Abstract
This article presents a detailed comprehensive investigation of the ortho fluoro- and chloro- substituted benzoic acids both, as isolated molecules and in the crystalline phase. Quantum chemical calculations performed within the density functional theory (DFT) formalism are used to investigate the potential energy landscapes of the molecules, taking into special consideration the effects of the interactions between the carboxylic group and the ortho halogen substituents, as well as the nature of these later on the structure and properties of the investigated systems. The structures of the relevant conformers of the molecules are discussed in comparative terms, and used to rationalize experimental data obtained for the compounds in the gas phase and isolated in low-temperature inert matrices. The UV-induced photofragmentation reactions of two of the compounds isolated in cryogenic inert matrices were studied as illustrative cases. The structures of the crystals reported previously in the literature are revisited and discussed also in a comparative basis. Particular emphasis is given to the analysis of the intermolecular interactions in the different crystals, using Hirshfeld surface analysis, the CE-B3LYP energy decomposition model and the HOMA index, and to their correlation with thermodynamic data.
Highlights
Fluoro- and chloro-substituted benzoic acid derivatives have been shown to exhibit relevant practical applications, namely as precursors of agrochemical and pharmaceutical products, food additives and dyes [1]
There is a significant amount of information on ortho chloro- and fluoro- substituted benzoic acids dispersed in the scientific literature, no systematic investigation has been reported hitherto that can be used as a comprehensive reference work on this family of compounds
The structure and properties of the ortho mono- and di-substituted fluoro- and chloro- benzoic acids were investigated in a comparative basis
Summary
Fluoro- and chloro-substituted benzoic acid derivatives have been shown to exhibit relevant practical applications, namely as precursors of agrochemical and pharmaceutical products, food additives and dyes [1]. The fluoro-substituted compounds are considered to be environmentally acceptable alternatives to chlorinated compounds [2], which makes them presently relevant. They have been used as artificial tracers to investigate flow dynamics in geothermal, hydrothermal and oil well applications to optimize oil recovery [3,4,5]. The chloro-substituted benzoic acids are amongst the more versatile precursors or intermediates in the synthesis of pesticides [14]. Diclofenac (2-[2-(2,6-dichloroanilino)phenyl]acetic acid), which is Molecules 2020, 25, 4908; doi:10.3390/molecules25214908 www.mdpi.com/journal/molecules
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