The Substituent Effect. V. NMR Chemical Shifts of Hydrogen-bonding Hydroxyl Proton of Phenols in DMSO
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概要
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The chemical shifts of the hydrogen bonded OH proton of <I>m</I>- and <I>p</I>-substituted phenols, and 4-substituted 2-cresols, 3-cresols, and 2,6-xylenols were determined in DMSO. The effects of substituents on the hydroxyl chemical shift of these series were correlated linearly with each other (correlation coefficient>0.999), except for the bulky planar substituents in the 3-cresol series which may be subject to the steric loss of their coplanarity with the benzene ring. The substituent effects were treated successfully with the equation, <I>Δ</I>δ=ρ(σ<SUP>0</SUP>+<I>r</I><SUP>−</SUP><I>Δ</I>\barσ<SUB>R</SUB><SUP>−</SUP>). The phenol series gave <I>r</I><SUP>−</SUP>=0.673 and ρ=1.530. The same <I>r</I><SUP>−</SUP> value appeared to be applicable to all the other series with negligible changes in the ρ value. Deviations from the correlation of particular substituents, in particular those having acidic hydrogen, were attributed to the modification of the electronic nature of substituents arising from the strong substituent-DMSO interaction.
- 公益社団法人 日本化学会の論文
著者
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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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TAKAI Yoshio
Institute of Scientific and Industrial Research, Osaka University
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Yukawa Yasuhide
Institute of Scientific and Industrial Research, Osaka University
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