Superacids and Their Derivatives. III. Kinetics of the Oxonium Ion Formation from Superacid Esters and Tetrahydropyran. Oxonium-Ester Equilibria
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概要
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Kinetic studies on the oxonium formation reaction between superacid esters (ROSO<SUB>2</SUB>X) and tetrahydropyran (THP) were carried out by means of NMR spectroscopy. The reaction was found to be an equilibrium process.<BR>(<U>Remark: Graphics omitted.</U>)<BR>The rate constant (<I>k</I>) of <I>S</I>N2 reaction and the equilibrium constant (1⁄<I>K</I>=<I>k</I>⁄<I>k</I>′) were determined. The solvent effect was examined and <I>k</I> was found to be in the order: nitrobenzene>chlorobenzene≈CH<SUB>2</SUB>Cl<SUB>2</SUB>>liquid SO<SUB>2</SUB>. The effects of R and X in ROSO<SUB>2</SUB>X were studied. Relative reactivities of primary alkyl series in the reaction of ROSO<SUB>2</SUB>C1 with THP were: Me: Et: <I>n</I>-Pr=4.63: 1.0: 0.294 in CH<SUB>2</SUB>Cl<SUB>2</SUB> and Me: Et: <I>n</I>-Pr=3.19: 1.0: 0.452 in nitrobenzene. The effect of X on <I>k</I> was in the order Cl≈CF<SUB>3</SUB>>F, the 1⁄<I>K</I> value being also extremely low when X=F. The result was discussed in relation to the kinetics of the polymerization of tetrahydrofuran (THF) by ROSO<SUB>2</SUB>X.
- 公益社団法人 日本化学会の論文
著者
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Saegusa Takeo
Department Of Synthetic Chemistry Faculty Of Engineering Kyoto University
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Kobayashi Shiro
Department Of Material Chemistry Graduate School Of Engineering Kyoto University
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Ashida Tadashi
Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University
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