2841-40-9Relevant articles and documents
Sequential formation of yellow, red, and orange 1-phenyl-3,3-biphenylene- allene dimers prior to blue tetracene formation: Helicity reversal in trans-3,4-diphenyl-1,2-bis(fluorenylidene)cyclobutane
Banide, Emilie V.,Ortin, Yannick,Seward, Corey M.,Harrington, Laura E.,Mueller-Bunz, Helge,McGlinchey, Michael J.
, p. 3275 - 3286 (2008/09/18)
1-Phenyl-3,3-biphenylene-allene (2), the base-catalyzed rearrangement product of 9-phenylethynylfluorene (1) yields a yellow, head-to-tail dimer 6 that, upon gentle warming, is converted to the red tail-to-tail isomer trans-3,4-diphenyl-1,2-bis(fluorenylidene)cyclobutane (7), in which the two fluorenylidene moieties severely overlap. The helical sense of the fluorenylidene moieties in 7 matches that of the phenyl substituents, and the interplanar angle between the fluorenylidene moieties is 41°. At 80°C, 6 isomerizes to orange cis-3,4-diphenyl-1,2-bis(fluorenylidene)cyclobutane (8), which at 110°C is converted to orange trans diastereomer 9, whereby the helicity of the overlapping fluorenylidene moiet ies is reversed from that in 7 such that they are aligned with the ring hydrogen atoms, and the interplanar angle between the fluorenylidene moieties is now 60°. At 180°C. 6 rearranges to dispirodihydrotetracene 3 and blue, electroluminescent diindenotetracene 4, which is readily oxidized to peroxide 5. In the solid state, both 3 and 4 adopt structures with Ci, symmetry (only an inversion center) such that the central polycyclic framework is nonplanar. Deprotonation of yellow head-to-tail allene dimer 6 with tBuOK in DMSO and reprotonation with HOAc yields the [1.3]-hydrogen migration product 10, in which the proton originally on the cyclobutane ring is now sited at C9 on the exocyclic fluorenyl substituent. Analogously, deprotonation and reprotonation of orange dimer 9 furnishes [1,3]-hydrogen migration product 11. Side product 17, formed during the synthesis of 1 from 9-phenylethynylfluoren-9-ol, BF3 and Et3SiH, was shown to be a silyl-indene spiro-linked to C9 of fluorene. All products were characterized by NMR spectroscopy and X-ray crystallography, and the mechanisms of these interconversions are discussed.
