A Theoretical Study on the Photochemical Isomerization of 2,6-Dimethylpyrazine

Abstract

DFT calculations on the photoisomerization of 2,6-dimethylpyrazine allowed us to confirm the role of benzvalene isomers in the isomerization of hexatomic heterocyclic compounds. 2,6-Dimethylpyrazine in the excited singlet states can be converted into the corresponding Dewar isomers. If the S2 state is populated, two Dewar isomers can be obtained, while the S1 state allows the formation of only one of the possible Dewar isomers. Both Dewar isomers can be converted into the benzvalene isomer, that is, the precursor of 4,5-dimethylpyrimidine, the reaction product. In fact, the benzvalene isomer can be obtained from the Dewar isomers in processes that occur without an activation energy, and it is the more stable benzvalene isomers that can be obtained from the Dewar isomers. CASSCF study indicates the presence of a conical intersection allowing the direct formation of the benzvalene isomer.