Evidence of the presence of minor tautomeric forms in selected nitroanilines
- Autores
- Colasurdo, Diego Damián; Pila, Matías Nicolás; Laurella, Sergio Luis; Allegretti, Patricia Ercilia; Ruiz, Danila Luján
- Año de publicación
- 2021
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Rationale: Nitroanilines can exist in several tautomeric forms: nitro-amino, nitro-imino, and aci-imino. The importance of evaluating minor tautomeric species comes from the fact that even less abundant tautomers have been proved to play important roles in reaction mechanisms. Methods: Electron ionization mass spectra of the pesticide Pendimethalin and four related nitroanilines were recorded at 70 eV to find information about the presence of minor tautomeric forms in the gas phase. The existence of the possible tautomers was evaluated by studying specific fragmentation pathways, which were confirmed by tandem mass spectrometry (MS/MS) experiments. Further supporting information was obtained by studying the structures of some intermediate compounds by theoretical calculations at the B3LYP 6-311++G(d,p) level. Results: The mass spectrum of Pendimethalin suggests the coexistence of the nitroamine tautomer (the most stable form) with four possible less stable tautomers in equilibrium. The fragmentation routes were used to explain analogous peaks in two related compounds. However, the spectra of two other related compounds that cannot follow the proposed route of fragmentation for nitro-imine tautomers do not show the analogous peak. Theoretical calculations were used to correlate the precursor cation with the proposed fragmentation pathway. Conclusions: By the study of mass spectra and proposed fragmentation pathways it can be concluded that, although the nitro-amine is the most abundant species within the system, minor tautomers (nitro-imine and aci-imine) coexist in the gas phase.
Fil: Colasurdo, Diego Damián. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina
Fil: Pila, Matías Nicolás. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina
Fil: Laurella, Sergio Luis. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina
Fil: Allegretti, Patricia Ercilia. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; Argentina
Fil: Ruiz, Danila Luján. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina - Materia
-
NITROANILINES
TAUTOMERS
EQUILIBRIUM
PESTICIDE - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/139147
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Evidence of the presence of minor tautomeric forms in selected nitroanilinesColasurdo, Diego DamiánPila, Matías NicolásLaurella, Sergio LuisAllegretti, Patricia ErciliaRuiz, Danila LujánNITROANILINESTAUTOMERSEQUILIBRIUMPESTICIDEhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Rationale: Nitroanilines can exist in several tautomeric forms: nitro-amino, nitro-imino, and aci-imino. The importance of evaluating minor tautomeric species comes from the fact that even less abundant tautomers have been proved to play important roles in reaction mechanisms. Methods: Electron ionization mass spectra of the pesticide Pendimethalin and four related nitroanilines were recorded at 70 eV to find information about the presence of minor tautomeric forms in the gas phase. The existence of the possible tautomers was evaluated by studying specific fragmentation pathways, which were confirmed by tandem mass spectrometry (MS/MS) experiments. Further supporting information was obtained by studying the structures of some intermediate compounds by theoretical calculations at the B3LYP 6-311++G(d,p) level. Results: The mass spectrum of Pendimethalin suggests the coexistence of the nitroamine tautomer (the most stable form) with four possible less stable tautomers in equilibrium. The fragmentation routes were used to explain analogous peaks in two related compounds. However, the spectra of two other related compounds that cannot follow the proposed route of fragmentation for nitro-imine tautomers do not show the analogous peak. Theoretical calculations were used to correlate the precursor cation with the proposed fragmentation pathway. Conclusions: By the study of mass spectra and proposed fragmentation pathways it can be concluded that, although the nitro-amine is the most abundant species within the system, minor tautomers (nitro-imine and aci-imine) coexist in the gas phase.Fil: Colasurdo, Diego Damián. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaFil: Pila, Matías Nicolás. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaFil: Laurella, Sergio Luis. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaFil: Allegretti, Patricia Ercilia. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; ArgentinaFil: Ruiz, Danila Luján. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaJohn Wiley & Sons Ltd2021-02-15info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/139147Colasurdo, Diego Damián; Pila, Matías Nicolás; Laurella, Sergio Luis; Allegretti, Patricia Ercilia; Ruiz, Danila Luján; Evidence of the presence of minor tautomeric forms in selected nitroanilines; John Wiley & Sons Ltd; Rapid Communications in Mass Spectrometry; 35; 3; 15-2-2021; 1-15; e90000951-41981097-0231CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/rcm.9000info:eu-repo/semantics/altIdentifier/doi/10.1002/rcm.9000info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:34:32Zoai:ri.conicet.gov.ar:11336/139147instacron: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 09:34:33.164CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Evidence of the presence of minor tautomeric forms in selected nitroanilines |
title |
Evidence of the presence of minor tautomeric forms in selected nitroanilines |
spellingShingle |
Evidence of the presence of minor tautomeric forms in selected nitroanilines Colasurdo, Diego Damián NITROANILINES TAUTOMERS EQUILIBRIUM PESTICIDE |
title_short |
Evidence of the presence of minor tautomeric forms in selected nitroanilines |
title_full |
