Kinetics and mechanism of the reactions of butenenitrile with imidazoles.
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概要
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The reaction kinetics of 3- and 2-butenenitriles with 2-alkylimidazoles were studied by using NMR, and a mechanism consistent with the results is proposed. The imidazoles were active in isomerizing 3-butenenitrile to 2-butenenitrile, and then reacted only with the 2-butenenitrile to give the corresponding 1-(2-cyano-1-methylethyl)imidazoles. These consecutive reactions, isomerization and cyanoethylation, are second-order over all. For example, in the reaction of 3-butenenitrile with imidazole, the rate measurements of the isomerization at various temperatures, ranging from 30 to 90 °C, afforded the activation parameters of <I>E</I><SUB>a</SUB>=14.6 kcal/mol and <I>ΔS</I><SUP>\neweq</SUP>=−35.3 cal/degree. On the other hand, in the case of 2-butenenitrile with imidazole, the measurements of the cyanoethylation at 60–100 °C gave these parameters; <I>E</I><SUB>a</SUB>=15.3 kcal/mol and <I>ΔS</I><SUP>\neweq</SUP>=−45.7 cal/degree. In this case, the rates of the isomerization (<I>k</I><SUB>1</SUB>=6.0×10<SUP>−6</SUP> l/mol s at 60 °C) are approximately ten times larger than those of the cyanoethylation (<I>k</I><SUB>2</SUB>=0.53×10<SUP>−6</SUP>). A mechanism is discussed on the basis of their NMR spectral and kinetic data.
- 公益社団法人 日本化学会の論文
著者
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Yamada Fukiko
Department of Applied Chemistry, Faculty of Engineering, Kansai University
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Ueda Harunori
Department of Applied Chemistry, Faculty of Engineering, Kansai University
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Kitano Osamu
Department of Applied Chemistry, Faculty of Engineering, Kansai University
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Shindo Soichi
Department of Applied Chemistry, Faculty of Engineering, Kansai University
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