A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

Safi, Zaki

doi:10.1016/j.arabjc.2015.03.016

Cited by 13 publications

(5 citation statements)

References 42 publications

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“…The diketo form shown in Figure a is the most stable form, and the relative stabilities of the tautomers are given in Table S1a (Supporting Information). Both the crystallographic study and the theoretical investigation showed that the most stable and predominant form of TZD is the diketo form. , The calculated optimized geometrical parameters for the diketo form in the present study compare well with the available crystallographic experimental data and are shown in Table S1b. The HOMO–LUMO transition energy of TZD was calculated with time-dependent density functional theory (TD-DFT) method using the B3LYP functional with the aug-cc-pvdz basis set.…”

Section: Computational Detailssupporting

confidence: 76%

“…TZD exists in five tautomeric forms: thiazolidine (diketo), thiazoline (oxo-enol), and thiazole (dienol). , The optimized geometries of all the tautomeric forms were calculated and are shown in Figure . The diketo form shown in Figure a is the most stable form, and the relative stabilities of the tautomers are given in Table S1a (Supporting Information).…”

Section: Computational Detailsmentioning

confidence: 99%

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Plasmon-Induced Dimerization of Thiazolidine-2,4-dione on Silver Nanoparticles: Revealed by Surface-Enhanced Raman Scattering Study

Kumar

Thomas²,

Rao

et al. 2019

J. Phys. Chem. A

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Surface-enhanced Raman scattering (SERS) study carried on thiazolidine-2,4-dione (TZD), a pharmacologically active heterocyclic compound, points to the presence of TZD dimer formed by plasmon-induced dimerization reaction of TZD on the surface of silver nanoparticles (Ag NP) at TZD concentrations of 10 −3 M and above. The evidence for the presence of dimer was obtained from the appearance of a prominent band at 1566 cm −1 corresponding to the ν(CC) band (a characteristic vibrational band observed for the Knoevenagel condensation reaction products) which is absent in the normal Raman scattering (NRS) spectra of TZD solid/solution. The observed spectrum compares well with the calculated spectrum of dimer obtained using density functional theory (DFT) calculations. The dimerization reaction is plausibly induced by the transfer of hot electrons generated by the nonradiative plasmon decay of Ag NP, and the proposed reaction mechanism is discussed. However, at lower concentrations (10 −4 −10 −6 M), the characteristic dimer peak (1566 cm −1 ) is absent and the SERS spectra resemble more the NRS spectrum of TZD with a few changes. The spectral analysis supported by DFT calculations showed that TZD molecules undergo deprotonation and get adsorbed on the Ag NP surface as enolate forms. The proximity of TZD molecules on the surface of Ag NP is a necessary factor for the dimerization to occur. At lower concentrations, most molecules lie apart and reactions between molecules become less feasible, and they remain as monomers on the surface, while at higher concentrations the molecules are closer to each other on the Ag NP surface favoring the dimerization reaction to take place, leading to the formation of the dimer.

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Section: Computational Detailssupporting

confidence: 76%

Section: Computational Detailsmentioning

confidence: 99%

Plasmon-Induced Dimerization of Thiazolidine-2,4-dione on Silver Nanoparticles: Revealed by Surface-Enhanced Raman Scattering Study

Kumar

Thomas²,

Rao

et al. 2019

J. Phys. Chem. A

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“…In most cases, hydrogen transfer is the main reason for the keto-enol formation. The keto-enol are formed also in heterocyclic compounds containing the carbonyl group with acidic methylene protons connected to the heteroatom or to electro-withdrawing species, such as thiazolidine-2,4-dione [ 25 ], phenacyl bezoyl pyridinium [ 26 ], and 2-phenacyl benzoxazoles [ 27 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Spectroscopic Studies and Keto-Enol Tautomerism of Novel 1,3,4-Thiadiazole Derivative Containing 3-Mercaptobutan-2-one and Quinazolin-4-one Moieties

