A study about regioisomeric hydroquinones with multiple intramolecular hydrogen bonding

Maximiliano Martínez-Cifuentes, Wilson Cardona, Claudio Saitz, Boris Weiss-López, Ramiro Araya-Maturana

Resultado de la investigación: Article

5 Citas (Scopus)

Resumen

A theoretical exploration about hydrogen bonding in a series of synthetic regioisomeric antitumor tricyclic hydroquinones is presented. The stabilization energy for the intramolecular hydrogen bond (IHB) formation in four structurally different situations were evaluated: (a) IHB between the proton of a phenolic hydroxyl group and an ortho-carbonyl group (forming a six-membered ring); (b) between the oxygen atom of a phenolic hydroxyl group and the proton of an hydroxyalkyl group (seven membered ring); (c) between the proton of a phenolic hydroxyl group with the oxygen atom of the hydroxyl group of a hydroxyalkyl moiety (seven-membered ring); and (d) between the proton of a phenolic hydroxyl group and an oxygen atom directly bonded to the aromatic ring in ortho position (five-membered ring). A conformational analysis for the rotation around the hydroxyalkyl substituent is also performed. It is observed that there is a correspondence between the conformational energies and the IHB. The strongest intramolecular hydrogen bonds are those involving a phenolic proton and a carbonyl oxygen atom, forming a six-membered ring, and the weakest are those involving a phenolic proton with the oxygen atom of the chromenone, forming five-membered rings. Additionally, the synthesis and structural assignment of two pairs of regioisomeric hydroquinones, by 2D-NMR experiments, are reported. These results can be useful in the design of biologically-active molecules.

Idioma originalEnglish
Número de artículo593
PublicaciónMolecules
Volumen22
N.º4
DOI
EstadoPublished - 1 abr 2017

Huella dactilar

Hydroquinones
Hydrogen Bonding
Protons
Hydrogen bonds
Hydroxyl Radical
oxygen atoms
Oxygen
Hydrogen
rings
hydrogen
Atoms
protons
hydrogen bonds
Stabilization
Nuclear magnetic resonance
stabilization
Molecules
nuclear magnetic resonance
energy
synthesis

ASJC Scopus subject areas

  • Medicine(all)
  • Organic Chemistry

Citar esto

Martínez-Cifuentes, M., Cardona, W., Saitz, C., Weiss-López, B., & Araya-Maturana, R. (2017). A study about regioisomeric hydroquinones with multiple intramolecular hydrogen bonding. Molecules, 22(4), [593]. https://doi.org/10.3390/molecules22040593
Martínez-Cifuentes, Maximiliano ; Cardona, Wilson ; Saitz, Claudio ; Weiss-López, Boris ; Araya-Maturana, Ramiro. / A study about regioisomeric hydroquinones with multiple intramolecular hydrogen bonding. En: Molecules. 2017 ; Vol. 22, N.º 4.
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abstract = "A theoretical exploration about hydrogen bonding in a series of synthetic regioisomeric antitumor tricyclic hydroquinones is presented. The stabilization energy for the intramolecular hydrogen bond (IHB) formation in four structurally different situations were evaluated: (a) IHB between the proton of a phenolic hydroxyl group and an ortho-carbonyl group (forming a six-membered ring); (b) between the oxygen atom of a phenolic hydroxyl group and the proton of an hydroxyalkyl group (seven membered ring); (c) between the proton of a phenolic hydroxyl group with the oxygen atom of the hydroxyl group of a hydroxyalkyl moiety (seven-membered ring); and (d) between the proton of a phenolic hydroxyl group and an oxygen atom directly bonded to the aromatic ring in ortho position (five-membered ring). A conformational analysis for the rotation around the hydroxyalkyl substituent is also performed. It is observed that there is a correspondence between the conformational energies and the IHB. The strongest intramolecular hydrogen bonds are those involving a phenolic proton and a carbonyl oxygen atom, forming a six-membered ring, and the weakest are those involving a phenolic proton with the oxygen atom of the chromenone, forming five-membered rings. Additionally, the synthesis and structural assignment of two pairs of regioisomeric hydroquinones, by 2D-NMR experiments, are reported. These results can be useful in the design of biologically-active molecules.",
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Martínez-Cifuentes, M, Cardona, W, Saitz, C, Weiss-López, B & Araya-Maturana, R 2017, 'A study about regioisomeric hydroquinones with multiple intramolecular hydrogen bonding', Molecules, vol. 22, n.º 4, 593. https://doi.org/10.3390/molecules22040593

