Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO2, Cl, and NH2 Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles

Variously substituted N-heterocyclic compounds are widespread across bio- and medicinal chemistry. The work aims to computationally evaluate the influence of the type of N-heterocyclic compound and the substitution position on the properties of three model substituents: NO2, C...

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Autores principales:	Paweł A. Wieczorkiewicz, Halina Szatylowicz, Tadeusz M. Krygowski
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	substituent effect heterocyclic compounds pyridine substituent energy Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/18e6c9bed2a74d999e2b205b38721773
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spelling	oai:doaj.org-article:18e6c9bed2a74d999e2b205b387217732021-11-11T18:31:43ZEnergetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles10.3390/molecules262165431420-3049https://doaj.org/article/18e6c9bed2a74d999e2b205b387217732021-10-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6543https://doaj.org/toc/1420-3049Variously substituted N-heterocyclic compounds are widespread across bio- and medicinal chemistry. The work aims to computationally evaluate the influence of the type of N-heterocyclic compound and the substitution position on the properties of three model substituents: NO<sub>2</sub>, Cl, and NH<sub>2</sub>. For this reason, the energetic descriptor of global substituent effect (<i>E</i><sub>rel</sub>), geometry of substituents, and electronic descriptors (cSAR, pEDA, sEDA) are considered, and interdependences between these characteristics are discussed. Furthermore, the existence of an endocyclic N atom may induce proximity effects specific for a given substituent. Therefore, various quantum chemistry methods are used to assess them: the quantum theory of atoms in molecules (QTAIM), analysis of non-covalent interactions using reduced density gradient (RDG) function, and electrostatic potential maps (ESP). The study shows that the energetic effect associated with the substitution is highly dependent on the number and position of N atoms in the heterocyclic ring. Moreover, this effect due to interaction with more than one endo N atom (e.g., in pyrimidines) can be assessed with reasonable accuracy by adding the effects calculated for interactions with one endo N atom in substituted pyridines. Finally, all possible cases of proximity interactions for the NO<sub>2</sub>, Cl, and NH<sub>2</sub> groups are thoroughly discussed.Paweł A. WieczorkiewiczHalina SzatylowiczTadeusz M. KrygowskiMDPI AGarticlesubstituent effectheterocyclic compoundspyridinesubstituent energyOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6543, p 6543 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	substituent effect heterocyclic compounds pyridine substituent energy Organic chemistry QD241-441
spellingShingle	substituent effect heterocyclic compounds pyridine substituent energy Organic chemistry QD241-441 Paweł A. Wieczorkiewicz Halina Szatylowicz Tadeusz M. Krygowski Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles
description	Variously substituted N-heterocyclic compounds are widespread across bio- and medicinal chemistry. The work aims to computationally evaluate the influence of the type of N-heterocyclic compound and the substitution position on the properties of three model substituents: NO<sub>2</sub>, Cl, and NH<sub>2</sub>. For this reason, the energetic descriptor of global substituent effect (<i>E</i><sub>rel</sub>), geometry of substituents, and electronic descriptors (cSAR, pEDA, sEDA) are considered, and interdependences between these characteristics are discussed. Furthermore, the existence of an endocyclic N atom may induce proximity effects specific for a given substituent. Therefore, various quantum chemistry methods are used to assess them: the quantum theory of atoms in molecules (QTAIM), analysis of non-covalent interactions using reduced density gradient (RDG) function, and electrostatic potential maps (ESP). The study shows that the energetic effect associated with the substitution is highly dependent on the number and position of N atoms in the heterocyclic ring. Moreover, this effect due to interaction with more than one endo N atom (e.g., in pyrimidines) can be assessed with reasonable accuracy by adding the effects calculated for interactions with one endo N atom in substituted pyridines. Finally, all possible cases of proximity interactions for the NO<sub>2</sub>, Cl, and NH<sub>2</sub> groups are thoroughly discussed.
format	article
author	Paweł A. Wieczorkiewicz Halina Szatylowicz Tadeusz M. Krygowski
author_facet	Paweł A. Wieczorkiewicz Halina Szatylowicz Tadeusz M. Krygowski
author_sort	Paweł A. Wieczorkiewicz
title	Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles
title_short	Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles
title_full	Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles
title_fullStr	Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles
title_full_unstemmed	Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles
title_sort	energetic and geometric characteristics of the substituents: part 2: the case of no<sub>2</sub>, cl, and nh<sub>2</sub> groups in their mono-substituted derivatives of simple nitrogen heterocycles
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/18e6c9bed2a74d999e2b205b38721773
work_keys_str_mv	AT paweławieczorkiewicz energeticandgeometriccharacteristicsofthesubstituentspart2thecaseofnosub2subclandnhsub2subgroupsintheirmonosubstitutedderivativesofsimplenitrogenheterocycles AT halinaszatylowicz energeticandgeometriccharacteristicsofthesubstituentspart2thecaseofnosub2subclandnhsub2subgroupsintheirmonosubstitutedderivativesofsimplenitrogenheterocycles AT tadeuszmkrygowski energeticandgeometriccharacteristicsofthesubstituentspart2thecaseofnosub2subclandnhsub2subgroupsintheirmonosubstitutedderivativesofsimplenitrogenheterocycles
_version_	1718431808518881280

Energetic and Geometric Characteristics of the Substituents: Part 2: The Case of NO<sub>2</sub>, Cl, and NH<sub>2</sub> Groups in Their Mono-Substituted Derivatives of Simple Nitrogen Heterocycles

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