Solution Structure of Succinylacetone, An Unsymmetrical β-Diketone, As Studied by <sup>13</sup>C NMR and GIAO−DFT Calculations

Bal, Dominika; Kraska-Dziadecka, Anna; Gryff‐Keller, Adam

doi:10.1021/jo901673j

Cited by 12 publications

(7 citation statements)

References 35 publications

(59 reference statements)

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“…Continuing our NMR studies on solution structures of biologically important compounds, − we devote this work to orotic acid, known also as vitamin B-13, which is an important natural product, structurally related to uracil. In living organisms it is a precursor of pyrimidine bases of nucleic acids .…”

Section: Introductionmentioning

confidence: 99%

Orotic Acid in Water Solution, a DFT and ¹³C NMR Spectroscopic Study

Kubica

Gryff‐Keller

2015

J. Phys. Chem. B

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Orotic acid, a biologically important compound, can exist in aqueous solutions in several ionic and tautomeric forms. Interpretation of the experimental (13)C NMR chemical shifts of this compound based on the results of energy and magnetic shielding calculations performed by DFT B3LYP/6-311++G(2d,p)/PCM method has shown that in water solutions the diketo tautomers are the dominant structural forms of this acid and its anions. For neutral molecules the anti conformation is preferable, monoanion occurs as the conventional carboxylate anion, whereas the orotic dianion exists in two tautomeric forms in the proportion of ca. 4:1. It has been found that the experimental (13)C NMR chemical shifts can be reproduced well by the results of DFT calculations, although for the orotate monoanion some small but characteristic divergences can be noticed. Similar divergences have been also observed for a few other aromatic carboxylates. It seems that the specific solute-solvent interactions occurring in our systems can be the cause of this inconsistency. To support this hypothesis, a simple and effective method of including the specific hydration into the theoretical calculations has been proposed.

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Section: Introductionmentioning

confidence: 99%

Orotic Acid in Water Solution, a DFT and ¹³C NMR Spectroscopic Study

Kubica

Gryff‐Keller

2015

J. Phys. Chem. B

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“…As a result, averaged, population‐weighted spectra are observed in NMR. This problem was widely discussed in the literature and also in several papers from our laboratory 10, 14, 21–26. In Ref.…”

Section: Resultsmentioning

confidence: 91%

NMR and DFT calculation study on structures of 2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione (NTBC) and its two metabolites isolated from urine of patients suffering from tyrosinemia type I

Gryff‐Keller

Szczeciński

Kraska-Dziadecka

2011

J of Physical Organic Chem

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Abstract2‐[2‐Nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione (NTBC) is an active component of nitisinone, a medicine against tyrosinemia type I. Using 1H, 13C and 19F NMR spectroscopy it has been found that in the urine of patients treated with nitisinone two compounds possessing CF3 group are always present. They have been isolated by using TLC technique and identified as 4‐hydroxy‐2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione and 5‐hydroxy‐2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione, the latter being previously unknown. The constitution, tautomerism and stereochemistry of these compounds have been thoroughly investigated using 1H and 13C NMR spectroscopy supported by theoretical calculations. Molecular structures have been optimized using density functional theory (DFT) with PBE1PBE functional and 6‐31G* basis set. In NMR parameter calculations, the larger 6‐311++G(2d,p) basis set has been used. At both calculation stages, the polarizable continuum model of the solvent has been employed. Copyright © 2010 John Wiley & Sons, Ltd.

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“…1 H NMR (400 MHz, CDCl 3 ): δ 6.97 (s, 1H, ArH), 4.64 (s, 2H, benzyl CH 2 ), 2.31 (s, 6H, ArCH 3 ), 2.26 (s, 6H, ArCH 3 ). 13 2,3,5,6-Tetramethylbenzyltrimethyl Phosphonium Bromide (2[Br]). 2,3,5,6-Tetramethylbenzyl bromide (370 mg, 1.6 mmol, 1 equiv) was dissolved in diethyl ether (75 mL) and sparged with N 2 for 10 min.…”

Section: ' Conclusionmentioning

confidence: 99%

“…1 H NMR (500 MHz, CD 3 OD): δ 6.96 (s, 1H, ArH), 3.90 (d, J = 16.5 Hz, 2H, benzyl CH 2 ), 2.20 (br, 12H, ArCH 3 ), 1.81 (d, J = 14.4 Hz, 9H, PMe 3 ). 13 ' ASSOCIATED CONTENT b S Supporting Information. 2D EXSY NMR spectrum of guest 2, atom coordinates used for all GIAO NMR shift calculations.…”

Section: ' Conclusionmentioning

confidence: 99%

¹H NMR Chemical Shift Calculations as a Probe of Supramolecular Host–Guest Geometry

2011

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The self-assembled supramolecular host [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) can encapsulate cationic guest molecules within its hydrophobic cavity and catalyze the chemical transformations of bound guests. The cavity of host 1 is lined with aromatic naphthalene groups, which create a magnetically shielded interior environment, resulting in upfield shifted (1-3 ppm) NMR resonances for encapsulated guest molecules. Using gauge independent atomic orbital (GIAO) DFT computations, we show that (1)H NMR chemical shifts for guests encapsulated in 1 can be efficiently and accurately calculated and that valuable structural information is obtained by comparing calculated and experimental chemical shifts. The (1)H NMR chemical shift calculations are used to map the magnetic environment of the interior of 1, discriminate between different host-guest geometries, and explain the unexpected downfield chemical shift observed for a particular guest molecule interacting with host 1.

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Solution Structure of Succinylacetone, An Unsymmetrical β-Diketone, As Studied by ¹³C NMR and GIAO−DFT Calculations

Cited by 12 publications

References 35 publications

Orotic Acid in Water Solution, a DFT and ¹³C NMR Spectroscopic Study

Orotic Acid in Water Solution, a DFT and ¹³C NMR Spectroscopic Study

NMR and DFT calculation study on structures of 2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione (NTBC) and its two metabolites isolated from urine of patients suffering from tyrosinemia type I

¹H NMR Chemical Shift Calculations as a Probe of Supramolecular Host–Guest Geometry

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Solution Structure of Succinylacetone, An Unsymmetrical β-Diketone, As Studied by 13C NMR and GIAO−DFT Calculations

Cited by 12 publications

References 35 publications

Orotic Acid in Water Solution, a DFT and 13C NMR Spectroscopic Study

Orotic Acid in Water Solution, a DFT and 13C NMR Spectroscopic Study

NMR and DFT calculation study on structures of 2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione (NTBC) and its two metabolites isolated from urine of patients suffering from tyrosinemia type I

1H NMR Chemical Shift Calculations as a Probe of Supramolecular Host–Guest Geometry

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Solution Structure of Succinylacetone, An Unsymmetrical β-Diketone, As Studied by ¹³C NMR and GIAO−DFT Calculations

Orotic Acid in Water Solution, a DFT and ¹³C NMR Spectroscopic Study

Orotic Acid in Water Solution, a DFT and ¹³C NMR Spectroscopic Study

¹H NMR Chemical Shift Calculations as a Probe of Supramolecular Host–Guest Geometry