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The mechanism of thermal eliminations. Part XXVIII [1]: Thermal decomposition of benzoylformic acid
Author(s) -
Taylor Roger
Publication year - 1991
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550230307
Subject(s) - chemistry , thermal decomposition , acetaldehyde , oxalic acid , pyruvic acid , carbon dioxide , decomposition , benzaldehyde , medicinal chemistry , inorganic chemistry , organic chemistry , ethanol , catalysis
The thermal decomposition of benzoylformic acid into carbon dioxide and benzaldehyde is a unimolecular first‐order reaction which takes place according to the rate equation log k = 15.3–42,500/4.575 K. At 600 K the reaction takes place 18 times faster than the corresponding decomposition of pyruvic acid into carbon dioxide and acetaldehyde. This is consistent with the 4‐center process proposed previously for pyruvic acid, in which a partial negative charge develops on the carbon of the α‐carbonyl group in the transition state. Benzoylformic acid is considerably less reactive towards thermal elimination than is oxalic acid, which also accords with the proposed mechanism.