PHOTOCHEMISTRY OF 2-AMINO-2H-BENZOCHROMENES

Article abstract of DOI:10.1007/BF00480829

Diabatic photoinduced ring opening of the chromene ring of 2-amino-5,6-benzo-2H-chromenes and 2-amino-6-methyl-7,8-benzo-2H-chromenes leads, in the same way as a thermally induced reaction, to the establishment of ring-chain tautomer equilibrium in the ground electronic state, the position of this equilibrium depending on the polarity of the solvent, the temperature, and structural factors. o-Quinoid tautomers exist as several stable isomeric forms: an acoplanar cis-S-cis-trans-form absorbing in the shortwave region, and S-trans-isomers absorbing in the longwave regionof the spectrum.Photoexcitation of the o-quinoid forms in the temperature range 125-190 K initiates mutual conversions of these and the initial 2H-chromene structure.The relative stability of the conformers of the o-quinoid form depends on steric and electronic factors: benzanellation in positions 5,6 leads to stabilization of the cis-S-cis-trans-isomer and in positions 7,8 the S-trans-isomers are more preferred: ?-acceptor substituents on the amine component increase the stability of the cis-S-cis-trans isomer and electron-donor substituents stabilize the S-trans-isomer.