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Understanding the Mechanism of Base-Assisted Decomposition of (N-halo),N-alkylalcoholamines
dc.contributor.author | Andrés, Juan | |
dc.contributor.author | Armesto Barbeito, Xosé Luís | |
dc.contributor.author | Canle, Moisés | |
dc.contributor.author | García-Dopico, María-Victoria | |
dc.contributor.author | Ramos, Daniel R. | |
dc.contributor.author | Santaballa, J. Arturo | |
dc.date.accessioned | 2024-06-13T18:36:18Z | |
dc.date.available | 2024-06-13T18:36:18Z | |
dc.date.issued | 2003-09-29 | |
dc.identifier.citation | J. Andrés, X. L. Armesto, M. Canle L., M. V. García, D. R. Ramos and J. A. Santaballa, Understanding the mechanism of base-assisted decomposition of (N-halo),N-alkylalcoholamines, Org. Biomol. Chem., 2003, 1, 4323 DOI: 10.1039/B306076D | es_ES |
dc.identifier.issn | 1477-0539 | |
dc.identifier.uri | http://hdl.handle.net/2183/36916 | |
dc.description | This document is the Accepted Manuscript version of a Published Work, after peer review and technical editing by the publisher. To access the final edited and published work see DOI https://doi.org/10.1039/B306076D | es_ES |
dc.description.abstract | [Abstract] The base-assisted decomposition of (N-X),N-methylethanolamine (X = Cl, Br) takes place mainly through two concurrent processes: a fragmentation and an intramolecular elimination. The global process follows second order kinetics, first order relative to both (N-X),N-methylethanolamine and base. Interaction of the base with the ionizable hydroxylic hydrogen triggers the reaction. The intramolecular elimination pathway leads to formaldehyde and 2-aminoethanol as reaction products via base-assisted proton transfer from the methyl to the partially unprotonated hydroxylic oxygen, with loss of halide. Meanwhile, the fragmentation pathway leads to methylamine and two equivalents of formaldehyde via bimolecular base-promoted concerted breakage of the molecule into formaldehyde, halide ion and N-methylmethanimine. Kinetic evidences allow a crude estimation of the concertedness and characterization of the transition structure for both processes, which are slightly asynchronous, the proton transfer to the base taking place ahead of the rest of the molecular events. The degree of asynchroneity increases as the bases become weaker. Electronic structure calculations, at the B3LYP/6-31++G** level, on the fragmentation pathway support the proposed mechanism. | es_ES |
dc.description.sponsorship | D. R. R. thanks the Spanish Ministerio de Educación, Cultura y Deporte for a PhD F.P.U. grant. This work was funded by the autonomous government Xunta de Galicia through project PGIDT99PX110302B. Thanks are also due to the Centro de Supercomputación de Galicia (CESGA) and the Centro de Cálculo (UJI, Castelló) for providing computing facilities through access to Fujitsu® VPP 300E and Silicon Graphics® Origin 2000 computers, respectively | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Royal Society of Chemistry (Gran Bretaña) | es_ES |
dc.relation.uri | https://doi.org/10.1039/B306076D | es_ES |
dc.rights | © The Royal Society of Chemistry | es_ES |
dc.title | Understanding the Mechanism of Base-Assisted Decomposition of (N-halo),N-alkylalcoholamines | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.access | info:eu-repo/semantics/openAccess | es_ES |
UDC.journalTitle | Organic and Biomolecular Chemistry | es_ES |
UDC.volume | 1 (2003) | es_ES |
UDC.startPage | 4323 | es_ES |
UDC.endPage | 4328 | es_ES |
dc.identifier.doi | 10.1039/B306076D |
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