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.
Fil: Saeed, Aamer. Quaid-I-Azam University; Pakistán
Fil: Shabir, Ghulam. Quaid-I-Azam University; Pakistán
Fil: Hökelek, Tuncer. Hacettepe University; Turquía
Fil: Flörke, Ülrich. Universität Paderborn; Alemania
Fil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Materia
BENZO[D]OXAZOLE-2(3H)-THIONE
HIRSHFELD SURFACE ANALYSIS
MOLECULAR STRUCTURE
NATURAL BOND ORBITAL
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/181067
Acceder
id CONICETDig_60bb939e59c1951a90d5695bc2bf7660
oai_identifier_str oai:ri.conicet.gov.ar:11336/181067
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocyclesSaeed, AamerShabir, GhulamHökelek, TuncerFlörke, ÜlrichErben, Mauricio FedericoBENZO[D]OXAZOLE-2(3H)-THIONEHIRSHFELD SURFACE ANALYSISMOLECULAR STRUCTURENATURAL BOND ORBITALhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Solventless 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.Fil: Saeed, Aamer. Quaid-I-Azam University; PakistánFil: Shabir, Ghulam. Quaid-I-Azam University; PakistánFil: Hökelek, Tuncer. Hacettepe University; TurquíaFil: Flörke, Ülrich. Universität Paderborn; AlemaniaFil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaCell Press2021-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/181067Saeed, Aamer; Shabir, Ghulam; Hökelek, Tuncer; Flörke, Ülrich; Erben, Mauricio Federico; Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles; Cell Press; Heliyon; 7; 9; 9-2021; 1-72405-8440CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://linkinghub.elsevier.com/retrieve/pii/S2405844021021459info:eu-repo/semantics/altIdentifier/doi/10.1016/j.heliyon.2021.e08042info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:13:26Zoai:ri.conicet.gov.ar:11336/181067instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:13:27.073CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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
BENZO[D]OXAZOLE-2(3H)-THIONE
HIRSHFELD SURFACE ANALYSIS
MOLECULAR STRUCTURE
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 BENZO[D]OXAZOLE-2(3H)-THIONE
HIRSHFELD SURFACE ANALYSIS
MOLECULAR STRUCTURE
NATURAL BOND ORBITAL
topic BENZO[D]OXAZOLE-2(3H)-THIONE
HIRSHFELD SURFACE ANALYSIS
MOLECULAR STRUCTURE
NATURAL BOND ORBITAL
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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.
Fil: Saeed, Aamer. Quaid-I-Azam University; Pakistán
Fil: Shabir, Ghulam. Quaid-I-Azam University; Pakistán
Fil: Hökelek, Tuncer. Hacettepe University; Turquía
Fil: Flörke, Ülrich. Universität Paderborn; Alemania
Fil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
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 2021-09
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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://hdl.handle.net/11336/181067
Saeed, Aamer; Shabir, Ghulam; Hökelek, Tuncer; Flörke, Ülrich; Erben, Mauricio Federico; Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles; Cell Press; Heliyon; 7; 9; 9-2021; 1-7
2405-8440
CONICET Digital
CONICET
url http://hdl.handle.net/11336/181067
identifier_str_mv Saeed, Aamer; Shabir, Ghulam; Hökelek, Tuncer; Flörke, Ülrich; Erben, Mauricio Federico; Synthesis, conformation and Hirshfeld surface analysis of benzoxazole methyl ester as a versatile building block for heterocycles; Cell Press; Heliyon; 7; 9; 9-2021; 1-7
2405-8440
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://linkinghub.elsevier.com/retrieve/pii/S2405844021021459
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.heliyon.2021.e08042
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Cell Press
publisher.none.fl_str_mv Cell Press
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1844614051100884992
score 13.070432

Publicaciones similares