Bent Acenes: Synthesis and Molecular Structure of [6](1,4)Naphthalenophane and [6](1,4)Anthracenophane

Yoshito Tobe*, Tohru Takahashi, Takatoshi Ishikawa, Masashi Yoshimura, Mitsuhito Suwa, Kazuya Kobiro, Kiyomi Kakiuch, Rolf Gleiter

*Corresponding author for this work

Research output: Contribution to journalArticle

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Abstract

The first total syntheses and structural studies of [6](1,4)naphthalenophane (4) and [6](1,4)anthracenophane (5), the smallest-bridged isolable cyclophanes with bent acene nuclei, are disclosed. The acenophanes 4 and 5 were successfully synthesized by the oxidative decarboxylation of the benzo- and naphtho-fused propellenecarboxylic acids 10 and 11 to give the bridgehead olefins 12 and 13 followed by subsequent treatment with potassium tert-butoxide. The acids 10 and 11 were obtained conveniently by the Diels-Alder reactions of the diene 7 followed by ring contraction. The electronic spectra and photoclcctron spectra of 4 and 5 were measured and were compared with the corresponding 1,4-diethyl derivatives 14 and 15. The bathochromic shift of the first transition in the UV spectrum, as well as the shift of the first ionization energies of 4 and 5 in comparison to 14 and 15, respectively, can be ascribed mainly to the inductive effect of the hexamethylene chain and not to a bending of the π-system. The 1H NMR chemical shifts of 4 and 5 as well as their dynamic NMR behavior suggest that the bridging methylene groups of 4 and 5 are more relaxed than that of 1. The X-ray crystallographic structure analysis of 5 strongly supports these observations. The bent angle of the bridged aromatic ring of 5 is greater (by 1.5-1.6°) than those of the [6]paracyclophane derivatives 16 and 17, whereas the deformation of the bridging methylene group of 5 is smaller than those of the latter.

Original languageEnglish
Pages (from-to)8889-8894
Number of pages6
JournalJournal of the American Chemical Society
Volume112
Issue number24
DOIs
StatePublished - 1 Jan 1990

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    Tobe, Y., Takahashi, T., Ishikawa, T., Yoshimura, M., Suwa, M., Kobiro, K., Kakiuch, K., & Gleiter, R. (1990). Bent Acenes: Synthesis and Molecular Structure of [6](1,4)Naphthalenophane and [6](1,4)Anthracenophane. Journal of the American Chemical Society, 112(24), 8889-8894. https://doi.org/10.1021/ja00180a036