Facile Aromatic Nucleophilic Substitutions Observed for the Triarylcarbenium Ions, [(4-YC_6H_4)φ_2C]^+ [φ=2,6-(MeO)_2C_6H_3; Y=MeO, Cl, Me_2N, HO]

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著者

    • WADA Masanori
    • Department of Materials Science, Faculty of Engineering, Tottori University
    • WATANABE Tetsuya
    • Department of Materials Science, Faculty of Engineering, Tottori University
    • NATSUME Satoko
    • Department of Materials Science, Faculty of Engineering, Tottori University
    • MISHIMA Hisashi
    • Department of Materials Science, Faculty of Engineering, Tottori University
    • ERABI Tatsuo
    • Department of Materials Science, Faculty of Engineering, Tottori University

抄録

Triarylmethanols of type (4-YC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>COH {<i>Φ</i> = 2,6-(MeO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>; Y = MeO, Cl, Me<sub>2</sub>N} were prepared. The methanol, (4-MeOC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>COH, reacted with acids in a variety of solvents to give the triarylcarbenium salts, [(4-MeOC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X or [(4-HOC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X, or 4-bis(2,6-dimethoxyphenyl)methylene-2,5-cyclohexadienone, O=C<sub>6</sub>H<sub>4</sub>=C<i>Φ</i><sub>2</sub>, depending on the conditions. These carbenium salts further reacted in alcohols, ROH, to give the triarylmethanes, (4-ROC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>CH (R = Me, Et), where the <i>para</i>-substituent, MeO or HO, was substituted by the solvent, accompanied by a reduction at the central carbon. The methanol, (4-ClC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>COH, also reacted with acid to give the carbenium salt or the triarylmethane, depending on the conditions. While the methanol, (4-Me<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>COH, also gave the carbenium salt, [(4-Me<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X, it was inert against the formation of the triarylmethane under analogous conditions. It reacted with aqueous sodium hydroxide to give O=C<sub>6</sub>H<sub>4</sub>=C<i>Φ</i><sub>2</sub> rather than the original methanol. The <i>para</i>-substituent of [(4-MeOC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X was substituted by di- and monoalkylamines, RR′NH, to give [(4-RR′ NC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X (R,R′ = Me,Me; Et,Et; Me,H; Et,H; Bu,H). While [(4-ClC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X reacted with the dialkylamines to give [(4-RR′NC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X, it reacted with monoalkylamines, RNH<sub>2</sub>, to give [(4-ClC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C–NRH<sub>2</sub>]X. [(4-Me<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>)<i>Φ</i><sub>2</sub>C]X was hydrolyzed in the presence of diethylamine to give O=C<sub>6</sub>H<sub>4</sub>=C<i>Φ</i><sub>2</sub>, but reacted with monoalkylamines to give RN=C<sub>6</sub>H<sub>4</sub>=C<i>Φ</i><sub>2</sub>.

収録刊行物

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 68(11), 3233-3240, 1995-11-15

    The Chemical Society of Japan

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各種コード

  • NII論文ID(NAID)
    10008895527
  • NII書誌ID(NCID)
    AA00580132
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    00092673
  • データ提供元
    CJP書誌  J-STAGE 
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