et al. 2020

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In this study, a novel 1,3,4-thiadiazole derivative containing 3-mercaptobutan-2-one and quinazolin-4-one moieties (Compound 3) is synthesized by the coupling of 2-amino-1,3,4-thiadiazole-5-(3-mercaptobutan-2-one) (Compound 1) with 2-Phenyl-4H-3,1-benzoxazin-4-one (Compound 2) in one molecule moiety. Compound 3 is found to exist as two types of intra-molecular hydrogen bonding with keto-enol tautomerism characters, which is further confirmed using FTIR, 1H-NMR, 13C-NMR, mass spectrometer, and UV-Visible spectra. The 1H-NMR and UV-Visible spectra of Compound 3 are investigated in different solvents such as methanol, chloroform, and DMSO. Compound 3 exhibits keto-enol tautomeric forms in solvents with different percentage ratios depending on the solvent polarity. The 1H-NMR and UV-Visible spectral results show that Compound 3 favors the keto over the enol form in polar aprotic solvents such as DMSO and the enol over the keto form in non-polar solvents such as chloroform. The 13C-NMR spectrum gives two singles at δ 204.5 ppm, due to ketonic carbon, and δ 155.5 ppm, due to enolic carbon, confirming the keto-enol tautomerism of Compound 3. Furthermore, the molecular ion at m/z 43 and m/z 407 in the mass spectrum of Compound 3 and fragmentation mechanisms proposed reveal the existence of the keto and enol forms, respectively.

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“…In systems with multiple sites of the same basic element type, the most basic site has the most negative MEP value, indicating a stronger molecular basicity. This understanding is essential for understanding proton affinity and gas-phase basicity 66 , 67 .…”

Section: Resultsmentioning

confidence: 99%

Computational analysis of substituent effects on proton affinity and gas-phase basicity of TEMPO derivatives and their hydrogen bonding interactions with water molecules

Shiroudi,

Śmiechowski,

Czub

et al. 2024

Sci Rep

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The study investigates the molecular structure of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its derivatives in the gas phase using B3LYP and M06-2X functional methods. Intermolecular interactions are analyzed using natural bond orbital (NBO) and atoms in molecules (AIM) techniques. NO2-substituted TEMPO displays high reactivity, less stability, and softer properties. The study reveals that the stability of TEMPO derivatives is mainly influenced by LP(e) → σ∗ electronic delocalization effects, with the highest stabilization observed on the oxygen atom of the nitroxide moiety. This work also considers electron density, atomic charges, and energetic and thermodynamic properties of the studied NO radicals, and their relative stability. The proton affinity and gas-phase basicity of the studied compounds were computed at T = 298 K for O-protonation and N-protonation, respectively. The studied DFT method calculations show that O-protonation is more stable than N-protonation, with an energy difference of 16.64–20.77 kcal/mol (22.80–25.68 kcal/mol) at the B3LYP (M06-2X) method. The AIM analysis reveals that the N–O…H interaction in H2O complexes has the most favorable hydrogen bond energy computed at bond critical points (3, − 1), and the planar configurations of TEMPO derivatives exhibit the highest EHB values. This indicates stronger hydrogen bonding interactions between the N–O group and water molecules.

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A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

Cited by 13 publications

References 42 publications

Plasmon-Induced Dimerization of Thiazolidine-2,4-dione on Silver Nanoparticles: Revealed by Surface-Enhanced Raman Scattering Study

Plasmon-Induced Dimerization of Thiazolidine-2,4-dione on Silver Nanoparticles: Revealed by Surface-Enhanced Raman Scattering Study

Synthesis, Spectroscopic Studies and Keto-Enol Tautomerism of Novel 1,3,4-Thiadiazole Derivative Containing 3-Mercaptobutan-2-one and Quinazolin-4-one Moieties

Computational analysis of substituent effects on proton affinity and gas-phase basicity of TEMPO derivatives and their hydrogen bonding interactions with water molecules

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