Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles

Autores
Saeed, Aamer; Shabir, Ghulam; Hökelek, Tuncer; Flörke, Ülrich; Erben, Mauricio Federico
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Solventless cyclocondensation of 2-aminothiophenol with thiourea afforded the benzo[d]oxazole-2-thiol (3a) capable of existing also in the tautomeric form benzo[d]oxazole-2(3H)-thione (3b). Acylation with methyl chloroacetate in dry ethanol in absence of any base or catalyst selectively afforded the S-substituted ester 2-(methoxycarbonylmethylthio)benzo[d]oxazole (4a) in preference to the corresponding N-substituted ester N-(methoxycarbonylmethyl)thioxobenzoxazole (4b). Quantum chemical calculations were conducted to determine the conformational landscape and NBO population analysis showed the strong electronic delocalization via resonance interactions on the 2-mercaptobenzaxazole group. The anomeric effect and the occurrence of a 1,4-S···O intramolecular interactions suggest the relevance of chalcogen bonding in the conformational preference. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (33.2%), H⋯O/O⋯H (19.9%) and H⋯C/C⋯H (17.8%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, the C–H⋯O hydrogen-bond energy is 44.8 kJ mol⁻¹.
Centro de Química Inorgánica
Materia
Química
Molecular structure
benzo[d]oxazole-2(3H)-thione
Hirshfeld surface analysis
Natural bond orbital
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/129907
Acceder
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oai_identifier_str oai:sedici.unlp.edu.ar:10915/129907
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocyclesSaeed, AamerShabir, GhulamHökelek, TuncerFlörke, ÜlrichErben, Mauricio FedericoQuímicaMolecular structurebenzo[d]oxazole-2(3H)-thioneHirshfeld surface analysisNatural bond orbitalSolventless cyclocondensation of 2-aminothiophenol with thiourea afforded the benzo[d]oxazole-2-thiol (3a) capable of existing also in the tautomeric form benzo[d]oxazole-2(3H)-thione (3b). Acylation with methyl chloroacetate in dry ethanol in absence of any base or catalyst selectively afforded the S-substituted ester 2-(methoxycarbonylmethylthio)benzo[d]oxazole (4a) in preference to the corresponding N-substituted ester N-(methoxycarbonylmethyl)thioxobenzoxazole (4b). Quantum chemical calculations were conducted to determine the conformational landscape and NBO population analysis showed the strong electronic delocalization via resonance interactions on the 2-mercaptobenzaxazole group. The anomeric effect and the occurrence of a 1,4-S···O intramolecular interactions suggest the relevance of chalcogen bonding in the conformational preference. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (33.2%), H⋯O/O⋯H (19.9%) and H⋯C/C⋯H (17.8%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, the C–H⋯O hydrogen-bond energy is 44.8 kJ mol⁻¹.Centro de Química Inorgánica2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttp://sedici.unlp.edu.ar/handle/10915/129907enginfo:eu-repo/semantics/altIdentifier/issn/2405-8440info:eu-repo/semantics/altIdentifier/doi/10.1016/j.heliyon.2021.e08042info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/4.0/Creative Commons Attribution 4.0 International (CC BY 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:32:37Zoai:sedici.unlp.edu.ar:10915/129907Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:32:38.13SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
title Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
spellingShingle Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
Saeed, Aamer
Química
Molecular structure
benzo[d]oxazole-2(3H)-thione
Hirshfeld surface analysis
Natural bond orbital
title_short Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
title_full Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
title_fullStr Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
title_full_unstemmed Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
title_sort Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles
dc.creator.none.fl_str_mv Saeed, Aamer
Shabir, Ghulam
Hökelek, Tuncer
Flörke, Ülrich
Erben, Mauricio Federico
author Saeed, Aamer
author_facet Saeed, Aamer
Shabir, Ghulam
Hökelek, Tuncer
Flörke, Ülrich
Erben, Mauricio Federico
author_role author
author2 Shabir, Ghulam
Hökelek, Tuncer
Flörke, Ülrich
Erben, Mauricio Federico
author2_role author
author
author
author
dc.subject.none.fl_str_mv Química
Molecular structure
benzo[d]oxazole-2(3H)-thione
Hirshfeld surface analysis
Natural bond orbital
topic Química
Molecular structure
benzo[d]oxazole-2(3H)-thione
Hirshfeld surface analysis
Natural bond orbital
dc.description.none.fl_txt_mv Solventless cyclocondensation of 2-aminothiophenol with thiourea afforded the benzo[d]oxazole-2-thiol (3a) capable of existing also in the tautomeric form benzo[d]oxazole-2(3H)-thione (3b). Acylation with methyl chloroacetate in dry ethanol in absence of any base or catalyst selectively afforded the S-substituted ester 2-(methoxycarbonylmethylthio)benzo[d]oxazole (4a) in preference to the corresponding N-substituted ester N-(methoxycarbonylmethyl)thioxobenzoxazole (4b). Quantum chemical calculations were conducted to determine the conformational landscape and NBO population analysis showed the strong electronic delocalization via resonance interactions on the 2-mercaptobenzaxazole group. The anomeric effect and the occurrence of a 1,4-S···O intramolecular interactions suggest the relevance of chalcogen bonding in the conformational preference. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (33.2%), H⋯O/O⋯H (19.9%) and H⋯C/C⋯H (17.8%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, the C–H⋯O hydrogen-bond energy is 44.8 kJ mol⁻¹.
Centro de Química Inorgánica
description Solventless cyclocondensation of 2-aminothiophenol with thiourea afforded the benzo[d]oxazole-2-thiol (3a) capable of existing also in the tautomeric form benzo[d]oxazole-2(3H)-thione (3b). Acylation with methyl chloroacetate in dry ethanol in absence of any base or catalyst selectively afforded the S-substituted ester 2-(methoxycarbonylmethylthio)benzo[d]oxazole (4a) in preference to the corresponding N-substituted ester N-(methoxycarbonylmethyl)thioxobenzoxazole (4b). Quantum chemical calculations were conducted to determine the conformational landscape and NBO population analysis showed the strong electronic delocalization via resonance interactions on the 2-mercaptobenzaxazole group. The anomeric effect and the occurrence of a 1,4-S···O intramolecular interactions suggest the relevance of chalcogen bonding in the conformational preference. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (33.2%), H⋯O/O⋯H (19.9%) and H⋯C/C⋯H (17.8%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, the C–H⋯O hydrogen-bond energy is 44.8 kJ mol⁻¹.
publishDate 2021
dc.date.none.fl_str_mv 2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/129907
url http://sedici.unlp.edu.ar/handle/10915/129907
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/2405-8440
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.heliyon.2021.e08042
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/4.0/
Creative Commons Attribution 4.0 International (CC BY 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/4.0/
Creative Commons Attribution 4.0 International (CC BY 4.0)
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
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reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
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repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
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