UNIMOLECULAR REACTIONS OF ORTO-VINYL-PHENYLNITROSO OXIDE
The article is devoted to investigating of the unimolecular reactions of the representative of aromatic nitroso oxides, namely an ortho-vinyl-phenylnitroso oxide (1). A surface of potential energy of (1) was explored at the UB3LYP level of theory with the 6-311+G(d,p) basis set. Geometries of isomeric forms were localized, and activation barriers of their mutual transitions are calculated. Possible routes of unimolecular transformations of (1) were considered: (3+2)-cycloaddition; transition of terminal O-atom to the ortho-aromatic carbon atom; one-centered addition of NOO-group to double bond of vinyl group; epoxidation; H-transfer from alpha-carbon of vinyl group to nitroso oxide group thus leading to ketene derivative; formation of dioxaziridine. Among them, the most probable reaction (Ea = 51.7 kJ/mol) is bonding of the terminal oxygen atom to ortho-carbon atom.