Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate
- Autores
- Tundo, Pietro; Bressanello, Salimo; Loris, Alessandro; Sathicq, Angel 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 BAc2 mechanisms, respectively), in the presence of bases, the BAc2 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.
Fil: Tundo, Pietro. Universita' Ca' Foscari Di Venezia; Italia
Fil: Bressanello, Salimo. Universita' Ca' Foscari Di Venezia; Italia
Fil: Loris, Alessandro. Universita' Ca' Foscari Di Venezia; Italia
Fil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina - Materia
-
Amines
Carbamates
Dimethyl Carbonate
Green Chemistry
N-Methylamines - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/55329
Ver los metadatos del registro completo
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oai:ri.conicet.gov.ar:11336/55329 |
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Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonateTundo, PietroBressanello, SalimoLoris, AlessandroSathicq, Angel GabrielAminesCarbamatesDimethyl CarbonateGreen ChemistryN-Methylamineshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The 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 BAc2 mechanisms, respectively), in the presence of bases, the BAc2 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.Fil: Tundo, Pietro. Universita' Ca' Foscari Di Venezia; ItaliaFil: Bressanello, Salimo. Universita' Ca' Foscari Di Venezia; ItaliaFil: Loris, Alessandro. Universita' Ca' Foscari Di Venezia; ItaliaFil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaInt Union Pure Applied Chemistry2005-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/55329Tundo, Pietro; Bressanello, Salimo; Loris, Alessandro; Sathicq, Angel Gabriel; Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate; Int Union Pure Applied Chemistry; Pure and Applied Chemistry; 77; 10; 10-2005; 1719-17250033-45451365-3075CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1351/pac200577101719info:eu-repo/semantics/altIdentifier/url/http://iupac.org/publications/pac/77/10/index.htmlinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:51:13Zoai:ri.conicet.gov.ar:11336/55329instacron: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 09:51:13.338CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
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 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, Salimo Loris, Alessandro Sathicq, Angel Gabriel |
author |
Tundo, Pietro |
author_facet |
Tundo, Pietro Bressanello, Salimo Loris, Alessandro Sathicq, Angel Gabriel |
author_role |
author |
author2 |
Bressanello, Salimo Loris, Alessandro Sathicq, Angel Gabriel |
author2_role |
author author author |
dc.subject.none.fl_str_mv |
Amines Carbamates Dimethyl Carbonate Green Chemistry N-Methylamines |
topic |
Amines Carbamates Dimethyl Carbonate Green Chemistry N-Methylamines |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
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 BAc2 mechanisms, respectively), in the presence of bases, the BAc2 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. Fil: Tundo, Pietro. Universita' Ca' Foscari Di Venezia; Italia Fil: Bressanello, Salimo. Universita' Ca' Foscari Di Venezia; Italia Fil: Loris, Alessandro. Universita' Ca' Foscari Di Venezia; Italia Fil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina |
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 BAc2 mechanisms, respectively), in the presence of bases, the BAc2 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 |
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/11336/55329 Tundo, Pietro; Bressanello, Salimo; Loris, Alessandro; Sathicq, Angel Gabriel; Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate; Int Union Pure Applied Chemistry; Pure and Applied Chemistry; 77; 10; 10-2005; 1719-1725 0033-4545 1365-3075 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/55329 |
identifier_str_mv |
Tundo, Pietro; Bressanello, Salimo; Loris, Alessandro; Sathicq, Angel Gabriel; Direct synthesis of N-methylurethanes from primary amines with dimethyl carbonate; Int Union Pure Applied Chemistry; Pure and Applied Chemistry; 77; 10; 10-2005; 1719-1725 0033-4545 1365-3075 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/doi/10.1351/pac200577101719 info:eu-repo/semantics/altIdentifier/url/http://iupac.org/publications/pac/77/10/index.html |
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 |
Int Union Pure Applied Chemistry |
publisher.none.fl_str_mv |
Int Union Pure Applied Chemistry |
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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1844613575149092864 |
score |
13.070432 |