2020
DOI: 10.3390/molecules25204819
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How Do Aromatic Nitro Compounds React with Nucleophiles? Theoretical Description Using Aromaticity, Nucleophilicity and Electrophilicity Indices

Abstract: In this study, we present a complete description of the addition of a model nucleophile to the nitroaromatic ring in positions occupied either by hydrogen (the first step of the SNAr-H reaction) or a leaving group (SNAr-X reaction) using theoretical parameters including aromaticity (HOMA), electrophilicity and nucleophilicity indices. It was shown both experimentally and by our calculations, including kinetic isotope effect modeling, that the addition of a nucleophile to the electron-deficient aromatic ring is… Show more

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Cited by 9 publications
(6 citation statements)
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“…It is a quantitative evidence of the intramolecular features reorganization associated with the presence of cooperativity of the non-covalent intramolecular interactions. We have applied the Fukui functions [ 58 , 59 ] to follow the electrophilicity and nucleophilicity changes related to the bridged proton position on the one site of the molecule from global minimum (Min_1) to the intermediate structure (Min_2). The atoms involved in the quasi-rings formation were taken into consideration as showed in Figure 5 .…”
Section: Resultsmentioning
confidence: 99%
“…It is a quantitative evidence of the intramolecular features reorganization associated with the presence of cooperativity of the non-covalent intramolecular interactions. We have applied the Fukui functions [ 58 , 59 ] to follow the electrophilicity and nucleophilicity changes related to the bridged proton position on the one site of the molecule from global minimum (Min_1) to the intermediate structure (Min_2). The atoms involved in the quasi-rings formation were taken into consideration as showed in Figure 5 .…”
Section: Resultsmentioning
confidence: 99%
“…These materials feature high stability and offer outstanding gas separation and storage properties [56] . In theory, a single electron‐withdrawing group on a benzene ring can activate three positions, namely two ortho ‐ and one para ‐, for S N Ar reactions [57] . Thus, it was hypothesized that using trifluorobenzene that contains a strong electron‐withdrawing group, such as nitro, would lead to the desired piperazine intermediates necessary for the subsequent synthesis of tri‐ and hexacarboxylate ligands.…”
Section: Resultsmentioning
confidence: 99%
“…[56] In theory, a single electron-withdrawing group on a benzene ring can activate three positions, namely two ortho-and one para-, for S N Ar reactions. [57] Thus, it was hypothesized that using trifluorobenzene that contains a strong electron-withdrawing group,…”
Section: Methodsmentioning
confidence: 99%
“…[56] In theory, a single electron-withdrawing group on a benzene ring can activate three positions, namely two ortho-and one para-, for S N Ar reactions. [57] Thus, it was hypothesized that using trifluorobenzene that contains a strong electron-withdrawing group, such as nitro, would lead to the desired piperazine intermediates necessary for the subsequent synthesis of triand hexacarboxylate ligands. To start, piperazine-carboxylate precursors were first synthesized (Scheme 5) from the corresponding commercially available aromatic amines [58] to obtain the known 4-pip-CO 2 Et•HCl [59] and the new 5-pip-diCO 2 Me•HCl (Section S3.8).…”
Section: Resultsmentioning
confidence: 99%