Palladium-catalyzed synthesis of oligo(methylthio) aniline and conversion to polyacene-type electrolytes bearing phenothiazinium repeating units

Kenichi Oyaizu, Fumio Mitsuhashi, Eishun Tsuchida

    Research output: Contribution to journalArticle

    14 Citations (Scopus)

    Abstract

    The synthetic routes to ladder polymers which consist of benzenetetrayl subunits with imino and methyl-sulfonio linkages are described. As the key intermediate, oligo- and polyaniline derivatives having pendant methylthio groups are prepared by the Pd-catalyzed aryl amination from various monomers. The Oxidation of the polymers with H2O2 in the presence of CH3COOH effects the high yielding conversion of methylthio to methylsulfinyl groups without the formation of the undesired methylsulfonyl groups. The superacid-induced condensation of the resulting polymers under dilution conditions induced the polymer-analogous intramolecular electrophilic ring closure reaction of the hydroxy(methyl)(phenyl)sulfonium cation onto the adjacent benzene ring to yield the required ladder polymers which have proved to be semiconductors with intrinsic electric conductivities of ca. 10-5 S · cm-1.

    Original languageEnglish
    Pages (from-to)1328-1336
    Number of pages9
    JournalMacromolecular Chemistry and Physics
    Volume203
    Issue number10-11
    DOIs
    Publication statusPublished - 2002 Jul 29

    Fingerprint

    Bearings (structural)
    Palladium
    Aniline
    aniline
    Electrolytes
    palladium
    Polymers
    electrolytes
    polymers
    synthesis
    Ladders
    ladders
    Amination
    rings
    Polyaniline
    Benzene
    linkages
    Dilution
    closures
    dilution

    Keywords

    • Charge transfer
    • Conjugated polymers
    • Heteroatom-containing polymers
    • Polycondensation
    • Polyelectrolytes

    ASJC Scopus subject areas

    • Polymers and Plastics
    • Materials Chemistry
    • Organic Chemistry
    • Physical and Theoretical Chemistry

    Cite this

    Palladium-catalyzed synthesis of oligo(methylthio) aniline and conversion to polyacene-type electrolytes bearing phenothiazinium repeating units. / Oyaizu, Kenichi; Mitsuhashi, Fumio; Tsuchida, Eishun.

    In: Macromolecular Chemistry and Physics, Vol. 203, No. 10-11, 29.07.2002, p. 1328-1336.

    Research output: Contribution to journalArticle

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