3642-12-4Relevant articles and documents
The Energy-Well of Diradicals, IV. - 2-Methylene-1,4-cyclohexadiyl
Roth, Wolfgang R.,Wollweber, Detlef,Offerhaus, Rolf,Rekowski, Volker,Lennartz, Hans-Werner,et al.
, p. 2701 - 2716 (2007/10/02)
The energy surface of the title compound 2 is derived from the kinetics of its precursors 5, 6, 7, and 8, the oxygen dependance of its trapping rate, and heat of hydrogenation measurements of 5, 6, 7, and 15.These data lead to a heat of formation of the diradical 2 of 69.8 kcal/mol and an energy well of 8.2 kcal mol-1.From the Curie plot of the ESR spectrum and oxygen trapping experiments a singlet-triplet splitting of 1.4 kcal mol-1 is indicated, with the triplet being the ground state. - Key Words: Diradical / Oxygen trapping / Heat of formation / Energy well / ESR spectrum / Singlet-triplet splitting / Cope rearrangement, nonconcerted
Organic Photochemistry with 6.7-eV Photons: The Photochemistry of Bicyclohept-2-ene (2-Norcarene)
Leigh, William J.,Srinivasan, R.
, p. 514 - 519 (2007/10/02)
The photochemistry of bicyclohept-2-ene (2-norcarene) upon direct and triplet-sensitized photolysis has been investigated.The results differ significantly from those of previous studies on related systems.Direct photolysis with monochromatic radiation in the region 185-230 nm leads to a variety of products, of which cis-1,3,6-heptadiene, the major product, is shown by deuterium labeling studies to result from formal electrocyclic ring opening in a manner analogous to the 1,3-cyclohexadiene/1,3,5-hexatriene interconversion.The evidence suggests that this process may occur via a concerted mechanism in the singlet state.The other products arise from activation of the two cyclopropane bonds that are in conjugation with the olefinic group.The product distribution is independent of both solvent and excitation wavelength and is unchanged by the addition of naphthalene.Toluene-sensitized photolysis results in the formation of cis-1,3,6-heptatriene and bicyclohept-2-ene, which can be rationalized as resulting from decay of a common biradical intermediate.