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
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/55329
Acceder
id CONICETDig_4e2ee612f01275a198958d73e7576ed4
oai_identifier_str oai:ri.conicet.gov.ar:11336/55329
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling 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 Técnicas2025-10-15T14:45:49Zoai: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:34982025-10-15 14:45:49.383CONICET 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
_version_ 1846082968665194496
score 13.22299

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