Photochemical generation, intramolecular reactions, and spectroscopic detection of oxonium ylide and carbene intermediates in a crystalline ortho-(1,3-dioxolan-2-yl)-diaryldiazomethane

Photochemical excitation of a diaryldiazomethane with an ortho-acetal both in solution and in crystals led to products that originate from the expected diarylcarbene and form an intramolecular oxonium ylide. While crystals strongly favored the formation of a benzocyclobutane by intramolecular hydrogen abstraction in the triplet carbene, reactions in benzene led exclusively to products that derive from the oxonium ylide. Studies in methyl cyclohexane glasses and in mixed crystals at 77 K led to the spectroscopic detection of triplet carbene 3C, which partially transformed into a new species that we assign as the sought-after oxonium ylideY. The formation of a formally ionic intermediate suggests that the scope of reactions by reactive intermediates in crystalline solids may be broader than it is generally assumed.