Mechanism of intramolecular catalysis in the hydrolysis of alkyl monoesters of 1,8-naphthalic acid (original) (raw)
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a Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis-SC, Brazil
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Abstract
Hydrolysis of alkyl 1,8-naphthalic acid monoesters 1a–d is subject to highly efficient intramolecular nucleophilic catalysis by the neighboring COOH group. The reactivity for the COOH reaction depends on the leaving group p_K_a, with values of _β_LG of −0.50, consistent with a mechanism involving rate determining breakdown of tetrahedral addition intermediates. The release of the steric strain of the _peri_-substitiuents in the highly reactive alkyl 1,8-naphthalic acid monoesters is fundamental to understand the observed special reactivity in this intramolecular reaction. DFT calculations show how the proton transfers involved in the cleavage of the neutral ester can be catalyzed by solvent water, thus facilitating the departure of poor alkoxide leaving groups.
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Article information
DOI
https://doi.org/10.1039/C1OB05574G
Article type
Paper
Submitted
11 Apr 2011
Accepted
03 Jun 2011
First published
06 Jun 2011
Download Citation
Org. Biomol. Chem., 2011,9, 6163-6170
Permissions
Mechanism of intramolecular catalysis in the hydrolysis of alkyl monoesters of 1,8-naphthalic acid
B. S. Souza, S. F. Yunes, M. F. Lima, J. C. Gesser, M. M. Sá, H. D. Fiedler and F. Nome,Org. Biomol. Chem., 2011, 9, 6163DOI: 10.1039/C1OB05574G
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