265-49-6Relevant articles and documents
Stepwise mechanisms in cyclopropylcarbene reactions
Cummins, Jordan M.,Porter, Timothy A.,Jones Jr., Maitland
, p. 6473 - 6476 (1998)
Decomposition of a naphtho-fused cyclopropyldiazomethane leads to benzocyclooctatetraene, 1-vinylnaphthalene, 2-vinylnaphthalene, and small amounts of benzobarrelene. Diradical intermediates are postulated.
The photochemistry of 2,3-benzobicycloocta-2,4,7-triene
Asplund, Charlotte Lee,Bender, Christopher Owen,Dolman, Douglas
, p. 1999 - 2004 (2007/10/02)
2,3-Benzobicycloocta-2,4,7-triene (11) was prepared by Shapiro reaction from 2,3-benzobicycloocta-2,7-dien-4-one (10).Triene 11 was found to be thermally and photochemically reactive.Benzocyclooctatetraene (i.e., COT 12) was the unique product formed when solutions of 11 were heated at 150 deg C for 5.5 h.The direct irradiation of triene 11 gave benzosemibullvalene (i.e., SB 14, 23percent, Φ = 0.069), COT 12 (39percent, Φ = 0.11), and naphthalene (8percent, Φ = 0.025).Sensitized irradiations of 11 gave SB 14, (54percent, Φ = 0.082), COT 12 (2percent, Φ = 0.003), and naphthalene (4percent, Φ = 0.009).Studies with deuterium-labelled triene (11a) indicated that the formation of SB 14 from the direct irradiation of triene 11 derives from the operation of two reaction pathways, the major one (83percent) of which appears to be a Zimmerman di-?-methane rearrangement; the minor pathway involves a 1,2-shift of the C1-C6 bond to C1-C5.By contrast, SB 14 formed from sensitized irradiation appears to be provided uniquely by a Zimmerman di-?-methane rearrangement.
