40154-60-7Relevant articles and documents
Access to the naphthylcarbene rearrangement manifold via isomeric benzodiazocycloheptatrienes
Bonvallet, Paul A.,Todd, Eric M.,Kim, Yong Seol,McMahon, Robert J.
, p. 9031 - 9042 (2002)
Irradiation (λ = 670 or >613 nm) of 4,5-benzodiazocycloheptatriene (15), matrix isolated in argon at 10 K, produces primarily 2,3-benzobicyclo[4.1.0]hepta-2,4,6-triene (9) accompanied by small amounts of triplet 4,5-benzocycloheptatrienylidene (2) and 2-naphthylcarbene (10). A reversible photoequilibrium is established in which 9 is converted to 10 at λ = 290 nm and then regenerated at λ = 360 nm. Similarly, matrix-isolated 2,3-benzodiazocycloheptatriene (16) produces 4,5-benzobicyclo[4.1.0]hepta-2,4,6-triene (11) at λ = 670 or >613 nm, but without detection of 2,3-benzocycloheptatrienylidene (4). Irradiation of 11 at λ = 290 nm induces ring opening to triplet 1-naphthylcarbene (12), which, in turn, cyclizes back to 11 at λ = 342 or >497 nm. The diazo compounds and photoproducts are characterized by IR, UV/visible, and ESR spectroscopy, where appropriate, and by comparison of the experimental and B3LYP/6-31G* calculated IR spectra for each species. Alternate rearrangement products such as allenes 6, 7, and 8 are not detected in the photolysis of either diazo compound.