A study about regioisomeric hydroquinones with multiple intramolecular hydrogen bonding. / Martínez-Cifuentes, Maximiliano; Cardona, Wilson; Saitz, Claudio; Weiss-López, Boris; Araya-Maturana, Ramiro.

En: Molecules, Vol. 22, N.º 4, 593, 01.04.2017.

Resultado de la investigación: Article

TY - JOUR

T1 - A study about regioisomeric hydroquinones with multiple intramolecular hydrogen bonding

AU - Martínez-Cifuentes, Maximiliano

AU - Cardona, Wilson

AU - Saitz, Claudio

AU - Weiss-López, Boris

AU - Araya-Maturana, Ramiro

PY - 2017/4/1

Y1 - 2017/4/1

N2 - A theoretical exploration about hydrogen bonding in a series of synthetic regioisomeric antitumor tricyclic hydroquinones is presented. The stabilization energy for the intramolecular hydrogen bond (IHB) formation in four structurally different situations were evaluated: (a) IHB between the proton of a phenolic hydroxyl group and an ortho-carbonyl group (forming a six-membered ring); (b) between the oxygen atom of a phenolic hydroxyl group and the proton of an hydroxyalkyl group (seven membered ring); (c) between the proton of a phenolic hydroxyl group with the oxygen atom of the hydroxyl group of a hydroxyalkyl moiety (seven-membered ring); and (d) between the proton of a phenolic hydroxyl group and an oxygen atom directly bonded to the aromatic ring in ortho position (five-membered ring). A conformational analysis for the rotation around the hydroxyalkyl substituent is also performed. It is observed that there is a correspondence between the conformational energies and the IHB. The strongest intramolecular hydrogen bonds are those involving a phenolic proton and a carbonyl oxygen atom, forming a six-membered ring, and the weakest are those involving a phenolic proton with the oxygen atom of the chromenone, forming five-membered rings. Additionally, the synthesis and structural assignment of two pairs of regioisomeric hydroquinones, by 2D-NMR experiments, are reported. These results can be useful in the design of biologically-active molecules.

AB - A theoretical exploration about hydrogen bonding in a series of synthetic regioisomeric antitumor tricyclic hydroquinones is presented. The stabilization energy for the intramolecular hydrogen bond (IHB) formation in four structurally different situations were evaluated: (a) IHB between the proton of a phenolic hydroxyl group and an ortho-carbonyl group (forming a six-membered ring); (b) between the oxygen atom of a phenolic hydroxyl group and the proton of an hydroxyalkyl group (seven membered ring); (c) between the proton of a phenolic hydroxyl group with the oxygen atom of the hydroxyl group of a hydroxyalkyl moiety (seven-membered ring); and (d) between the proton of a phenolic hydroxyl group and an oxygen atom directly bonded to the aromatic ring in ortho position (five-membered ring). A conformational analysis for the rotation around the hydroxyalkyl substituent is also performed. It is observed that there is a correspondence between the conformational energies and the IHB. The strongest intramolecular hydrogen bonds are those involving a phenolic proton and a carbonyl oxygen atom, forming a six-membered ring, and the weakest are those involving a phenolic proton with the oxygen atom of the chromenone, forming five-membered rings. Additionally, the synthesis and structural assignment of two pairs of regioisomeric hydroquinones, by 2D-NMR experiments, are reported. These results can be useful in the design of biologically-active molecules.

KW - AIM

KW - DFT

KW - Hydrogen bond

KW - Hydroquinone

KW - NBO

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U2 - 10.3390/molecules22040593

DO - 10.3390/molecules22040593

M3 - Article

AN - SCOPUS:85019762677

VL - 22

JO - Molecules

JF - Molecules

SN - 1420-3049

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ER -