57015-38-0Relevant academic research and scientific papers
Einige Reaktionen des 8,8-Dibromtetracyclo2,4.03,5>octans
Christl, Manfred,Lechner, Monika
, p. 1 - 13 (2007/10/02)
The title compound 2, easily prepared by addition of dibromocarbene to homobenzvalene (7), forms 5-ethinyl-1,3-cyclohexadiene (9) on treatment with methyllithium.Its structure was proved through the additions to 4-phenyl-1,2,4-triazolinedione and 2,3,5,6-tetramethylbenzonitrile oxide, leading to 10 and 12 respectively. 2H and 12C labeled 2 were used to determine the reorganization of the carbon atoms.The results support the proposed reaction mechanism.On heating of 2 the dibromocyclopropane moiety remains intact and dibromo-trans-bishomobenzene (20) is formed, with boron trifluoride-ether 2 rearranges to 20 already at room temperature.Sodium in liquid ammonia debrominates 2 as well as 20 to produce the known parent hydrocarbons 8 and 21 respectively.
Chemistry of 2-Carbenabicyclooctadiene
Freeman, Peter K.,Swenson, Karl E.
, p. 2033 - 2039 (2007/10/02)
Pyrolytic decomposition of the lithium or potassium salt of the tosylhydrazone of bicycloocta-3,6-dien-2-one (11) or photolysis of the lithium salt of 11 results in the formation of bicycloocta-2,6-diene (12), tricyclo2,7>oct-3-ene (13), tetracyclo2,8.04,6>octane (14), semibullvalene (15), 5-ethynyl-1,3-cyclohexadiene (16), and endo-6-ethynylbicyclohex-2-ene (17).The formation of the C8H8 fraction (15-17) is ascribed to insertion and rearrangement reactions of singlet 2-carbenabicyclooctadiene, whereas the formation ofthe C8H10 fraction (12-14) appears to be the result of hydrogen abstraction reactions of the corresponding triplet carbene or closely related species.
