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https://doi.org/10.5562/cca2495

Nucleofugality of Aliphatic Carboxylates in Mixtures of Aprotic Solvents and Water

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

Puni tekst: engleski, pdf (19 MB) str. 375-384 preuzimanja: 299* citiraj
APA 6th Edition
Matić, M., Denegri, B. i Kronja, O. (2014). Nucleofugality of Aliphatic Carboxylates in Mixtures of Aprotic Solvents and Water. Croatica Chemica Acta, 87 (4), 375-384. https://doi.org/10.5562/cca2495
MLA 8th Edition
Matić, Mirela, et al. "Nucleofugality of Aliphatic Carboxylates in Mixtures of Aprotic Solvents and Water." Croatica Chemica Acta, vol. 87, br. 4, 2014, str. 375-384. https://doi.org/10.5562/cca2495. Citirano 16.09.2019.
Chicago 17th Edition
Matić, Mirela, Bernard Denegri i Olga Kronja. "Nucleofugality of Aliphatic Carboxylates in Mixtures of Aprotic Solvents and Water." Croatica Chemica Acta 87, br. 4 (2014): 375-384. https://doi.org/10.5562/cca2495
Harvard
Matić, M., Denegri, B., i Kronja, O. (2014). 'Nucleofugality of Aliphatic Carboxylates in Mixtures of Aprotic Solvents and Water', Croatica Chemica Acta, 87(4), str. 375-384. https://doi.org/10.5562/cca2495
Vancouver
Matić M, Denegri B, Kronja O. Nucleofugality of Aliphatic Carboxylates in Mixtures of Aprotic Solvents and Water. Croatica Chemica Acta [Internet]. 2014 [pristupljeno 16.09.2019.];87(4):375-384. https://doi.org/10.5562/cca2495
IEEE
M. Matić, B. Denegri i O. Kronja, "Nucleofugality of Aliphatic Carboxylates in Mixtures of Aprotic Solvents and Water", Croatica Chemica Acta, vol.87, br. 4, str. 375-384, 2014. [Online]. https://doi.org/10.5562/cca2495

Sažetak
The leaving group ability (nucleofugality) of fluoroacetate, chloroacetate, bromoacetate, dichloroace-tate, trifluoroacetate, trichloroacetate, heptafluorobutyrate, formate, isobutyrate, and pivalate have been derived from the solvolysis rate constants of the corresponding X,Y-substituted benzhydryl car-boxylates in 60 % and 80 % aqueous acetonitrile and 60 % aqueous acetone, applying the LFER equa-tion: log k = sf (Ef + Nf). The experimental barriers (∆G‡,exp) for solvolyses of 11 reference dianisylme-thyl carboxylates in these solvents correlate very well (r = 0.994 in all solvents) with ∆G‡,model of the model
σ-assisted heterolytic displacement reaction of cis-2,3-dihydroxycyclopropyl trans-carboxylates cal-culated earlier. Linear correlation observed between the log k for the reference dianisylmethyl car-boxylates and the sf values enables estimation of the reaction constant Using the ∆G‡,exp vs. ∆G‡,model correlation, and taking the estimated the nucleofugality parameters for other 34 ali-phatic carboxylates have been determined in 60 % and 80 % aqueous acetonitrile and 60 % aqueous acetone. The most important variable that determines the reactivity of aliphatic carboxylates in apro-tic solvent/water mixtures is the inductive effect of the group(s) attached onto the carboxylate moiety.

Ključne riječi
nucleofugality; reactivity; aliphatic carboxylates; benzhydryl; hydrolysis; solvolysis; model reaction; correlation

Hrčak ID: 131534

URI
https://hrcak.srce.hr/131534

Posjeta: 473 *