Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate

Autores
Tundo, Pietro; Bressanello, Salima; Loris, Alessandro; Sathicq, Ángel Gabriel
Año de publicación
2005
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The mechanism of the reaction between amines with dimethyl carbonate (DMC) has been investigated. Whereas in the absence of bases, they give methylation and carboxymethylation reactions without selectivity (BAl2 and B Ac2 mechanisms, respectively), in the presence of bases, the B Ac2 mechanism prevails. The carbamate already formed reacts further with DMC via the BAl2 mechanism to give the corresponding N-methyl derivative. Such pronounced double selectivity has been explained in terms of Pearson's Hard-Soft Acid-Base (HSAB) theory. Accordingly, N-methylcarbamates have been prepared from primary aliphatic and aromatic amines, either at reflux temperature of DMC (90 °C) or at 230 °C in autoclave. The reaction can be carried out in one step or through the isolation of the carbamate and the subsequent methylation reaction with DMC. This method is the direct synthesis, in high yield and selectivity, of secondary N-methylamines from the corresponding primary amines.
Facultad de Ciencias Exactas
Materia
Química
Amines
Carbamates
Dimethyl carbonate
Green chemistry
N-methylamines
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/83369
Acceder
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oai_identifier_str oai:sedici.unlp.edu.ar:10915/83369
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonateTundo, PietroBressanello, SalimaLoris, AlessandroSathicq, Ángel GabrielQuímicaAminesCarbamatesDimethyl carbonateGreen chemistryN-methylaminesThe mechanism of the reaction between amines with dimethyl carbonate (DMC) has been investigated. Whereas in the absence of bases, they give methylation and carboxymethylation reactions without selectivity (BAl2 and B Ac2 mechanisms, respectively), in the presence of bases, the B Ac2 mechanism prevails. The carbamate already formed reacts further with DMC via the BAl2 mechanism to give the corresponding N-methyl derivative. Such pronounced double selectivity has been explained in terms of Pearson's Hard-Soft Acid-Base (HSAB) theory. Accordingly, N-methylcarbamates have been prepared from primary aliphatic and aromatic amines, either at reflux temperature of DMC (90 °C) or at 230 °C in autoclave. The reaction can be carried out in one step or through the isolation of the carbamate and the subsequent methylation reaction with DMC. This method is the direct synthesis, in high yield and selectivity, of secondary N-methylamines from the corresponding primary amines.Facultad de Ciencias Exactas2005-10-18info: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/10915/83369enginfo:eu-repo/semantics/altIdentifier/issn/0033-4545info:eu-repo/semantics/altIdentifier/doi/10.1351/pac200577101719info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-10-15T11:07:42Zoai:sedici.unlp.edu.ar:10915/83369Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-10-15 11:07:42.583SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
title Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
spellingShingle Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
Tundo, Pietro
Química
Amines
Carbamates
Dimethyl carbonate
Green chemistry
N-methylamines
title_short Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
title_full Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
title_fullStr Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
title_full_unstemmed Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
title_sort Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
dc.creator.none.fl_str_mv Tundo, Pietro
Bressanello, Salima
Loris, Alessandro
Sathicq, Ángel Gabriel
author Tundo, Pietro
author_facet Tundo, Pietro
Bressanello, Salima
Loris, Alessandro
Sathicq, Ángel Gabriel
author_role author
author2 Bressanello, Salima
Loris, Alessandro
Sathicq, Ángel Gabriel
author2_role author
author
author
dc.subject.none.fl_str_mv Química
Amines
Carbamates
Dimethyl carbonate
Green chemistry
N-methylamines
topic Química
Amines
Carbamates
Dimethyl carbonate
Green chemistry
N-methylamines
dc.description.none.fl_txt_mv The mechanism of the reaction between amines with dimethyl carbonate (DMC) has been investigated. Whereas in the absence of bases, they give methylation and carboxymethylation reactions without selectivity (BAl2 and B Ac2 mechanisms, respectively), in the presence of bases, the B Ac2 mechanism prevails. The carbamate already formed reacts further with DMC via the BAl2 mechanism to give the corresponding N-methyl derivative. Such pronounced double selectivity has been explained in terms of Pearson's Hard-Soft Acid-Base (HSAB) theory. Accordingly, N-methylcarbamates have been prepared from primary aliphatic and aromatic amines, either at reflux temperature of DMC (90 °C) or at 230 °C in autoclave. The reaction can be carried out in one step or through the isolation of the carbamate and the subsequent methylation reaction with DMC. This method is the direct synthesis, in high yield and selectivity, of secondary N-methylamines from the corresponding primary amines.
Facultad de Ciencias Exactas
description The mechanism of the reaction between amines with dimethyl carbonate (DMC) has been investigated. Whereas in the absence of bases, they give methylation and carboxymethylation reactions without selectivity (BAl2 and B Ac2 mechanisms, respectively), in the presence of bases, the B Ac2 mechanism prevails. The carbamate already formed reacts further with DMC via the BAl2 mechanism to give the corresponding N-methyl derivative. Such pronounced double selectivity has been explained in terms of Pearson's Hard-Soft Acid-Base (HSAB) theory. Accordingly, N-methylcarbamates have been prepared from primary aliphatic and aromatic amines, either at reflux temperature of DMC (90 °C) or at 230 °C in autoclave. The reaction can be carried out in one step or through the isolation of the carbamate and the subsequent methylation reaction with DMC. This method is the direct synthesis, in high yield and selectivity, of secondary N-methylamines from the corresponding primary amines.
publishDate 2005
dc.date.none.fl_str_mv 2005-10-18
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/10915/83369
url http://sedici.unlp.edu.ar/handle/10915/83369
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/0033-4545
info:eu-repo/semantics/altIdentifier/doi/10.1351/pac200577101719
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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score 13.22299

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