The Ei reaction of substituted threo- and erythro-1-phenylethyl phenyl sulfoxides.
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概要
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Substituted (<I>RS</I>,<I>SR</I>)-1-phenylethyl phenyl sulfoxides (threo) (XC<SUB>6</SUB>H<SUB>4</SUB>S(O)CH(CH<SUB>3</SUB>)C<SUB>6</SUB>H<SUB>4</SUB>Y) and some substituted (<I>RR</I>,<I>SS</I>)-sulfoxides (erythro) were prepared and kinetic investigation for the thermal decomposition was carried out at 80.0, 90.0, and 100.0 °C in dioxane. Hammett plots for <I>threo</I>-XC<SUB>6</SUB>H<SUB>4</SUB>S(O)CH(CH<SUB>3</SUB>)C<SUB>6</SUB>H<SUB>5</SUB> gave positive ρ-values (ρ<SUB>X</SUB>=0.60–0.64 at three temperatures), while those for <I>threo</I>- and <I>erythro</I>-C<SUB>6</SUB>H<SUB>5</SUB>S(O)CH(CH<SUB>3</SUB>)C<SUB>6</SUB>H<SUB>4</SUB>Y snowed V-shape lines with bottoms at the <I>m</I>-OCH<SUB>3</SUB> substituent though the effects of the substituents are small. Meanwhile, large kinetic isotope effects for <I>threo</I>- and <I>erythro</I>-C<SUB>6</SUB>H<SUB>5</SUB>S(O)CH(CD<SUB>3</SUB>)C<SUB>6</SUB>H<SUB>4</SUB>Y (Y=H, <I>p</I>-OMe, <I>m</I>-Cl) (<I>k</I><SUB>H</SUB>⁄<I>k</I><SUB>D</SUB>=4–6) were observed at all temperatures. The activation energies were in the range of 104–121 kJ mol<SUP>−1</SUP> for all sulfoxides, while the activation entropies were relatively large (7–37 J K<SUP>−1</SUP> mol<SUP>−1</SUP>) and were correlated with Hammett σ-values to give small negative trend. Reactions of all erythro-isomers examined were 2–3 times faster than those of the corresponding threo-isomers. From these results, it is suggested that the pyrolysis of 1-arylethyl aryl sulfoxides proceeds via a concerted mechanism in which the transition state is variable from an El-like to a conjugated one. In the latter transition state, conjugation of the phenyl group bearing the electron-withdrawing substituent with the developing π-bond electron acidifies the β-proton.
- 公益社団法人 日本化学会の論文
著者
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Shimasaki Choichiro
Department Of Chemical And Biochemical Engineering Faculty Of Engineering Toyama University
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Tsukurimichi Eiichi
Department Of Chemical And Biochemical Engineering Faculty Of Engineering Toyama University
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Yoshimura Toshiaki
Department of Applied Chemistry, Faculty of Engineering, Osaka City University
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Isaji Hiroshi
Department of Industrial Chemistry, Faculty of Engineering, Toyama University
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Iizuka Yukihiko
Department of Industrial Chemistry, Faculty of Engineering, Toyama University
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Mizuno Hironobu
Department of Industrial Chemistry, Faculty of Engineering, Toyama University
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