Mechanism of carboxylic acid-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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Mechanism of carboxylic acid-catalyzed reduction of substituted nitrosobenzenes by 1-benzyl-3,5-bis(1-pyrrolidinylcarbonyl)-1,4-dihydropyridine has been studied in acetonitrile at 25 °C. The major product was hydroxylamine when the dihydropyridine was used in excess over nitrosobenzene, while that was azoxybenzene in the reverse case. The observed second-order rate constant <I>k</I><SUB>2</SUB><SUP>R</SUP> are dependent on acid concentration in a first-order manner with the acid-catalyzed third-order rate constant <I>k</I><SUB>H</SUB><SUP>R</SUP>. The Hammett relationship for <I>k</I><SUB>H</SUB><SUP>R</SUP> for substituted nitrosobenzenes gave a ρ=−0.93. The Brönsted plot of log <I>k</I><SUB>H</SUB><SUP>R</SUP> vs. p<I>K</I><SUB>a</SUB> of acids gave a straight line with a slope of −0.34. The deuterium isotope effect for the catalysis by dichloroacetic acid was found to be <I>k</I><SUB>H</SUB><SUP>R</SUP>⁄<I>k</I><SUB>D</SUB><SUP>R</SUP>=2.80. These results indicate that a general acid catalysis by carboxylic acids plays an important role in the reduction of nitrosobenzene by dihydropyridine in acetonitrile.
- 公益社団法人 日本化学会の論文
著者
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Tagaki Waichiro
Department of Applied Chemistry, Faculty of Engineering Osaka City University
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Awano Hiroshi
Department of Applied Chemistry, Faculty of Engineering, Osaka City University
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