Ion/molecule reactions in gaseous isopropyl alcohol.
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概要
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The ion/molecule reactions observed in 4 Torr CH<SUB>4</SUB> containing known small amounts of <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>OH or <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>OH/H<SUB>2</SUB>O mixture were studied over the temperature range 40–400 °C. The experiments were carried out using a pulsed electron beam mass spectrometer. At low temperatures (<150 °C), the major ions are <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>OH<SUB>2</SUB><SUP>+</SUP>(<I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>OH)<I><SUB>n</SUB></I>. By increasing the temperature, the slow growth of ions with <I>m</I>⁄<I>z</I>=59, 85, and 101 is observed. These ions are assigned to (CH<SUB>3</SUB>)<SUB>2</SUB>COH<SUP>+</SUP>, (CH<SUB>3</SUB>)<SUB>2</SUB>CHC<SUP>+</SUP>(CH<SUB>3</SUB>)<SUB>2</SUB>, and C<SUB>6</SUB>H<SUB>13</SUB>O<SUP>+</SUP>, respectively. They are probably produced from reactions of <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB><SUP>+</SUP> with isopropyl alcohol. The (CH<SUB>3</SUB>)<SUB>2</SUB>COH<SUP>+</SUP> ion may be produced from the electrophilic attack of <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB><SUP>+</SUP> onto the secondary carbon atom of <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>OH. At high temperatures (≈400 °C), the (CH<SUB>3</SUB>)<SUB>2</SUB>COH<SUP>+</SUP> ion becomes dominant. Acid-catalyzed dehydration of isopropyl alcohol, <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>OH<SUB>2</SUB><SUP>+</SUP>+H<SUB>2</SUB>O→H<SUB>3</SUB>O<SUP>+</SUP>(H<SUB>2</SUB>O)+C<SUB>3</SUB>H<SUB>6</SUB>, is also observed. Ion/molecule reactions involved in the present experiment are discussed according to the frontier-orbital theory.
- 公益社団法人 日本化学会の論文
著者
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Yamabe Shinichi
Department Of Chemistry Nara University Of Education
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Hiraoka Kenzo
Faculty Of Engineering Yamanashi University
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Yamabe Shinichi
Department of Chemistry, Nara University of Education
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Takimoto Hajime
Faculty of Engineering, Yamanashi University
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