Evidence of the presence of minor tautomeric forms in selected nitroanilines |
title_fullStr |
Evidence of the presence of minor tautomeric forms in selected nitroanilines |
title_full_unstemmed |
Evidence of the presence of minor tautomeric forms in selected nitroanilines |
title_sort |
Evidence of the presence of minor tautomeric forms in selected nitroanilines |
dc.creator.none.fl_str_mv |
Colasurdo, Diego Damián Pila, Matías Nicolás Laurella, Sergio Luis Allegretti, Patricia Ercilia Ruiz, Danila Luján |
author |
Colasurdo, Diego Damián |
author_facet |
Colasurdo, Diego Damián Pila, Matías Nicolás Laurella, Sergio Luis Allegretti, Patricia Ercilia Ruiz, Danila Luján |
author_role |
author |
author2 |
Pila, Matías Nicolás Laurella, Sergio Luis Allegretti, Patricia Ercilia Ruiz, Danila Luján |
author2_role |
author author author author |
dc.subject.none.fl_str_mv |
NITROANILINES TAUTOMERS EQUILIBRIUM PESTICIDE |
topic |
NITROANILINES TAUTOMERS EQUILIBRIUM PESTICIDE |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
Rationale: Nitroanilines can exist in several tautomeric forms: nitro-amino, nitro-imino, and aci-imino. The importance of evaluating minor tautomeric species comes from the fact that even less abundant tautomers have been proved to play important roles in reaction mechanisms. Methods: Electron ionization mass spectra of the pesticide Pendimethalin and four related nitroanilines were recorded at 70 eV to find information about the presence of minor tautomeric forms in the gas phase. The existence of the possible tautomers was evaluated by studying specific fragmentation pathways, which were confirmed by tandem mass spectrometry (MS/MS) experiments. Further supporting information was obtained by studying the structures of some intermediate compounds by theoretical calculations at the B3LYP 6-311++G(d,p) level. Results: The mass spectrum of Pendimethalin suggests the coexistence of the nitroamine tautomer (the most stable form) with four possible less stable tautomers in equilibrium. The fragmentation routes were used to explain analogous peaks in two related compounds. However, the spectra of two other related compounds that cannot follow the proposed route of fragmentation for nitro-imine tautomers do not show the analogous peak. Theoretical calculations were used to correlate the precursor cation with the proposed fragmentation pathway. Conclusions: By the study of mass spectra and proposed fragmentation pathways it can be concluded that, although the nitro-amine is the most abundant species within the system, minor tautomers (nitro-imine and aci-imine) coexist in the gas phase. Fil: Colasurdo, Diego Damián. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina Fil: Pila, Matías Nicolás. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina Fil: Laurella, Sergio Luis. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina Fil: Allegretti, Patricia Ercilia. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; Argentina Fil: Ruiz, Danila Luján. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina |
description |
Rationale: Nitroanilines can exist in several tautomeric forms: nitro-amino, nitro-imino, and aci-imino. The importance of evaluating minor tautomeric species comes from the fact that even less abundant tautomers have been proved to play important roles in reaction mechanisms. Methods: Electron ionization mass spectra of the pesticide Pendimethalin and four related nitroanilines were recorded at 70 eV to find information about the presence of minor tautomeric forms in the gas phase. The existence of the possible tautomers was evaluated by studying specific fragmentation pathways, which were confirmed by tandem mass spectrometry (MS/MS) experiments. Further supporting information was obtained by studying the structures of some intermediate compounds by theoretical calculations at the B3LYP 6-311++G(d,p) level. Results: The mass spectrum of Pendimethalin suggests the coexistence of the nitroamine tautomer (the most stable form) with four possible less stable tautomers in equilibrium. The fragmentation routes were used to explain analogous peaks in two related compounds. However, the spectra of two other related compounds that cannot follow the proposed route of fragmentation for nitro-imine tautomers do not show the analogous peak. Theoretical calculations were used to correlate the precursor cation with the proposed fragmentation pathway. Conclusions: By the study of mass spectra and proposed fragmentation pathways it can be concluded that, although the nitro-amine is the most abundant species within the system, minor tautomers (nitro-imine and aci-imine) coexist in the gas phase. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-02-15 |
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/11336/139147 Colasurdo, Diego Damián; Pila, Matías Nicolás; Laurella, Sergio Luis; Allegretti, Patricia Ercilia; Ruiz, Danila Luján; Evidence of the presence of minor tautomeric forms in selected nitroanilines; John Wiley & Sons Ltd; Rapid Communications in Mass Spectrometry; 35; 3; 15-2-2021; 1-15; e9000 0951-4198 1097-0231 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/139147 |
identifier_str_mv |
Colasurdo, Diego Damián; Pila, Matías Nicolás; Laurella, Sergio Luis; Allegretti, Patricia Ercilia; Ruiz, Danila Luján; Evidence of the presence of minor tautomeric forms in selected nitroanilines; John Wiley & Sons Ltd; Rapid Communications in Mass Spectrometry; 35; 3; 15-2-2021; 1-15; e9000 0951-4198 1097-0231 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://onlinelibrary.wiley.com/doi/10.1002/rcm.9000 info:eu-repo/semantics/altIdentifier/doi/10.1002/rcm.9000 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-nd/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
John Wiley & Sons Ltd |
publisher.none.fl_str_mv |
John Wiley & Sons Ltd |
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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1844613068819005440 |
score |
13.070432 |