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Self‐catalyzed keto‐enol tautomerization of malonic acid
Author(s) -
Sutton Catherine C. R.,
Lim ChiaYang,
Silva Gabriel
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26114
Subject(s) - tautomer , malonic acid , chemistry , enol , catalysis , keto–enol tautomerism , aqueous solution , carboxylic acid , photochemistry , computational chemistry , organic chemistry , inorganic chemistry
We demonstrate through quantum chemical calculations that the keto‐enol tautomerization of malonic acid can be catalyzed by the two tautomers of malonic acid itself. This self‐catalyzed process proceeds with a relatively low barrier (Gibbs energy ca. 13 kcal/mol in gas phase, 20 kcal/mol in aqueous phase), and involves the concerted transfer of two protons between the substrate and the carboxylic acid functionality of the malonic acid catalyst. This mechanism is expected to compete with the proton relay mechanism currently favored to explain the tautomerization of malonic acid in aqueous media. Malonic acid is an important constituent of secondary organic aerosol where the present chemistry may play a role in determining chemical composition.