A Novel Reduction in the Presence of Precipitated Metals. II. The Behavior of Precipitated Metals and Water in Catalytic Reduction
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概要
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The ppt-metal-catalyzed reduction, which is performed by refluxing the substrates with water in the presence of ppt-metals, was investigated in detail. The participation of water as a hydrogen donor was demonstrated by the fact that benzaldehyde was reduced to the corresponding deuterated alcohols when heated with D<SUB>2</SUB>O in the presence of ppt-Ni. The scope of the reduction was established by the reaction of cyclohexanone with ppt-metals and water. The most preferable H<SUB>2</SUB>O/cyclohexanone molar ratio was found to be about 15 : 1. The reaction was accelerated when a 0.25N aqueous solution of sodium chloride was used instead of water. It was found that the order of the abilities of various ppt-metals to decompose water is different from that of the abilities to catalyze the reduction of cyclohexanone. The values of the activation energies for the reduction catalyzed by ppt-Ni and ppt-Ni,Co were found to be 4.0 kcal/mol and 7.5 kcal/mol respectively. From these facts, it was concluded that the ppt-metal-catalyzed reduction consists of two steps: the reaction of water with zinc or zinc compounds to supply a hydrogen source necessary for the hydrogenation, followed by ordinary catalytic hydrogenation.
- 公益社団法人 日本化学会の論文
著者
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SAKAI Koji
Department of Cardiovascular Medicine, Kyushu University Graduate School of Medical Sciences
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Watanabe Ken-ichi
Department Of Biology And Geosciences Faculty Of Science Shizuoka University
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Hata Kazuo
Department of Chemistry, Faculty of Science, Tokyo Metropolitan University
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Ishige Masayoshi
Department of Chemistry, Faculty of Science, Tokyo Metropolitan University
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WATANABE Ken-ichi
Department of Agricultural Chemistry, Faculty of Agriculture, Tohoku University
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