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A combined matrix isolation and molecular orbital study of the vibrational spectra and photochemistry of 4,6-dimethyl-α-pyrone (DMAP) was undertaken. Two types of photoreactions: ring opening leading to conjugated ketene and valence isomerization to the Dewar form (1,5-dimethyl-2-oxa-3-oxobicyclo[2.2.0]hex-5-ene; DOOBH), occurred upon UV (λ>315nm) irradiation. The latter reaction was efficient,...
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