skip to main content
Idioma:

Conformational Space, IR-Induced, and UV-Induced Chemistry of Carvacrol Isolated in a Low-Temperature Argon Matrix

Lopes Jesus, A. J ; Fausto, Rui ; Reva, Igor

The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2021-09, Vol.125 (37), p.8215-8229 [Periódico revisado por pares]

American Chemical Society

Texto completo disponível

Citações Citado por
  • Título:
    Conformational Space, IR-Induced, and UV-Induced Chemistry of Carvacrol Isolated in a Low-Temperature Argon Matrix
  • Autor: Lopes Jesus, A. J ; Fausto, Rui ; Reva, Igor
  • Assuntos: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
  • É parte de: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2021-09, Vol.125 (37), p.8215-8229
  • Notas: ObjectType-Article-1
    SourceType-Scholarly Journals-1
    ObjectType-Feature-2
    content type line 23
  • Descrição: In this work, monomers of carvacrol (5-isopropyl-2-methylphenol), a natural monoterpene exhibiting wide range bioactivity, were trapped in a cryogenic argon matrix and characterized by infrared spectroscopy, while quantum chemical calculations at the B3LYP and MP2 levels were employed to characterize the conformational landscape of the isolated molecule. Four conformers have been localized on the potential energy surface, and the factors accounting for their relative stability were analyzed. The two most stable conformers of carvacrol, differing in the relative orientation of the isopropyl group and both having the OH group pointing away from the vicinal methyl fragment, were identified in the cryomatrix for the first time. The individual spectral signatures of the two conformers were distinguished based on the change in their relative abundance induced by exposing the matrix to broadband infrared light. Matrix-isolated carvacrol was also irradiated with broadband UV light (λ > 200 nm), which resulted in the cleavage of the OH group. Recombination of the released H atom at the ortho- or para-position of the ring resulted in the formation of alkyl-substituted cyclohexadienones. These were found to undergo subsequent valence and open-ring isomerizations, leading, respectively, to the formation of a Dewar isomer and open-chain conjugated ketenes. Decarbonylation of the photoproducts was also observed for longer irradiation times. A mechanistic analysis of the observed photochemical transformations is presented.
  • Editor: American Chemical Society
  • Idioma: Inglês
Voltar para lista de resultados

  • Realização: ABCD-USP USP   Logos de Redes Sociais: Freepik

Buscando em bases de dados remotas. Favor aguardar.