Photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction: intramolecular cyclization of an ene-diene radical cation

Article Abstract:

The photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction of methanol with 7-methyl-3-methylene-1,6-octadiene or beta myrcene and 1,4-dicyanobenzene gives five 1:1:1 adducts, all of which are cyclic. Variation in the product ratio as it relates to methanol concentration shows 1,6-endo cyclization is taking place with the radical cation, which is formed first, and the beta-alkoxyalkyl radicals, which are intermediates. Based on comparison of the ionization and oxidation potential of beta-myrcene with model alkenes and with conjugated dienes, it appears the initial electron transfer is related to the trisubstituted mono alkene moiety. The oxidation of the diene moiety, mono-substituted at a nodal position, is higher.

Canada, Photochemical research, Aromatic compounds, Olefins, Alkenes

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The absolute kinetics for radical addition and electronic energy transfer to (1.1.1)propellane

Article Abstract:

Electronic energy transfer to (1.1.1) propellane has been studied because of its abnormal properties. Free radicals react more readily with (1.1.1)propellane than with styrene. There is a linear dependence of the log of the quenching rate constants on the excited-state energy of the donors when triplet bezophenone is quenched by (1.1.1) propellane. Mechanisms for electronic energy transfer and possible mechanisms for electronic relaxation of (1.1.1)propellane in an excited state have been proposed.

Measurement, Free radicals (Chemistry), Free radicals, Chemical reaction, Rate of, Chemical kinetics, Photochemistry, Propellanes

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