Naslov
Determination of nucleofugalities for benzoates based on theoretical model

Autori
Matić, Mirela ; Denegri, Bernard ; Kronja, Olga

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
The 14th European Symposium on Organic Reactivity (ESOR-14) - Book of abstracts / - Prag, 2013, 133-133

Skup
The 14th European Symposium on Organic Reactivity (ESOR-14)

Mjesto i datum
Prag, Češka Republika, 01.09.2013. - 06.09.2013

Vrsta sudjelovanja
Poster

Vrsta recenzije
Nije recenziran

Ključne riječi
benzoates; nucleofugality; reactivity; kinetics; dft; pcm

Sažetak
Solvolytic reactivities of some substituted benzoates in various solvents have been determined experimentally in the terms of nucleofugalities (Nf) according to the Mayr’s LFER equation log k (25 °C) = sf (Nf + Ef). A quantum-chemical model reaction based on the heterolytic dissociation of 2-oxyethyl benzoates has been developed for determining the reactivity of a vast number of benzoates. Experimentally determined ΔG‡ of 13 dianisylmethyl benzoates for solvolysis in 80% ethanol have been correlated with ΔH‡ of the model epoxy ring formation, calculated by DFT quantum-chemical method in the presence of the IEFPCM solvation model. Along with the excellent correlation (r = 0.997), very good agreement between the experimentally derived Nf parameters and calculated Nf parameters have been observed. The method for calculating the nucleofugalities of substituted benzoates, which includes this theoretical model, has been established, ultimately providing a possibility for determining the solvolytic SN1 reactivity for any benzoate in a given solvent.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA