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Nitrosation of amines in non-aqueous solvents: difference between N-N=O and O-N=O Nitroso donors

2004Journal article Restricted access
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dc.contributor.authorGarcía-Río, Luís
dc.contributor.authorLeis, J. R.
dc.contributor.authorMoreira, José
dc.contributor.authorSerantes, D.
dc.date.accessioned2013-12-05T15:08:56Z
dc.date.available2013-12-05T15:08:56Z
dc.date.issued2004
dc.date.updated2013-12-04T18:20:00Z
dc.description.abstractA kinetic study has been carried out on nitroso group transfer from substituted N-methyl-N-nitroso-benzenesulfonamides to different secondary amines: pyrrolidine, piperidine, Nmethylpiperazine,and morpholine in cyclohexane. The observed pseudo-first-order rate constant kobs shows a linear and quadratic dependency on the amine concentration with the existence of a primary kinetic isotope effect. Experiments carried out at different temperatures show Arrhenius-type behavior. Addition of isopropylamine(iPrNH2) to the reaction medium produces an increase in kobs. In the presence of a high iPrNH2 concentrations the influence of secondary amine concentration on kobs shows the disappearance of the quadratic dependency of kobs on the secondary amine. These results would be compatible with an addition-elimination mechanism, similar to that observed for the aminolysis of thealkyl nitrites in apolar solvents. The observed behavior in the presence of 18-crown-6 is very different, however. Addition of crown ether catalyses the reaction of aminolysis of alkyl nitrites insofar as it does not alter the rate of the nitroso group transfer from N-nitrososulfonamides. This behavior has been interpreted in terms of a concerted reaction mechanism through cyclical transition states, with four or six centers, involving one or two molecules of secondary amine. Addition of iPrNH2 to the reaction medium causes the appearance of a third reaction path, which emerges through a mixed transition state formed by a molecule of a secondary amine and a molecule of isopropylamine.por
dc.identifier.citationMoreira, José A.; Leis, Jose Ramon; García-Río, Luís; Serantes, David. Nitrosation of Amines in Non-Aqueous Solvents - Difference Between N-N=O and O-N=O Nitroso Donors, European Journal of Organic Chemistry, 2004, 3, 614-622, 2004.por
dc.identifier.doihttp://dx.doi.org/10.1002/ejoc.200300482
dc.identifier.issn1434-193X
dc.identifier.otherAUT: JMO01545;
dc.identifier.urihttp://hdl.handle.net/10400.1/3223
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherWiley-VCH Verlag / ChemPubSoc Europepor
dc.relation.publisherversionhttp://onlinelibrary.wiley.com/doi/10.1002/ejoc.200300482/pdfpor
dc.subjectKineticspor
dc.subjectMechanismpor
dc.subjectNitrosationpor
dc.subjectSolvent effectpor
dc.subjectSulfonamidepor
dc.titleNitrosation of amines in non-aqueous solvents: difference between N-N=O and O-N=O Nitroso donorspor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.conferencePlaceWeinheim, Germanypor
oaire.citation.endPage622por
oaire.citation.issue3
oaire.citation.startPage614por
oaire.citation.titleEuropean Journal of Organic Chemistrypor
oaire.citation.volume2004por
person.familyNameMoreira
person.givenNameJosé
person.identifier.ciencia-idDC11-4E1F-F13F
person.identifier.orcid0000-0001-8481-3436
person.identifier.ridF-3807-2010
person.identifier.scopus-author-id7201506886
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublication644799ac-df06-4840-9f12-52c5b3ff0a76
relation.isAuthorOfPublication.latestForDiscovery644799ac-df06-4840-9f12-52c5b3ff0a76

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