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
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/83369
Ver los metadatos del registro completo
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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:UNLP2025-09-29T11:15:46Zoai: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:13292025-09-29 11:15:46.885SEDICI (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 |
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SEDICI (UNLP) - Universidad Nacional de La Plata |
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