YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
アセト酢酸エチルの酸触媒過酢酸酸化の速度論的研究
古家 義朗河野 伸吾林 輝美上田 甫藤島 浩
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1988 年 108 巻 3 号 p. 215-220

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The oxidation of ethyl acetoacetate with peracetic acid in the presence of sulfuric acid in acetic acid has been followed by iodometry. The rate satisfied the following equation; -dCPAA/dt={kd+ktCH2SO4}CPAA+{k2+k2'CH2SO4}CPAACEAA. The first and the second terms correspond to the decomposition of peracetic acid and the acid-catalyzed reversible transformation to acetyl peroxide, while the third and the fourth terms represent the neutral and the acid-catalyzed oxidation of ethyl acetoacetate, respectively, with peracetic acid. Hammett plots of the third and the fourth terms for the oxidation of substituted phenyl acetoacetates gave straight lines with slopes of -0.91 and -1.36, respectively. As products, acetic and oxalic acids, acetaldehyde, ethanol, ethyl glyoxylate, ethyl glycolate, ethyl acetate and diethyl oxalate were confirmed by means of gaschromatography and/or thin layer chromatography. No Baeyer-Villiger reaction product was formed at all. From these findings, a mechanisms is postulated and discussed which involves an epoxidation of enol form of ethyl acetoacetate, as the rate determining step, by an attack of the positive oxygen atom of peracetic acid and/or of protonated one.

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