Unexpected formation of 1-diethylaminobutadiene in photosensitized oxidation of triethylamine induced by 2,3-dihydro-oxoisoaporphine dyes. A H-1 NMR and isotopic exchange study

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Unexpected formation of 1-diethylaminobutadiene in photosensitized oxidation of triethylamine induced by 2,3-dihydro-oxoisoaporphine dyes. A H-1 NMR and isotopic exchange study

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Unexpected formation of 1-diethylaminobutadiene in photosensitized oxidation of triethylamine induced by 2,3-dihydro-oxoisoaporphine dyes. A H-1 NMR and isotopic exchange study

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Título: Unexpected formation of 1-diethylaminobutadiene in photosensitized oxidation of triethylamine induced by 2,3-dihydro-oxoisoaporphine dyes. A H-1 NMR and isotopic exchange study
Autor: Fuente, J. de la; Jullian, Carolina; Saitz B., C.; Neira Pacheco, Verónica Alejandra; Pacheco, O.; Sobarzo Sánchez, Eduardo
Resumen: Photoreduction of oxoisoaporphine dyes occurs via a stepwise mechanism of electron-protonelectron transfer that leads to the N-hydrogen oxoisoaporphine anion. When triethylamine, TEA, was used as the electron donor in anaerobic conditions, 1-diethylaminobutadiene, DEAB, was one of the oxidation products of TEA, among diethylamine and acetaldehyde. DEAB was identified by H-1 NMR and GC-MS experiments by comparison with the authentic 1-diethylaminobutadiene. This is the first report of a butadienyl derivative formed in the dye-sensitized photooxidation of TEA. In addition, isotopic exchange experiments with TEA-d(15) and D2O show that the hydrogens at carbon-2 and carbon-4 of the butadienyl moiety are exchangeable. The observed isotopic exchange pattern could be explained by the head-to-tail coupling of an N,N-diethylvinylamine intermediate that exchanges hydrogens at the C-beta via the enammonium ion.
URI: http://www.captura.uchile.cl/handle/2250/5269
Fecha: 2005-10-28
Cita del item: JOURNAL OF ORGANIC CHEMISTRY 70(22):8712-8716


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