Self quenching reaction of (Phenoxymethyl) chlorocarbene with diazirine

The combination of laser flash photolysis and product analysis demonstrates that even though (phenoxymethyl)chlorocarbene reacts with its diazirine precursor with a substantial rate constant of 3.5 x 10(8) M(-1)s(-1), the predicted azine product is not formed. These results indicate either carbene/diazirine reversibility or subsequent hydrogen migration of the carbene/diazirine adduct. Also, a rate constant of 2.0 x 10(7) s(-1) for the 12-hydrogen atom migration in (p-nitrophenoxymethyl)chlorocarbene has been determined using the pyridinium ylide technique.PT: J; CR: CHATEAUNEUF JE, 1991, J ORG CHEM, V56, P5942 GRAHAM WH, 1965, J AM CHEM SOC, V87, P4396 LIU MTH, 1992, J AM CHEM SOC, V114, P3604 LIU MTH, 1992, J PHOTOCH PHOTOBIO A, V63, P115 MORGAN S, 1991, J AM CHEM SOC, V113, P2782 MOSS RA, 1990, J AM CHEM SOC, V112, P5642 MOSS RA, 1990, KINETICS SPECTROSCOP; NR: 7; TC: 6; J9: RES CHEM INTERMEDIATES; PG: 5; GA: ND525Source type: Electronic(1