Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study

N-2-oxoethyl derivatives of nucleobases are useful starting materials for the preparation of potentially active nucleoside analogues. The <sup>1</sup>HNMR, <sup>13</sup>CNMR, DEPT and ESI-MS spectra of adenine and thymine N-2-oxoethyl derivatives reveal that the different spe...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autores principales: Nigro, Mariano J., Brardinelli, Juan I., Lewkowicz, Elizabeth S., Iribarren, Adolfo M., Laurella, Sergio Luis
Formato: Articulo
Lenguaje:Inglés
Publicado: 2017
Materias:
Ciencias Exactas
Química
adenine
thymine
aldehyde
hydrate
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/109461
https://www.sciencedirect.com/science/article/abs/pii/S0022286017305872
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-109461
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Ciencias Exactas
Química
adenine
thymine
aldehyde
hydrate
spellingShingle Ciencias Exactas
Química
adenine
thymine
aldehyde
hydrate
Nigro, Mariano J.
Brardinelli, Juan I.
Lewkowicz, Elizabeth S.
Iribarren, Adolfo M.
Laurella, Sergio Luis
Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study
topic_facet Ciencias Exactas
Química
adenine
thymine
aldehyde
hydrate
description N-2-oxoethyl derivatives of nucleobases are useful starting materials for the preparation of potentially active nucleoside analogues. The <sup>1</sup>HNMR, <sup>13</sup>CNMR, DEPT and ESI-MS spectra of adenine and thymine N-2-oxoethyl derivatives reveal that the different species in equilibrium exist mainly in two forms: aldehyde and hydrate. The NMR spectra show that the equilibrium is shifted towards the hydrate form in water-DMSO 2:1, giving equilibrium constants of 8.3 and 5.3 for adenine and thymine derivatives, respectively. ESI-MS experiments show the dependence of equilibrium shift on pH: in the case of the thymine derivative, the effect on the equilibrium is more important than in the case of the adenine derivative; this difference is explained considering different protonation sites in both structures. All assumptions are supported by theoretical calculations, which suggest the important role played by solvent in the stabilization of molecular structures and equilibrium shift. All aspects analyzed in this work are very important in order to understand the further reactivity of these nucleobase derivatives.
format Articulo
Articulo
author Nigro, Mariano J.
Brardinelli, Juan I.
Lewkowicz, Elizabeth S.
Iribarren, Adolfo M.
Laurella, Sergio Luis
author_facet Nigro, Mariano J.
Brardinelli, Juan I.
Lewkowicz, Elizabeth S.
Iribarren, Adolfo M.
Laurella, Sergio Luis
author_sort Nigro, Mariano J.
title Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study
title_short Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study
title_full Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study
title_fullStr Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study
title_full_unstemmed Aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: An NMR, ESI-MS and theoretical study
title_sort aldehyde-hydrate equilibrium in nucleobase 2-oxoethyl derivatives: an nmr, esi-ms and theoretical study
publishDate 2017
url http://sedici.unlp.edu.ar/handle/10915/109461
https://www.sciencedirect.com/science/article/abs/pii/S0022286017305872
work_keys_str_mv AT nigromarianoj aldehydehydrateequilibriuminnucleobase2oxoethylderivativesannmresimsandtheoreticalstudy
AT brardinellijuani aldehydehydrateequilibriuminnucleobase2oxoethylderivativesannmresimsandtheoreticalstudy
AT lewkowiczelizabeths aldehydehydrateequilibriuminnucleobase2oxoethylderivativesannmresimsandtheoreticalstudy
AT iribarrenadolfom aldehydehydrateequilibriuminnucleobase2oxoethylderivativesannmresimsandtheoreticalstudy
AT laurellasergioluis aldehydehydrateequilibriuminnucleobase2oxoethylderivativesannmresimsandtheoreticalstudy
bdutipo_str Repositorios
_version_ 1764820443875770371

Ejemplares similares