Carbonyl oxides reactions from geraniol-trans-(3,7-dimethylocta-2,6-dien-1-ol), 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis: kinetics and mechanisms.

ABSTRACT

A density functional theory (DFT) study of the mechanisms of carbonyl oxide reactions from geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis is presented. The geometries, energies, and harmonic vibrational frequencies of each stationary point were determined by B3LYP/6-31(d,p) and BH&HLYP/cc-pVDZ methods. According to the calculations, the ozonolysis reactions are initiated by the formation of van der Waals (VDW) complexes to yield primary ozonides, which rapidly open to carbonyl oxide compounds. These carbonyl oxide compounds react to form dioxanes and hydroperoxides. The hydroperoxides react by isomerization to form stable products. Glyoxal and methyl-glyoxal have been identified as the final product from geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis. Our results are in good agreement with the experimental studies.