On the reaction of (vinylimino)phosphorane and related compounds. 22. Syntheses and structural studies of methanocycloundeca[b]pyrrole ring systems

Nobuhiro Kanomata, Ken Ichi Kamae, Yukio Lino, Makoto Nitta

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    12 Citations (Scopus)

    Abstract

    Novel 2-phenyl-6,11- and 2-phenyl-4,9-methanocycloundeca[6]pyrroles (15a and 16a) were synthesized in moderate yields by the reaction of 3,8-methano[11]annulenone (3), a 10π-electron vinylogue of tropone, with [(1-phenylvinyl)imino]triphenylphosphorane (8a) and subsequent dehydrogenation. Similarly, the reaction of the annulenone 3 with (inden-3-ylimino)tributylphosphorane (8c) and subsequent aromatization afforded 7,12-and 9,14-methano-15H-cycloundeca[6]indeno[2,3-d]pyrroles (15c and 16c), which also have methanocycloundeca[b]pyrrole ring systems. Preparation of 2-phenyl-5,10-methanocycloundeca[6]pyrrole (17), an isomer of both 15a and 16a, was also accomplished in low yield by the reaction of 4,9-methano[11]annulenone (5) with an excess of [(1-phenylvinyl)imino]tributylphosphorane (8d). The reactivity of annulenone 5 with (vinylimino)phosphoranes was found to be quite low as compared to the higher reactivity of annulenone 3 and tropone. Compounds 15a,c, 16a,c, and 17 are the first nitrogen analogues of cyclopentacycloundecene ring systems which have vinylogous structures of 1-azaazulene. Structures of the products obtained were examined by 1H NMR spectra and UV spectra. The 1H NMR spectra clarified that the compounds 15a,c, 16a,c, and 17 are aromatic molecules having a diatropic 14π-electron system, and 5,10-methano derivative 17 has a more diatropic nature than the compounds 15a,c and 16a,c. The UV spectra of 15a,c, 16a,c, and 17 exhibited increased cyclic conjugation of the aromatic perimeter according to a bathochromic shift of the longest absorption maxima as compared to the corresponding 1-azaazulene derivatives.

    Original languageEnglish
    Pages (from-to)5313-5318
    Number of pages6
    JournalJournal of Organic Chemistry
    Volume57
    Issue number20
    Publication statusPublished - 1992

    Fingerprint

    Phosphoranes
    Pyrroles
    Nuclear magnetic resonance
    Derivatives
    Aromatization
    Electrons
    Dehydrogenation
    Isomers
    Nitrogen
    annulenone
    Molecules

    ASJC Scopus subject areas

    • Organic Chemistry

    Cite this

    On the reaction of (vinylimino)phosphorane and related compounds. 22. Syntheses and structural studies of methanocycloundeca[b]pyrrole ring systems. / Kanomata, Nobuhiro; Kamae, Ken Ichi; Lino, Yukio; Nitta, Makoto.

    In: Journal of Organic Chemistry, Vol. 57, No. 20, 1992, p. 5313-5318.

    Research output: Contribution to journalArticle

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    abstract = "Novel 2-phenyl-6,11- and 2-phenyl-4,9-methanocycloundeca[6]pyrroles (15a and 16a) were synthesized in moderate yields by the reaction of 3,8-methano[11]annulenone (3), a 10π-electron vinylogue of tropone, with [(1-phenylvinyl)imino]triphenylphosphorane (8a) and subsequent dehydrogenation. Similarly, the reaction of the annulenone 3 with (inden-3-ylimino)tributylphosphorane (8c) and subsequent aromatization afforded 7,12-and 9,14-methano-15H-cycloundeca[6]indeno[2,3-d]pyrroles (15c and 16c), which also have methanocycloundeca[b]pyrrole ring systems. Preparation of 2-phenyl-5,10-methanocycloundeca[6]pyrrole (17), an isomer of both 15a and 16a, was also accomplished in low yield by the reaction of 4,9-methano[11]annulenone (5) with an excess of [(1-phenylvinyl)imino]tributylphosphorane (8d). The reactivity of annulenone 5 with (vinylimino)phosphoranes was found to be quite low as compared to the higher reactivity of annulenone 3 and tropone. Compounds 15a,c, 16a,c, and 17 are the first nitrogen analogues of cyclopentacycloundecene ring systems which have vinylogous structures of 1-azaazulene. Structures of the products obtained were examined by 1H NMR spectra and UV spectra. The 1H NMR spectra clarified that the compounds 15a,c, 16a,c, and 17 are aromatic molecules having a diatropic 14π-electron system, and 5,10-methano derivative 17 has a more diatropic nature than the compounds 15a,c and 16a,c. The UV spectra of 15a,c, 16a,c, and 17 exhibited increased cyclic conjugation of the aromatic perimeter according to a bathochromic shift of the longest absorption maxima as compared to the corresponding 1-azaazulene derivatives.",
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    T1 - On the reaction of (vinylimino)phosphorane and related compounds. 22. Syntheses and structural studies of methanocycloundeca[b]pyrrole ring systems

