23114-34-3Relevant academic research and scientific papers
Photochemistry of 2-Phenyl-1,2-dihydronaphthalene. A Competition between a Singlet State Di-?-methane Rearrangement and a Ring-Opening Reaction
Lamberts, Joseph J.M.,Laarhoven, Wim H.
, p. 1736 - 1739 (2007/10/02)
Irradiation of 2-phenyl-1,2-dihydronaphthalene (4) at 300 nm in hexane leds to three primary photoproducts: endo- and exo-6-phenylbenzobicyclohex-2-ene (endo-5 and exo-5) and 7,12-dihydrodibenzocyclooctatetraene (6).Irradiation of labeled 4 (4
Thermochemistry of Phenyl-Substituted Benzobicyclohex-2-enes
Lamberts, Joseph J.,Laarhoven, Wim H.
, p. 100 - 106 (2007/10/02)
The thermal rearrangements of benzobicyclohex-2-ene (21) and its phenyl-substituted analogues 22-25 (Scheme V) as models of sterically constrained phenylcyclopropanes have been studied by means of flash vacuum pyrolysis.In most cases the major pathway was cleavage of the "internal" C(1)-C(5) cyclopropane bond followed by a 1,2-hydrogen or a 1,2-phenylshift in the resulting biradical.For 6-phenylbenzobicyclohex-2-ene (25), substantial cleavage of the "external" C(1)-C(6) cyclopropane bond was observed, the phenyl substitution pattern being favorable for stabilization of the resulting biradical 62.Phenyl-substituted 1,2-dihydronaphthalenes 44, 47, 51, and 55 are among the major products.Comparison of the plots of the pyrolysis product composition of the 1,2-dihydronaphthalenes vs. pyrolysis temperature with similar plots of the title compounds (22-25) suggested that some of the minor products, viz., the 1,2-divinylbenzenes 31, 42, and 49, are formed via carbenes 30, 41, 50, 57, and 61 rather than via biradicals.Especially at higher pyrolysis temperatures, a large amount of an oxidation product, viz., 1- or 2-phenylnaphthalene (48 or 54), is formed.
Photochemistry of Phenyl-Substituted Benzobicyclohex-2-enes. A Reverse Di-?-methane Rearrangement
Lamberts, Joseph J. M.,Laarhoven, Wim H.
, p. 2202 - 2206 (2007/10/02)
The photochemical rearrangements of phenyl-substituted benzobicyclohex-2-enes can generally be explained by assuming that homolytic fission of that cyclopropane bond which leads to the most stable diradical is the primary step.The final products are formed by 1,2 hydrogen shifts in the intermediate.An exception to this general pattern was observed with 5-phenylbenzobicyclohex-2-ene (5).The photoproducts of 5 could only be explained by assuming reverse di-?-methane rearrangements followed by 1,3 hydrogen shifts.It is argued that this reaction path is followed because of the high rate to the back-reaction of the homolytic bond fission of 5.
