6221-55-2Relevant academic research and scientific papers
The Mechanism of 1,2-Bond Shift Rearrangements of Paraffins on Transition Metal Surfaces
Amir-Ebrahimi, Valia,Rooney, John J.
, p. 260 - 261 (1988)
Isomerization of protoadamantane to adamantane and of bicyclooctane to bicyclooctane occurs on reduced molybdenum powder or on reduced molybdena/alumina catalysts in excess of hydrogen at >/= 275 deg C; an olefin metathesis-type mechanism is precluded by the structures of these caged compounds, so simple bond shift in alkyl radicals on transition metal surfaces seems to be generally valid reaction pathway in heterogenous conversions of paraffins.
The vibrational spectra (100-1500 cm-1) of a series of bicyclooctanes assigned by means of scaled 3-21G ab initio harmonic force fields
Eggimann, Thomas,Ibrahim, Nan,Shaw, R. Anthony,Wieser, Hal
, p. 578 - 610 (2007/10/02)
The infrared absorption (vapor phase and solution) and Raman (liquid phase) spectra of bicyclooctane, 8-oxabicyclooctane, 6-oxabicyclooctane, 6,8-dioxabicyclooctane, and the 7,7-dideutero-substituted derivatives of the last two compounds are reported in the region 100-1500 cm-1 for the first time.The vibrational spectra are assigned almost completely with the guidance of ab initio 3-21G geometries and scaled force fields.A total of 14 force-field scale factors are transferred from smaller molecules, predicting the frequencies with an average error of 7.6 cm-1 (1.2percent) for 196 assigned transitions.After optimizing the factors in an overlay refinement involving all six molecules, the frequencies are within 5.7 cm-1 (0.75percent) of experiment.The ab initio absorption and Raman intensities are calculated with the 3-21G basis set and are demonstrated to be of such accuracy as to be useful for the spectral assignments.These intensities are calculated with uniformly and nonuniformly scaled force fields and compared to the experimental spectra.The intensities derived from the latter force fields are superior, meaning that nonuniform scaling is preferable at this level of theory for both vibrational frequencies and normal mode descriptions.
Hydroalumination of alkenes by the LiAlH4*3AlBr3 system
Gorobets, E. V.,Shitikova, O. V.,Lomakina, S. I.,Tolstikov, G. A.,Kuchin, A. V.
, p. 1573 - 1578 (2007/10/02)
The hydroalumination of a series of alkenes and some fused aromatic hydrocarbons by the LiAlH4*3AlBr3 system in low-polar solvents was studied.Alkenes with mono-, di-, tri-, and tetraalkyl substituted, mono- and diaryl substituted double bonds and anthracene react at room temperature to give the corresponding dibromoaluminoalkanes in high yields.Benzylidenefluorene, tetraphenylethylene, naphthalene, and phenanthrene do not undergo hydroalumination under these conditions.Camphene, bicyclooct-2-ene, and norbornene afford the corresponding organoaluminum compounds with high stereoselectivity.Oxidation and halo- and acyldemetallation of the resulting alkyl- and arylalanes were carried out.
Cyclisation of 5-Bromomethyl-cycloheptene and -cyclo-octene: a New Route to Bicyclooctanes and Bicyclononanes
MacCorquodale, Finlay,Walton, John C.
, p. 347 - 352 (2007/10/02)
Reduction of 5-(bromomethyl)cycloheptene with tributyltin hydride gave bicyclooctane; similar reduction of 5-(bromomethyl)cyclo-octene gave bicyclononane together with some bicyclononane.The cyclohept-4-enylmethyl radical intermediate
Formation of Bicyclooctane, Bicyclononane, and Bicyclononane by Transannular Radical Cyclisations
MacCorquodale, Finlay,Walton, John C.
, p. 1456 - 1457 (2007/10/02)
Cyclohept-4-enylmethyl radicals undergo transannular cyclisation to give bicyclooctane; likewise, bicyclononane and bicyclononane are obtained from cyclo-oct-4-enylmethyl radicals.
HYDROGENOLYSIS OF CUBANE
Stober, Reinhard,Musso, Hans,Osawa, Eiji
, p. 1757 - 1762 (2007/10/02)
On catalytic hydrogenation over Pd-C under normal conditions cubane (10) takes up 3 mol of hydrogen in a few hours.Bicyclooctane (13) is formed as the main product, and tetracyclo2.5.03.8>octane (11, secocubane) and tricyclo2.5>octane (12, nortwistbrendane) have been identified as intermediates.The hydrogenolysis of dimethyl 1,4-cubane dicarboxylate, as well as cuneane derivatives, have also been studied.Results are discussed in terms of strain relief calculated by the molecular mechanics method for cubane-like structures.
BICYCLOOCTA-2,6-DIEN-8-YLIDENE (HOMO-7-NORBORNADIENYLIDENE), A "FOILED" CARBENE
Brinker, Udo H.,Koenig, Lothar
, p. 45 - 48 (2007/10/02)
Bicycloocta-2,6-dien-8-ylidene nearly exclusively rearranges by 1,2-vinyl migrations.The interaction with the double bond of the six-membered ring dominates.
Photochemistry of Alkyl Halides. 8. Formation of a Bridgehead Alkene
Kropp, Paul J.,Worsham, Paul R.,Davidson, Robert I.,Jones, Tappey H.
, p. 3972 - 3980 (2007/10/02)
Irradiation of the bridgehead iodides 4,7,and 10 afforded principally the ionic products 6,9,and 12 accompanied by small amounts of the reduction products 5, 8, and 11.Studies in methanol-d indicated an absence of pathways leading to ethers 6, 9, and 12 i
