Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and T...

Autores
Han, Lu; Iguchi, Daniela; Gil, Phwey; Heyl, Tyler R.; Sedwick, Victoria M.; Rodriguez Arza, Carlos; Ohashi, Seishi; Lacks, Daniel J.; Ishida, Hatsuo
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O-C2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.
Fil: Han, Lu. Case Western Reserve University; Estados Unidos
Fil: Iguchi, Daniela. Case Western Reserve University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Gil, Phwey. Case Western Reserve University; Estados Unidos
Fil: Heyl, Tyler R.. Case Western Reserve University; Estados Unidos
Fil: Sedwick, Victoria M.. Case Western Reserve University; Estados Unidos
Fil: Rodriguez Arza, Carlos. Case Western Reserve University; Estados Unidos
Fil: Ohashi, Seishi. Case Western Reserve University; Estados Unidos
Fil: Lacks, Daniel J.. Case Western Reserve University; Estados Unidos
Fil: Ishida, Hatsuo. Case Western Reserve University; Estados Unidos
Materia
Benzoxazine
Ring Opening
Infrared
Isotopes
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:11336/49599
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/49599
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical CalculationsHan, LuIguchi, DanielaGil, PhweyHeyl, Tyler R.Sedwick, Victoria M.Rodriguez Arza, CarlosOhashi, SeishiLacks, Daniel J.Ishida, HatsuoBenzoxazineRing OpeningInfraredIsotopeshttps://purl.org/becyt/ford/2.5https://purl.org/becyt/ford/2Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O-C2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.Fil: Han, Lu. Case Western Reserve University; Estados UnidosFil: Iguchi, Daniela. Case Western Reserve University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Gil, Phwey. Case Western Reserve University; Estados UnidosFil: Heyl, Tyler R.. Case Western Reserve University; Estados UnidosFil: Sedwick, Victoria M.. Case Western Reserve University; Estados UnidosFil: Rodriguez Arza, Carlos. Case Western Reserve University; Estados UnidosFil: Ohashi, Seishi. Case Western Reserve University; Estados UnidosFil: Lacks, Daniel J.. Case Western Reserve University; Estados UnidosFil: Ishida, Hatsuo. Case Western Reserve University; Estados UnidosAmerican Chemical Society2017-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/49599Han, Lu; Iguchi, Daniela; Gil, Phwey; Heyl, Tyler R.; Sedwick, Victoria M.; et al.; Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations; American Chemical Society; Journal of Physical Chemistry A; 121; 33; 8-2017; 6269-62821089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.7b05249info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.7b05249info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:33:35Zoai:ri.conicet.gov.ar:11336/49599instacron: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 09:33:35.459CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
title Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
spellingShingle Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
Han, Lu
Benzoxazine
Ring Opening
Infrared
Isotopes
title_short Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
title_full Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
title_fullStr Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
title_full_unstemmed Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
title_sort Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
dc.creator.none.fl_str_mv Han, Lu
Iguchi, Daniela
Gil, Phwey
Heyl, Tyler R.
Sedwick, Victoria M.
Rodriguez Arza, Carlos
Ohashi, Seishi
Lacks, Daniel J.
Ishida, Hatsuo
author Han, Lu
author_facet Han, Lu
Iguchi, Daniela
Gil, Phwey
Heyl, Tyler R.
Sedwick, Victoria M.
Rodriguez Arza, Carlos
Ohashi, Seishi
Lacks, Daniel J.
Ishida, Hatsuo
author_role author
author2 Iguchi, Daniela
Gil, Phwey
Heyl, Tyler R.
Sedwick, Victoria M.
Rodriguez Arza, Carlos
Ohashi, Seishi
Lacks, Daniel J.
Ishida, Hatsuo
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Benzoxazine
Ring Opening
Infrared
Isotopes
topic Benzoxazine
Ring Opening
Infrared
Isotopes
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O-C2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.
Fil: Han, Lu. Case Western Reserve University; Estados Unidos
Fil: Iguchi, Daniela. Case Western Reserve University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Gil, Phwey. Case Western Reserve University; Estados Unidos
Fil: Heyl, Tyler R.. Case Western Reserve University; Estados Unidos
Fil: Sedwick, Victoria M.. Case Western Reserve University; Estados Unidos
Fil: Rodriguez Arza, Carlos. Case Western Reserve University; Estados Unidos
Fil: Ohashi, Seishi. Case Western Reserve University; Estados Unidos
Fil: Lacks, Daniel J.. Case Western Reserve University; Estados Unidos
Fil: Ishida, Hatsuo. Case Western Reserve University; Estados Unidos
description Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O-C2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.
publishDate 2017
dc.date.none.fl_str_mv 2017-08
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/11336/49599
Han, Lu; Iguchi, Daniela; Gil, Phwey; Heyl, Tyler R.; Sedwick, Victoria M.; et al.; Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations; American Chemical Society; Journal of Physical Chemistry A; 121; 33; 8-2017; 6269-6282
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/49599
identifier_str_mv Han, Lu; Iguchi, Daniela; Gil, Phwey; Heyl, Tyler R.; Sedwick, Victoria M.; et al.; Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations; American Chemical Society; Journal of Physical Chemistry A; 121; 33; 8-2017; 6269-6282
1089-5639
1520-5215
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.7b05249
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.7b05249
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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
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score 13.070432

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