KINETICS AND MECHANISMS FOR THE ACID-CATALYZED OXIDATIVE DECARBOXYLATION OF BENZOYLFORMIC ACID

被引：21
作者：
SIEGEL, B
LANPHEAR, J
机构：
[1] Department of Chemistry, The University of Minnesota, Minneapolis
来源：
JOURNAL OF ORGANIC CHEMISTRY | 1979年 / 44卷 / 06期
关键词：
D O I：
10.1021/jo01320a010
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The pH-rate profile for hydrogen peroxide promoted oxidative decarboxylation of benzoylformic acid to benzoic acid and carbon dioxide has been determined from HO -9 to pH +8. In aqueous solutions more acidic than pH 2, a combination of acid- and water-catalyzed reaction mechanisms accounts for the observed data. Similar kinetic results are obtained from perchloric, nitric, and sulfuric acid solutions. Saturation kinetics are observed for the reversible addition of hydrogen peroxide to the α-keto carbonyl group with a pH-dependent Kd value of 0.25 M at H0 -2; the pH-independent value for Kd is 2.0 M. The pKa of the proposed protonated (monocation) tetrahedral intermediate is -1.3. A linear free-energy relationship correlates the observed rate constant and the pKa of the leaving group produced by oxygen-oxygen bond cleavage for hydrogen peroxide, tert-butyl hydroperoxide, and peracetic acid promoted reactions. © 1979, American Chemical Society. All rights reserved.
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页码：942 / 946
页数：5
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