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The kinetics and mechanisms of the reactions of singlet perfluoro-4-biphenylnitrene and N -propyl- 4-nitreno-2,3,5,6-tetrafluorobenzylamide with various amines, pyridine, and dimethylsulfoxide were studied by laser flash photolysis. The reactions of singlet arylnitrenes with amines are two-step processes. The primary step of the process is adduct formation; the rate constant of this reaction is high and lies within the range 4 〈 10 7 -2 〈 10 8 l mol -1 s -1 for the tested secondary amines. The second step (1,2-hydrogen shift) was acceler- ated in the presence of water.