Ring-opening Reactions of Cyclic Ethers. VIII. Acid-catalyzed Ring-opening Reactions of Isobutylene Oxide in Alcohols
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概要
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The rates of the ring-opening reaction of isobutylene oxide have been measured in methyl, ethyl, w-propyl and isopropyl alcohols in the range from 10 to 40°C under conditions where the molar ratio of an alcohol to the epoxide was kept at 10 and the range of the concentration of boron trifluoride etherate was <I>ca.</I> 1.0×10<SUP>−3</SUP> to <I>ca.</I> 4.0×10<SUP>−3</SUP> mol/<I>l</I>. The rate equation is expressed as follows: −<I>d</I>[epoxide]⁄<I>dt</I>=<I>k</I><SUB>2</SUB>[C<SUB>0</SUB>][epoxide], where [C<SUB>0</SUB>] is the initial concentration of the catalyst and [epoxide] is the instantaneous concentration of the epoxide at time <I>t</I>. The rate constants (<I>k</I><SUB>2</SUB>) decreased in the order, CH<SUB>3</SUB>OH>C<SUB>2</SUB>H<SUB>5</SUB>OH><I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB>OH>i-C<SUB>3</SUB>H<SUB>7</SUB>OH. The entropies of activation decreased in the same order, while the energies of activation were not appreciably changed. A plot of log<I>k</I><SUB>2</SUB> against 1/<I>D</I> (<I>D</I>, the dielectric constant of the mixture of each alcohol and the epoxide) was found to be linear, its slope being −61.2. The results support the fact that the reaction is bimolecular.
- 公益社団法人 日本化学会の論文
著者
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Sekiguchi Shizen
Department of Chemistry, Faculty of Engineering, Gunma University
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Matsui Kohji
Department of Chemistry, Faculty of Engineering, Gunma University
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Sekiguchi Shizen
Department of Synthetic Chemistry, Faculty of Engineering, Gunma University
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Yasuraoka Yoshihiro
Department of Synthetic Chemistry, Faculty of Engineering, Gunma University
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