Metal ion-catalyzed reduction of substituted nitrosobenzenes by 1-benzyl-3,5-bis(1-pyrrolidinylcarbonyl)-1,4-dihydropyridine in acetonitrile.

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概要

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• Metal ion catalyzed reduction of substituted nitrosobenzenes by 1-benzyl-3,5-bis(1-pyrrolidinylcarbonyl)1,4-dihydropyridine (BPDH) in acetonitrile has been studied for seven bivalent metal ions. The reduction of <I>N</I>-methylacridinium salt (MA) has also been examined. In the former cases, it was found that the metal ions catalyze the reduction by forming a 1:1 complex with BPDH according to a Michaelis–Menten type saturation kinetics which allowed to derive the association constants, <I>K</I><SUB>M</SUB>, for the complexation and the second-order rate constants, <I>k</I><SUB>2</SUB>, for the reduction. A linear relationship was found between log<I>k</I><SUB>2</SUB> and the ionization potentials of metal ions with a positive slope. A linear Hammett relationship was also observed between log<I>k</I><SUB>2</SUB> and the Hammett σ constants with a positive ρ value for three metal ions. These results suggest that a bivalent metal ion is sandwiched between the BPDH and the substrate and acts as a Lewis acid to stabilize the incipient <I>N</I>-oxide anion of the substrate which is formed by hydride transfer in the transition state. In the cases of MA, all metal ions inhibited the reduction. Repulsion between the positive charges of the metal ion-BPDH complex and the substrate salt appears to be prevailing.

• 公益社団法人 日本化学会の論文

著者

• Tamagaki Seizo

  Department Of Applied & Bioapplied Chemistry Graduate School Of Engineering Osaka City Universit

• TAKEMOTO Kazuo

  Department of Public Health, Saitama Medical School

• Tagaki Waichiro

  Department of Applied Chemistry, Faculty of Engineering Osaka City University

• Awano Hiroshi

  Department of Applied Chemistry, Faculty of Engineering, Osaka City University

• Ohya Hirohisa

  Department of Applied Chemistry, Faculty of Engineering, Osaka City University

• Tomio Minaki

  Department of Applied Chemistry, Faculty of Engineering, Osaka City University

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