”

“…The indirect fluorination of some fluorocarbon nitrogen derivatives with AgF2 is said to give rise to products via an imido intermediate. For example, reaction of a fluorocarbon isocyanate with AgF2 gives carbonyl fluoride and the fluorocarbon azoalkane (341). and difluoromalononitrile and other dicarboxylic acid nitriles gives products which may arise by the internal dimerization of a diimido intermediate (108,161).…”

“…These reactions parallel those undergone by carbenes. Dimerization to the azo compound has been suggested in a few instances (258,341), and aromatic substitution has been shown to take place (35,175,285) n-hexadecane at 230°g ave n-octanal imine (32%) but no detectable amount of the pyrrolidine (VI), whereas photolysis resulted in a 35% yield of VI (R = CH3(CH2)8) (35). Conceivably, the imido intermediates produced under these different conditions are in different electronic states, e.g., singlet state from the thermal, and triplet from the photochemical decompositions.…”

Nitrogen Fluorides and their Organic Derivatives.

“…Although numerous products are formed, the major product being CF3N=NCF3, little evidence was found for the presence of organic compounds containing nitrogenfluorine bonds. The indirect fluorination of fluorocarbon nitrogen compounds by silver(II) fluoride under mild conditions has been studied (179,181). Reactions with this reagent wrere determined for the following functional groups: -N=C=, N=C-, C(Cs=N),, =NH, =NCOF, -N=C=0, -NHCOF, and -CONHs.…”