Reactivity of peroxomonophosphoric acid in the oxidation of benzaldehydes and dimethyl sulfoxide in aqueous ethanol.
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概要
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Oxidation of benzaldehydes and dimethyl sulfoxide with peroxomonophosphoric acid (PMPA) has been studied in 40% aqueous EtOH in order to examine the reactivity of undissociated and dissociated PMPA in comparison with that of peroxycarboxylic acid. The reactivity for DMSO was in the order RCO<SUB>3</SUB><SUP>−</SUP>>H<SUB>3</SUB>PO<SUB>5</SUB>>H<SUB>2</SUB>PO<SUB>5</SUB><SUP>−</SUP>>RCO<SUB>3</SUB>H>HPO<SUB>5</SUB><SUP>2−</SUP>. As in the peroxycarboxylic acid oxidation, PMPA oxidation of substituted benzaldehydes afforded phenols by aryl migration and benzoic acids by hydride migration. The product ratio changed with substituents and pH; salicylaldehyde (<I>o</I>-HO) gave only catechol by aryl migration, while <I>p</I>-chloro and unsubstituted benzaldehydes afforded benzoic acids predominantly. The oxidation of aldehydes bearing <I>p</I>-MeO and <I>p</I>-Me was a borderline case and the migratory ratio of Ar∼/H∼ was higher at lower pH, <I>i.e.</I>, the order being H<SUB>3</SUB>PO<SUB>5</SUB>>H<SUB>2</SUB>PO<SUB>5</SUB><SUP>−</SUP>>HPO<SUB>5</SUB><SUP>2−</SUP>. The substituent effect in the apparent <I>k</I><SUB>obsd</SUB> values was very small (<I>i.e.</I>, ρ≈0), but the effect for aryl migration (<I>k</I><SUB>Ar∼</SUB>) estimated from product selectivity gave ρ=−2.88(σ). The rate for hydride migration (<I>k</I><SUB>H∼</SUB>) resulted in ρ=1.7 and 2.0 (σ). Reactivity of PMPA in each dissociated form was compared with that of RCO<SUB>3</SUB>H.
- 公益社団法人 日本化学会の論文
著者
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Ogata Yoshiro
Department Of Mechanical Engineering Ii Faculty Of Engineering Kyoto University:(present Address)res
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Sawaki Yasuhiko
Department Of Applied Chemistry Faculty Of Engineering Nagoya University
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Sawaki Yasuhiko
Department of Applied Chemistry, Faculty of Engineering, Nagoya University
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Tsukamoto Yasuyuki
Department of Applied Chemistry, Faculty of Engineering, Nagoya University
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