A New Type of Intramolecular Hydrogen Bonding:  Hydroxyl−Methyl Interactions in the <i>o</i>-Cresol Cation

Fujii, Asuka; Fujimaki, Eiji; Ebata, Takayuki; Mikami, Naohiko

doi:10.1021/ja982922w

Cited by 31 publications

(29 citation statements)

References 11 publications

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“…The hydrogenation of o-cresol in the batch phase as monitored via in-situ ATR-IR spectra over Pt/C in dodecane reveals 2-methyl-cyclohexanone as an intermediate product as shown in consistent with the experimental observation that trans-cresol is more energetically stable [42][43][44]. We therefore chose trans-cresol for the following calculations whenever o-cresol was involved.…”

Section: Resultssupporting

confidence: 55%

Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

Liu

Xue

et al. 2017

Applied Surface Science

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Catalytic experiments were performed for the hydrogenation of o-cresol in n-dodecane over a platinum catalyst. Batch reactions analyzed with an in-situ ATR IR probe suggest that the hydrogenation results in the formation of the final product, 2-methyl-cyclohexanol, with 2-methyl-cyclohexanone as the intermediate product. Ab initio density-functional theory was employed to investigate the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone was found to involve two steps. The first step is a hydrogen abstraction, that is, the H atom in the hydroxyl group migrates to the Pt surface. The second step is hydrogenation, that is, the pre-existing H atoms on Pt react with the carbon atoms in the aromatic ring. On the other hand, 2-methyl-cyclohexanonol may be produced through two paths, with activation energies slightly greater than that for the formation of 2methyl-cyclohexanone. One path involves direct hydrogenation of the aromatic ring. Another path involves three steps, with the partial hydrogenation of the ring as the first step, hydrogen abstraction of the-OH group as the second, and hydrogenation of remaining C atoms and the O atom the last.

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Section: Resultssupporting

confidence: 55%

Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

Liu

Xue

et al. 2017

Applied Surface Science

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“…When first proposed many years ago (Glasstone, 1937;Dippy, 1939), there was some resistance due to the low electro negativity of C which was presumed to make it a weak proton donor. However, Support was later added to this idea on the basis of IR data (Allerhand and Schleyer, 1953;DeLaat and Ault, 1987;Kariuki et al, 1997) and the geometry of molecular complexes in the gas phase (Astrup and Aomar, 1975;Peterson and Klemperer, 1984;Fujii et al, 1998) and in crystalline environment (Sutor, 1962;Kaufmann et al, 1977). This CH.…”

Section: Introductionmentioning

confidence: 99%

Contribution of unconventional C-H…O bonds to the structural stability of Antimicrobial peptides

Ramanathan

Shanthi

Sethumadhavan

2009

Interdiscip Sci Comput Life Sci

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The native structure of Antimicrobial peptides is stabilized by a large number of individually weak forces; a complete understanding of folding implies the need to evaluate the contribution of each of these, including nonconventional hydrogen bonds. In this work, we have analyzed the influence of C-H...O interactions in the structural stability of Antimicrobial peptides by comparison with conventional hydrogen bond. There are a number of amino acid residues that can form hydrogen bonds via their side chains in addition to their peptide group. Perhaps highest contribution in this category is polar residue (Cys) and charged residues such as Lys and Arg. A total of 2513 C-H...O interactions were found in a data set of 53 Antimicrobial peptides. Among the 2513 nonconventional interactions observed in the data set, 40% of interactions are bonded to alpha carbon. This is consistent with the fact that the hydrogens are more acidic than others. Most prominent were side-chain to main-chain C-H...O interactions (SM-C-H...O). 92% of the stabilizing centers in the Antimicrobial peptides were found to be involved in C-H...O interactions. These interactions are mainly formed by short range contacts. Moreover, the study shows that, there is an average of more than one C-H...O interactions observed for every single residue in the Antimicrobial peptides data set. It is concluded that the C-H...O interaction can, indeed, be categorized as a true stabilizing force like hydrogen bond in Antimicrobial peptides.

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“…[21][22][23][24][25][26] In this technique, high Rydberg states just below the first ionization threshold are prepared by two-color double resonance excitation, and IR transitions of the ion core of the Rydberg states are measured by detecting the vibrational autoionization signal. The Rydberg electron plays the role of the messenger in ADIR spectroscopy, having a negligible perturbation to the ion core.…”

Section: Introductionmentioning

confidence: 99%

Infrared spectroscopy of CH stretching vibrations of jet-cooled alkylbenzene cations by using the “messenger” technique

Fujii¹,

Fujimaki²,

Ebata³

et al. 2000

The Journal of Chemical Physics

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A New Type of Intramolecular Hydrogen Bonding: Hydroxyl−Methyl Interactions in the o-Cresol Cation

Cited by 31 publications

References 11 publications

Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

Contribution of unconventional C-H…O bonds to the structural stability of Antimicrobial peptides

Infrared spectroscopy of CH stretching vibrations of jet-cooled alkylbenzene cations by using the “messenger” technique

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