Substituent effects. XIX. Solvolysis of 1-aryl-1-(trifluoromethyl)ethyl tosylates.
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概要
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The rates of solvolysis of 1-aryl-1-(trifluoromethyl)ethyl tosylates were determined in 80% aqueous ethanol for a series of substituents. The Brown ρ<SUP>+</SUP>σ<SUP>+</SUP> treatment fails to give a simple linear plot, but all the <I>p</I>-π-donors deviate upward from the meta-correlation line. On the other hand, the Yukawa–Tsuno LArSR Eq. gives a linear correlation over the whole range of substituents, log(<I>k</I>⁄<I>k</I><SUB>0</SUB>)=−6.287(σ°+1.388Δ\barσ<SUB>R</SUB><SUP>+</SUP>), with excellent precision. Strong destabilization of the carbocation intermediate by α-CF<SUB>3</SUB> appears to be reflected only in the extremely high <I>r</I> value, but not in the ρ value of the substituent effect. This conflicts seriously with the conclusion in the literature given for this reaction based on a simple Brown σ<SUP>+</SUP> treatment. This reaction, having an extremely high resonance demand <I>r</I>=1.4, should be far beyond the scope of the simple Brown σ<SUP>+</SUP> analysis. Varying resonance demand should be a basic requirement for adequately describing the substituent effect regarding conjugative carbocation reactions.
- 公益社団法人 日本化学会の論文
著者
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Fujiyama Ryoji
Department Of Material Science Faculty Of Science Kochi University
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Mishima Masaaki
Department Of Chemistry And Physics Of Condensed Matter Graduate School Of Sciences Kyushu Universit
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FUJIO Mizue
Department of Chemistry, Faculty of Science, Kyushu University
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Tsuno Yuho
Department Of Chemistry Faculty Of General Education Kumamoto University
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Goto Mutsuo
Department of Chemistry, Faculty of Science, Kyushu University
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Murata Akihisa
Department of Chemistry, Faculty of Science, Kyushu University
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Fujiyama Ryoji
Department of Chemistry, Faculty of Science, Kochi University
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