Abstract Laser-flash photolysis studies have been carried out on a solution of ap-and sp-9-(2- azido-4, 6-dimethylphenyl) fluorenes (3) in methanol-ether at 25 C. The rates of formation of azanorcaradiene (5) from ap-nitrene (4) ap, and of 9-methoxyfluorene (7) from o-quinoid intermediate (6) were determined. The deuterium isotope effect on the migration of the hydrogen is discussed.