Triarylcarbenium Salts Highly Reducible by Primary Alcohols

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著者

    • WADA Masanori
    • Department of Materials Science, Faculty of Engineering, Tottori University
    • MISHIMA Hisashi
    • 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
    • KONISHI Hideki
    • Department of Materials Science, Faculty of Engineering, Tottori University
    • HAYASE Shuichi
    • Department of Materials Science, Faculty of Engineering, Tottori University
    • ERABI Tatsuo
    • Department of Materials Science, Faculty of Engineering, Tottori University

抄録

A series of triarylmethanols bearing <i>o</i>-methoxyl groups (<b>1a</b>: [2,6-(MeO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]<sub>3</sub>COH, <b>1b</b>: (2-MeOC<sub>6</sub>H<sub>4</sub>)[2,6-(MeO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]<sub>2</sub>COH, <b>1c</b>: Ph[2,6-(MeO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]<sub>2</sub>COH, <b>1d</b>: [2,5-(MeO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]<sub>3</sub>COH, <b>1e</b>: Ph<sub>2</sub>[2,6-(MeO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]COH) were prepared. Corresponding carbenium salts, [Ar<sub>3</sub>C]X <b>2a</b>—<b>c</b>, were isolated by short-period treatments of Ar<sub>3</sub>COH <b>1a</b>—<b>c</b> with a slight excess of acid in some bulky alcohols, such as 2-propanol or 2-methyl-1-propanol. The high basicity of <b>1a</b>—<b>c</b> was explained by through-space interactions of a pair of 2p electrons of an <i>o</i>-methoxyl oxygen with an empty 2p orbital of the resulting carbenium carbon. In ethanol, 1-butanol or 3-methyl-1-butanol, <b>1c</b>, as well as <b>2c</b>, was reduced under very mild conditions to triarylmethane, Ar<sub>3</sub>C–H <b>3c</b>, and in other bulkier alcohols it was reduced under more forcing conditions. The formations of aldehyde or ketone, the by-product, were confirmed in some cases. Compounds <b>1a</b>,<b>b</b>,<b>d</b>,<b>e</b>, as well as <b>2a</b>,<b>b</b>, reacted in analogous manners under more forcing conditions. The reaction rates in several alcohols increased in the order <b>2a</b> < <b>2b</b> < <b>2c</b>, and the reaction rates of alcohol for <b>2c</b> decreased in the order ethanol > 3-methyl-1-butanol > 1-butanol > 2-propanol > methanol > 2-butanol > 2-methyl-1-propanol. Compounds <b>2b</b>,<b>c</b> were also reduced in tetrahydrofuran, and formed xanthene derivatives in dimethyl sulfoxide or in water.

収録刊行物

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 68(1), 243-249, 1995-01-15

    公益社団法人 日本化学会

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各種コード

  • NII論文ID(NAID)
    10008884906
  • 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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