7062-97-7Relevant articles and documents
Photoaddition of Biacetyl and Alkenes. Reaction Stereochemistry, Multiplicity, and Photokinetics
Jones, Guilford,Santhanam, Mahalingham,Chiang, Sheau-Hwa
, p. 6088 - 6095 (1980)
Quantum yields are reported for the photoaddition of biacetyl with the alkenes indene, 2,3-dimethyl-2-butene, furan, and 1,2-dimethoxyethene in benzene solution.The dependence of quantum efficiencies on alkene concentration is consistent with a photoaddition mechanism involving biacetyl triplets.The quenching of fluid solution biacetyl phosphorescence has been observed, and quenching constants correlate with the electron-donor ability (ionization potentials) of the alkenes.Photoaddition of biacetyl and 1,2-dimethoxyethene is nonstereospecific, and oxetane formation is accompanied by the isomerization of the starting alkene.Stereochemical results are used to estimate relative rates of cleavage, closure, and stereorandomizing bond rotation in biradicals, proposed intermediates in photoaddition.Exciplexes of triplet biacetyl and alkenes are proposed as primary photochemical intermediates (precursors to biradicals) on the basis of stereochemical, emission quenching, and other data.
17O, 13C and 1H NMR spectra of 1,2-dialkoxyethenes
Taskinen, Esko
, p. 573 - 578 (2007/10/03)
The 17O, 13C and 1H NMR spectra of a number of 1,2-dialkoxyethenes R1OCH=CHOR2 were recorded. The O atoms, in particular those of the E forms, are strongly shielded relative to the 17O nuclei of the corresponding alkyl vinyl ethers ROCH=CH2. Moreover, in compounds of the type ROCH=CHOMe, the difference δ(17O)Z - δ(17O)E of the MeO group decreases and that of the RO group increases with increasing bulkiness of R. These trends probably arise from changes, with the size of the alkyl group R, in the stereochemistry of the RO group of the E-isomer about the O - C(sp2) bond, whereas the stereochemistry of the Z-form seems to be independent of the size of R. Additional information on the stereochemistry of the title compounds is provided by their 13C and 1H NMR spectra.
Stereochemistry of Additions of m-Quinomethane to Olefins and Acyclic Dienes
Inglin, Thomas A.,Berson, Jerome A.
, p. 3394 - 3402 (2007/10/02)
The m-quinomethane biradical has a triplet ground state, as judged by the temperature dependence of the intensity of its EPR signal.When generated by pyrolysis or photolysis of 6-methylenebicyclohex-3-en-2-one, it adds to olefinic trapping agents to give phenolic indans.Retention of configuration dominates by a factor of 13-17 with cis-1,2-dimethoxyethene and by a factor of >100 with trans-1,2-dimethoxyethene.With the 2,4-hexadienes, which undergo addition to give phenolic 1-propenylindans, retention again is the favored pathway, but the preference is lower (up to 6-fold).The propenyl stereochemistry in the product is completely retained.A comparison with known results of cycloadditions of trimethylenemethane (singlet) biradical and of m-quinodimethane shows that m-quinomethane additions are intermediate between the other two in cis stereospecifity.A mechanistic rationale for this ordering is discussed.