Catalytic Aminolysis (Amide Formation) from Esters and Carboxylic Acids: Mechanism, Enhanced Ionic Liquid Effect, and its Origin

dc.creatorde Oliveira, VM
dc.creatorde Jesus, RS
dc.creatorGomes, AF
dc.creatorGozzo, FC
dc.creatorUmpierre, AP
dc.creatorSuarez, PAZ
dc.creatorRubim, JC
dc.creatorNeto, BAD
dc.date2011
dc.dateDEC
dc.date2014-08-01T18:24:44Z
dc.date2015-11-26T17:03:27Z
dc.date2014-08-01T18:24:44Z
dc.date2015-11-26T17:03:27Z
dc.date.accessioned2018-03-28T23:51:35Z
dc.date.available2018-03-28T23:51:35Z
dc.identifierChemcatchem. Wiley-blackwell, v. 3, n. 12, n. 1911, n. 1920, 2011.
dc.identifier1867-3880
dc.identifierWOS:000297791400013
dc.identifier10.1002/cctc.201100221
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/78502
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/78502
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1279078
dc.descriptionCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionThis paper describes the use of imidazolium-based ionic liquids {1-n-butyl-3-methylimidazolium tetrafluoroborate [BMI-BF4], 1-n-butyl-3-methylimidazolium hexafluorophosphate [BMI-PF6], and 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMI-NTf2]} as efficient supports for Lewis and Bronsted acids ,which are promoters of the aminolysis of some esters, fatty acids, and fatty acid esters (among others) to form amide derivatives. Some esters and carboxylic acids were tested to demonstrate the generality of the methodology, and the corresponding amides were obtained in high yields. Recycling reactions (at least eight reuses) without a notable loss in activity could be performed by using CdO and SnCl2 as catalysts in BMI-NTf2 as the ionic medium. Bronsted acids, such as H2SO4 and HCl, were also tested with impressive results; however, it was not possible to perform recycling reactions because of catalyst leaching. The same was true when using BF3 center dot OEt2 as the catalyst. Mechanistic insights and the ionic-liquid effect were investigated by using 13C{1H} NMR spectroscopy, which showed that there is a strong interaction of the imidazolium cation with the C=O and C=C bonds of methyl oleate, most likely through C-H...pi interactions, pi-stacking interactions, and ion-pair formation in the presence of a metal catalyst. Electrospray ionizationquadrupole time-of-flight experiments allowed a better understanding of the reaction mechanism. The results could explain the enhanced ionic-liquid effect on the stabilization of the formed intermediates, which facilitated the amide bond formation.
dc.description3
dc.description12
dc.description1911
dc.description1920
dc.descriptionCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionFINEP
dc.descriptionFINATEC
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionFAPDF
dc.descriptionCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.languageen
dc.publisherWiley-blackwell
dc.publisherMalden
dc.publisherEUA
dc.relationChemcatchem
dc.relationChemCatChem
dc.rightsfechado
dc.rightshttp://olabout.wiley.com/WileyCDA/Section/id-406071.html
dc.sourceWeb of Science
dc.subjectamides
dc.subjectcarboxylic acids
dc.subjectionic liquids
dc.subjectreaction mechanisms
dc.subjectsupported catalysis
dc.subjectSolvent-free Conditions
dc.subjectBond Formation
dc.subjectMolten-salt
dc.subjectFatty-acids
dc.subjectLipase
dc.subjectTransamidation
dc.subjectCommunication
dc.subjectDerivatives
dc.subjectConvenient
dc.subjectAmidation
dc.titleCatalytic Aminolysis (Amide Formation) from Esters and Carboxylic Acids: Mechanism, Enhanced Ionic Liquid Effect, and its Origin
dc.typeArtículos de revistas


Este ítem pertenece a la siguiente institución