55277-79-7Relevant academic research and scientific papers
The photochemistry of 5-cyano-2,3-benzobicycloocta-2,4,7-triene
Bender, Christopher Owen,Dolman, Douglas
, p. 82 - 87 (2007/10/02)
The direct irradation of 5-cyano-2,3-benzobicycloocta-2,4,7-triene (18) led to 6-cyanobenzocyclooctatetraene (17; Φ=0.00075), 6-cyanobenzosemibullvalene (14; Φ=0.0003), and 2-cyanonaphthalene (Φ=0.00015).The triplet excited state of 18, generated by sensitization with a variety of ketone sensitizers (e.g., Michler's ketone and acetophenone), showed no unimolecular reactivity.Compound 18 does not participate in Zimmerman di-?-methane rearrangement; the potential product from such a transformation, 8-cyanobenzosemibullvalene (19), was, however, isolated from direct (Corex filter; Φ=0.0010) irradation of the semibullvalene 14.Deuterium labelling experiments suggest that 14 derives from a mechanism involving initial C4-C8 bonding of 18, and that cyclooctatetraene 17 is probably formed by simple electrocyclic opening of the cyclobutene ring of 18. Keywords: photochemistry, rearrangement mechanism, di-?-methane, semibullvalenes.
The photochemistry of 8-cyano-2,3-benzobicycloocta-2,4,7-triene
Bender, Christopher Owen,Dolman, Douglas,Murphy, Gaetanne Kathryn
, p. 1656 - 1662 (2007/10/02)
The direct irradiation of 6-cyanobenzocyclooctatetraene (7) led to 5- and 8-cyano-2,3-benzobicycloocta-2,4,7-triene (9 and 8), isolated in 21 and 63percent yields, respectively.On triplet sensitized irradiation 8 gave 1- and 6-cyanobenzosemibullvalenes (4 and 12; Φ = 0.006 and 0.088, respectively) and naphthalene (Φ = 0.012).The direct irradiation of 8 yielded 12 (Φ = 0.050), naphthalene (Φ = 0.015),7 (Φ = 0.007), 7-cyanobenzocyclooctatetraene (13; Φ = 0.007), and 5-cyano-7,8-benzotetracyclo2,4,03,6>oct-7-ene (14; Φ = 0.004).Deuterium labelling studies suggest that 12 derives from Zimmerman di-?-methane rearrangement of 8, and that photoproduct cyclooctatetraene 7 is not formed by simple electrocyclic opening of the cyclobutene ring of 8.
