Título :	Regioselectivity in the nitration of eugenol is independent of inorganic reagents : an experimental and theoretical investigation with synthetic and mechanistic implications
Autor :	Barbosa, Jaqueline Rosa Cardoso Queiroz, Murillo Halo Rivelino, Roberto Oliveira, Gerlon de Almeida Ribeiro Lião, Luciano Morais Cunha, Silvio
metadata.dc.identifier.orcid:	https://orcid.org/0000-0003-0956-7903 https://orcid.org/0000-0003-2679-1640 https://orcid.org/0000-0001-9985-2980 https://orcid.org/0000-0002-8822-517X
metadata.dc.contributor.affiliation:	Universidade Federal da Bahia, Instituto de Química Universidade Federal da Bahia, Instituto de Química Universidade Federal da Bahia, Instituto de Química Universidade de Brasília, Faculdade de Ciências da Saúde, Departamento de Farmácia Universidade Federal de Goiás, Instituto de Química, Laboratório de RMN Universidade Federal da Bahia, Instituto de Química Instituto Nacional de Ciência e Tecnologia – INCT em Energia e Ambiente, Campus Ondina, Salvador
Assunto::	Energia Hidratação Estrutura molecular Moléculas Reações orgânicas
Fecha de publicación :	28-dic-2023
Editorial :	American Chemical Society
Citación :	BARBOSA, Jaqueline Rosa Cardoso et al. Regioselectivity in the nitration of eugenol is independent of inorganic reagents: an experimental and theoretical investigation with synthetic and mechanistic implications. The Journal of Organic Chemistry, [S. l.], v. 89, n. 2, p. 1120–1126, 2024. DOI: https://doi.org/10.1021/acs.joc.3c02298.
Abstract:	In this study, we reinvestigated the straightforward nitration of eugenol using traditional reagents and bismuth nitrate. NMR analysis of the obtained products revealed that the regioselectivity of eugenol nitration was independent of the inorganic nitrating reagent used, consistently resulting in the formation of 6-nitroeugenol. This contradicts previous literature reports because the elusive synthesis of 5-nitroeugenol using Bi(NO3)3·5H2O was not achievable through straightforward methods; instead, this isomer could only be prepared via the well-established three-step synthesis. Theoretical investigations using DFT calculations, considering both the dielectric constant of the medium and explicit water molecules, substantiated this regioselectivity. It was found that hydration water played a critical role in the formation of a Zundel cation, shifting the thermodynamic equilibrium toward the exclusive production of 6-nitroeugenol. These results imply that all biological studies involving eugenol derivatives synthesized via direct nitration with Bi(NO3)3·5H2O should be reviewed, as they dealt with 6-substituted eugenol derivatives rather than the previously assumed 5-substituted eugenol.
metadata.dc.description.unidade:	Faculdade de Ciências da Saúde (FS) Departamento de Farmácia (FS FAR)
DOI:	https://doi.org/10.1021/acs.joc.3c02298
metadata.dc.relation.publisherversion:	https://pubs.acs.org/doi/10.1021/acs.joc.3c02298?ref=PDF#
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