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Molecules 2015, 20(9), 17493-17510; doi:10.3390/molecules200917493

Quantitative Structure–Property Relationship (QSPR) Models for a Local Quantum Descriptor: Investigation of the 4- and 3-Substituted-Cinnamic Acid Esterification

1
Departamento de Química, Instituto de Ciências Exatas, Universidade Federal Rural do Rio de Janeiro-RJ, Seropédica 23890-900, Brazil
2
Departamento de Engenharia de Alimentos, Universidade Federal da Fronteira Sul, Laranjeiras do Sul-PR 85303-775, Brazil
3
Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis-SC 88040-900, Brazil
These authors contributed equally to this work.
*
Author to whom correspondence should be addressed.
Academic Editor: Derek J. McPhee
Received: 27 June 2015 / Revised: 12 September 2015 / Accepted: 15 September 2015 / Published: 22 September 2015
(This article belongs to the Section Medicinal Chemistry)
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Abstract

In this work, the theoretical description of the 4- and 3-substituted-cinnamic acid esterification with different electron donating and electron withdrawing groups was performed at the B3LYP and M06-2X levels, as a two-step process: the O-protonation and the nucleophile attack by ethanol. In parallel, an experimental work devoted to the synthesis and characterization of the substituted-cinnamate esters has also been performed. In order to quantify the substituents effects, quantitative structure–property relationship (QSPR) models based on the atomic charges, Fukui functions and the Frontier Effective-for-Reaction Molecular Orbitals (FERMO) energies were investigated. In fact, the Fukui functions, ƒ+C and ƒO, indicated poor correlations for each individual step, and in contrast with the general literature, the O-protonation step is affected both by the FERMO energies and the O-charges of the carbonyl group. Since the process was shown to not be totally described by either charge- or frontier-orbitals, it is proposed to be frontier-charge-miscere controlled. Moreover, the observed trend for the experimental reaction yields suggests that the electron withdrawing groups favor the reaction and the same was observed for Step 2, which can thus be pointed out as the determining step. View Full-Text
Keywords: O-protonation; cinnamic acid; FERMO; Fukui functions O-protonation; cinnamic acid; FERMO; Fukui functions
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MDPI and ACS Style

Rodrigues-Santos, C.E.; Echevarria, A.; Sant’Anna, C.M.R.; Bitencourt, T.B.; Nascimento, M.G.; Bauerfeldt, G.F. Quantitative Structure–Property Relationship (QSPR) Models for a Local Quantum Descriptor: Investigation of the 4- and 3-Substituted-Cinnamic Acid Esterification. Molecules 2015, 20, 17493-17510.

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