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https://doi.org/10.5562/cca2179

The Reactivity of Benzoates in Mixtures of Water and Aprotic Solvents

Mirela Matić ; Faculty of Pharmacy and Biochemistry, University of Zagreb, Ante Kovačića 1, HR-10000 Zagreb, Croatia
Bernard Denegri   ORCID icon orcid.org/0000-0001-6335-6723 ; Faculty of Pharmacy and Biochemistry, University of Zagreb, Ante Kovačića 1, HR-10000 Zagreb, Croatia
Olga Kronja ; Faculty of Pharmacy and Biochemistry, University of Zagreb, Ante Kovačića 1, HR-10000 Zagreb, Croatia

Puni tekst: engleski, pdf (1 MB) str. 585-594 preuzimanja: 662* citiraj
APA 6th Edition
Matić, M., Denegri, B. i Kronja, O. (2012). The Reactivity of Benzoates in Mixtures of Water and Aprotic Solvents. Croatica Chemica Acta, 85 (4), 585-594. https://doi.org/10.5562/cca2179
MLA 8th Edition
Matić, Mirela, et al. "The Reactivity of Benzoates in Mixtures of Water and Aprotic Solvents." Croatica Chemica Acta, vol. 85, br. 4, 2012, str. 585-594. https://doi.org/10.5562/cca2179. Citirano 05.03.2021.
Chicago 17th Edition
Matić, Mirela, Bernard Denegri i Olga Kronja. "The Reactivity of Benzoates in Mixtures of Water and Aprotic Solvents." Croatica Chemica Acta 85, br. 4 (2012): 585-594. https://doi.org/10.5562/cca2179
Harvard
Matić, M., Denegri, B., i Kronja, O. (2012). 'The Reactivity of Benzoates in Mixtures of Water and Aprotic Solvents', Croatica Chemica Acta, 85(4), str. 585-594. https://doi.org/10.5562/cca2179
Vancouver
Matić M, Denegri B, Kronja O. The Reactivity of Benzoates in Mixtures of Water and Aprotic Solvents. Croatica Chemica Acta [Internet]. 2012 [pristupljeno 05.03.2021.];85(4):585-594. https://doi.org/10.5562/cca2179
IEEE
M. Matić, B. Denegri i O. Kronja, "The Reactivity of Benzoates in Mixtures of Water and Aprotic Solvents", Croatica Chemica Acta, vol.85, br. 4, str. 585-594, 2012. [Online]. https://doi.org/10.5562/cca2179

Sažetak
Nucleofugalities of pentafluorobenzoate (PFB), 2,4,6-trifluorobenzoate (TFB), 2-nitrobenzoate,
and 3,5-dinitrobenzoate (DNB) leaving groups have been derived from the solvolysis rate constants of the
corresponding X,Y-substituted Z-benzhydryl benzoates in 60 % and 80 % aqueous acetonitrile and 60 %
aqueous acetone, by applying the LFER equation: log k = f s (Ef + Nf). The experimental barriers (ΔG‡
exp) for
solvolyses of 13 dianisylmethyl Z-substituted benzoates in these solvents correlate very well with the ΔH‡
calc
of the model epoxy ring formation (calculated earlier by the B3LYP-PCM quantum-chemical method). Using
the ΔG‡
exp vs. ΔH‡
calc correlation, and taking f s based on similarity, the nucleofugality parameters for about
70 benzoates have been determined in 60 % and 80 % aqueous acetonitrile and 60 % aqueous acetone.
Z-Substituents on the phenyl ring have larger impact on the solvolytic reactivity in the less polar solvent than
in the more polar solvent due to the more carbocation-like transition state. (doi: 10.5562/cca2179)

Ključne riječi
nucleofugality; reactivity; substituted benzoate; aprotic solvent

Hrčak ID: 94471

URI
https://hrcak.srce.hr/94471

Posjeta: 916 *