Dimerization of 9-phenylethynylfluorene to di-indeno-naphthacene and dispiro-[fluorene-dihydronaphthacene-fluorene]: an X-ray crystallographic and NMR study.

The attempted Diels-Alder reaction between 9-phenylethynylfluorene and tetracyclone yields instead three products resulting from the dimerization of the isomeric allene. The major product is 8,16-diphenyl-diindeno[1,2,3-de:1',2',3'-mn]naphthacene, in which each terminal ring is derived from a fluorenyl unit; aerial oxidation then yields a peroxide. A dihydronaphthacene bearing fluorenyl moieties spiro-bonded at the C(5) and C(11) positions was also identified. The structures of the naphthacenes were elucidated by X-ray crystallography, and a mechanistic rationale is offered. [reaction: see text]