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Título: Regioselectivity in the nitration of eugenol is independent of inorganic reagents : an experimental and theoretical investigation with synthetic and mechanistic implications
Autor(es): Barbosa, Jaqueline Rosa Cardoso
Queiroz, Murillo Halo
Rivelino, Roberto
Oliveira, Gerlon de Almeida Ribeiro
Lião, Luciano Morais
Cunha, Silvio
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
Afiliação do autor: 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
Data de publicação: 28-Dez-2023
Editora: American Chemical Society
Referência: 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.
Unidade Acadêmica: Faculdade de Ciências da Saúde (FS)
Departamento de Farmácia (FS FAR)
DOI: https://doi.org/10.1021/acs.joc.3c02298
Versão da editora: https://pubs.acs.org/doi/10.1021/acs.joc.3c02298?ref=PDF#
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