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New insights into the mechanism of Schiff base synthesis from aromatic amines in the absence of acid catalyst or polar solvents

dc.contributor.authorSilva, Pedro J.
dc.date.accessioned2021-02-12T01:22:18Z
dc.date.available2021-02-12T01:22:18Z
dc.date.issued2020
dc.description.abstractExtensive computational studies of the imine synthesis from amines and aldehydes in water have shown that the large-scale structure of water is needed to afford appropriate charge delocalization and enable sufficient transition state stabilization. These insights cannot, however, be applied to the understanding of the reaction pathway in apolar solvents due their inability to form extensive hydrogen-bonding networks. In this work, we perform the first computational studies of this reaction in nonpolar conditions. This density-functional study of the reaction of benzaldehyde with four closely related aromatic amines (aniline, o-toluidine, m-toluidine and p-toluidine) shows that, although an additional molecule of amine may provide some stabilization of the first transition state even in the absence of a hydrogen bonding network, this is insufficient to achieve high reaction rates. Our computations also show that when an extra proton is added to the spectator amine, the activation energies become so low that even picomolar amounts of protonated base are enough to achieve realistic rates. Additional computations show that those minute amounts of protonated base may be obtained under reaction conditions without the addition of extraneous acid through the auto-protolysis of the amines themselves. To our knowledge, this is the first report of a role for the auto-protolysis of anilines in their extensive reactional repertoire.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationSilva, P.J. (2020). New insights into the mechanism of Schiff base synthesis from aromatic amines in the absence of acid catalyst or polar solvents. PeerJ Organic Chemistry. https://doi.org/10.7717/peerj-ochem.4. ISSN 2167-8359.
dc.identifier.doi10.7717/peerj-ochem.4pt_PT
dc.identifier.issn2167-8359
dc.identifier.urihttp://hdl.handle.net/10284/9387
dc.language.isoengpt_PT
dc.publisherPeerJpt_PT
dc.subjectReaction mechanismpt_PT
dc.subjectDFTpt_PT
dc.subjectIminept_PT
dc.subjectAuto-protolysispt_PT
dc.titleNew insights into the mechanism of Schiff base synthesis from aromatic amines in the absence of acid catalyst or polar solventspt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage12pt_PT
oaire.citation.startPage1pt_PT
oaire.citation.titlePeerJ Organic Chemistrypt_PT
person.familyNameSilva
person.givenNamePedro
person.identifier.orcid0000-0001-9316-9275
person.identifier.scopus-author-id55310885700
rcaap.rightsopenAccesspt_PT
rcaap.typearticlept_PT
relation.isAuthorOfPublicationf4a9230e-0a0e-45b6-b894-e71ded186ef2
relation.isAuthorOfPublication.latestForDiscoveryf4a9230e-0a0e-45b6-b894-e71ded186ef2

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