    AU - Kanomata, Nobuhiro

    AU - Kamae, Ken Ichi

    AU - Lino, Yukio

    AU - Nitta, Makoto

    PY - 1992

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    N2 - Novel 2-phenyl-6,11- and 2-phenyl-4,9-methanocycloundeca[6]pyrroles (15a and 16a) were synthesized in moderate yields by the reaction of 3,8-methano[11]annulenone (3), a 10π-electron vinylogue of tropone, with [(1-phenylvinyl)imino]triphenylphosphorane (8a) and subsequent dehydrogenation. Similarly, the reaction of the annulenone 3 with (inden-3-ylimino)tributylphosphorane (8c) and subsequent aromatization afforded 7,12-and 9,14-methano-15H-cycloundeca[6]indeno[2,3-d]pyrroles (15c and 16c), which also have methanocycloundeca[b]pyrrole ring systems. Preparation of 2-phenyl-5,10-methanocycloundeca[6]pyrrole (17), an isomer of both 15a and 16a, was also accomplished in low yield by the reaction of 4,9-methano[11]annulenone (5) with an excess of [(1-phenylvinyl)imino]tributylphosphorane (8d). The reactivity of annulenone 5 with (vinylimino)phosphoranes was found to be quite low as compared to the higher reactivity of annulenone 3 and tropone. Compounds 15a,c, 16a,c, and 17 are the first nitrogen analogues of cyclopentacycloundecene ring systems which have vinylogous structures of 1-azaazulene. Structures of the products obtained were examined by 1H NMR spectra and UV spectra. The 1H NMR spectra clarified that the compounds 15a,c, 16a,c, and 17 are aromatic molecules having a diatropic 14π-electron system, and 5,10-methano derivative 17 has a more diatropic nature than the compounds 15a,c and 16a,c. The UV spectra of 15a,c, 16a,c, and 17 exhibited increased cyclic conjugation of the aromatic perimeter according to a bathochromic shift of the longest absorption maxima as compared to the corresponding 1-azaazulene derivatives.

    AB - Novel 2-phenyl-6,11- and 2-phenyl-4,9-methanocycloundeca[6]pyrroles (15a and 16a) were synthesized in moderate yields by the reaction of 3,8-methano[11]annulenone (3), a 10π-electron vinylogue of tropone, with [(1-phenylvinyl)imino]triphenylphosphorane (8a) and subsequent dehydrogenation. Similarly, the reaction of the annulenone 3 with (inden-3-ylimino)tributylphosphorane (8c) and subsequent aromatization afforded 7,12-and 9,14-methano-15H-cycloundeca[6]indeno[2,3-d]pyrroles (15c and 16c), which also have methanocycloundeca[b]pyrrole ring systems. Preparation of 2-phenyl-5,10-methanocycloundeca[6]pyrrole (17), an isomer of both 15a and 16a, was also accomplished in low yield by the reaction of 4,9-methano[11]annulenone (5) with an excess of [(1-phenylvinyl)imino]tributylphosphorane (8d). The reactivity of annulenone 5 with (vinylimino)phosphoranes was found to be quite low as compared to the higher reactivity of annulenone 3 and tropone. Compounds 15a,c, 16a,c, and 17 are the first nitrogen analogues of cyclopentacycloundecene ring systems which have vinylogous structures of 1-azaazulene. Structures of the products obtained were examined by 1H NMR spectra and UV spectra. The 1H NMR spectra clarified that the compounds 15a,c, 16a,c, and 17 are aromatic molecules having a diatropic 14π-electron system, and 5,10-methano derivative 17 has a more diatropic nature than the compounds 15a,c and 16a,c. The UV spectra of 15a,c, 16a,c, and 17 exhibited increased cyclic conjugation of the aromatic perimeter according to a bathochromic shift of the longest absorption maxima as compared to the corresponding 1-azaazulene derivatives.

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