Tertiary amine-catalyzed acyl group exchange reaction of N,O-diacyl-o-aminophenols. Its mechanism and factors determining the relative stability of acyl exchanged isomer pairs.
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概要
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Acyl substituent effects on the equilibrium and rate constants for the acyl group exchange reactions of various <I>N</I>,<I>O</I>-diacyl-<I>o</I>-aminophenols have been investigated in solvents with different polarities. It was found that the relative stability of acyl exchanged isomer pairs is determined solely by the inductive effect of acyl groups, provided that the steric hindrance of acyl substituents bonded to amide nitrogen affects the stability to the same extent. The importance of steric hindrance exerted by a bulky acyl group in determining the relative stability was demonstrated by analyzing the correlation between the standard free energy change (Δ<I>G</I>°) and p<I>K</I><SUB>a</SUB>, which were used as the measure of the relative stability of isomer pairs and of the electron-withdrawing ability of acyl groups, respectively. On the other hand, the logarithms of catalytic rate constants for the acyl migration reactions were correlated well to the p<I>K</I><SUB>a</SUB> values. In addition to this finding, a large negative value of activation entropy Δ<I>S</I><SUP>\neweq</SUP>=−160 J K<SUP>−1</SUP> mol<SUP>−1</SUP>) and the Brønsted coefficient β of 0.65 for the reaction of <I>N</I>,<I>O</I>-(acetyl)-(1-naphthoyl) pair of <I>N</I>,<I>O</I>-diacyl-<I>o</I>-aminophenol provide a definitive evidence for the rate-determining proton transfer from this derivative to amine catalyst in the transition state.
- 公益社団法人 日本化学会の論文
著者
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Sakurai Tadamitsu
Department Of Applied Chemistry Faculty Of Engineering Kanagawa University
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Inoue Hiroyasu
Department Of Applied Chemistry Faculty Of Technology Kanagawa University
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KOJIMA Shuichi
Department of Industrial Chemistry, Faculty of Engineering, The University of Tokyo
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Kojima Shuichi
Department of Applied Chemistry, Faculty of Technology, Kanagawa University
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