How Acid-Catalyzed Decarboxylation of 2,4-Dimethoxybenzoic Acid Avoids Formation of Protonated CO2

The decarboxylation of 2,4-dimethoxybenzoic acid (1) is accelerated in acidic solutions. The rate of reaction depends upon solution acidity in a manner that is consistent with the formation of the conjugate acid of 1 (RCO2H2 +), with its higher energy ring-protonated tautomer allowing the requisite...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2016-06, Vol.138 (24), p.7568-7573
Main Authors: Howe, Graeme W, Vandersteen, Adelle A, Kluger, Ronald
Format: Article
Language:English
Online Access:Get full text
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Summary:The decarboxylation of 2,4-dimethoxybenzoic acid (1) is accelerated in acidic solutions. The rate of reaction depends upon solution acidity in a manner that is consistent with the formation of the conjugate acid of 1 (RCO2H2 +), with its higher energy ring-protonated tautomer allowing the requisite C–C bond cleavage. However, this would produce the conjugate acid of CO2, a species that would be too energetic to form. Considerations of mechanisms that fit the observed rate law were supplemented with DFT calculations. Those results indicate that the lowest energy pathway from the ring-protonated reactive intermediate involves early proton transfer from the carboxyl group to water along with C–C bond cleavage, producing 1,3-dimethoxybenzene and CO2 directly.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b01770