5259-71-2Relevant articles and documents
Discontinuous pressure effect upon enantiodifferentiating photosensitized isomerization of cyclooctene
Kaneda, Masayuki,Asaoka, Sadayuki,Ikeda, Haruhiko,Mori, Tadashi,Wada, Takehiko,Inoue, Yoshihisa
, p. 1272 - 1273 (2007/10/03)
A hydrostatic pressure of up to 750 MPa induced discontinuous changes in the enantiomeric excess of the (E)-isomer obtained in the enantiodifferentiating photoisomerization of (Z)-cyclooctene and (Z,Z)-cycloocta-1,5-diene, sensitized by chiral benzene-1,2,4,5-tetracarboxylates; indicating a switching of the enantiodifferentiation mechanism, which is attributable to dramatic conformational changes of chiral alkoxycarbonyl auxiliaries at a specific pressure.
The C8H12-Energy Hypersurface Thermolysis of syn- and anti-Tricyclo2,5>octane. Experimental and Theoretical Studies
Martin, Hans-Dieter,Eisenmann, Erwin,Kunze, Michael,Bonacic-Koutecky, Vlasta
, p. 1153 - 1179 (2007/10/02)
The thermal behaviour of syn- and anti-tricyclo2,5>octanes 9 and 10 in the gas phase as well as in solution is investigated.Two main products are formed in parallel reactions: cis,cis-1,5-cyclooctadiene (11) and cis,trans-1,5-cyclooctadiene (15), the latter being partly isomerized to 11 under the reaction conditions.Minor products are cis-1,2-divinylcyclobutane (6), trans-1,2-divinylcyclobutane (16) and 4-vinyl-1-cyclohexene (17).Thermolysis of cis-1,2-divinylcyclobutane leads to small amounts of cis,trans-cyclooctadiene, presumably via a four-centre transition state.The tricyclics most likely prefer a stepwise isomerization.The decisive product-controlling factor seems to be the conformational mobility of intermediate diradicals.By comparison with the boat-Cope reaction of divinylcyclobutane the pericyclic six-centre transition state of this rearrangements is shown to lie energetically about 19 kcal/mol below the transition states in the thermolysis of 9 and 10.The azo compound 12 on heating fragments predominantly in a concerted manner in contrast to the photolysis.Theoretical methods are applied to unveil structure and bonding in the supposed intermediate diradicals.
Photoelimination of nitrogen from cyclic azo alkanes. An exceptionally labile and an exceptionally reluctant diazabicyclo[2.2.2]octene
Turro, Nicholas J.,Liu, Jonq-Min,Martin, Hans-Dieter,Kunze, Michael
, p. 1299 - 1302 (2007/10/02)
The photochemistry of an unusually reactive diazabicyclo[2.2.2]octene has been found to be extremely solvent and temperature dependent; an exceptionally stable diazabicyclo[2.2.2]octene has been found to undergo a novel fragmentation as a result of vapor phase photoexcitation.