DFT computational study on decarboxylation mechanism of salicylic acid and its derivatives in the anionic state

Gao, Lu; Hu, Yingkao; Zhang, Huitu; Song, Zhidan; Dai, Yujie

doi:10.1016/j.molstruc.2016.03.005

Cited by 14 publications

(10 citation statements)

References 16 publications

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“…It is plausible that the ortho–OH group supports the decarboxylation step. − The apparent difference in the photochemical behavior of 1,8-DHN versus 1,6-DHN, which both display a meta-like substitution pattern, may be due to the intramolecular interactions between the hydroxyl groups operating in the case of 1,8-DHN but not of 1,6-DHN. In this perspective, comparative experiments at low temperature would be highly clarifying.…”

Section: Resultsmentioning

confidence: 99%

Solid State Photochemistry of Hydroxylated Naphthalenes on Minerals: Probing Polycyclic Aromatic Hydrocarbon Transformation Pathways under Astrochemically-Relevant Conditions

Potenti

Manini

Fornaro

et al. 2018

ACS Earth Space Chem.

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Oxygenated derivatives of polycyclic aromatic hydrocarbons (PAHs), or oxyPAHs, recently captured the interest of the scientific community for their photochemical reactivity in a water–ice matrix mimicking the interstellar medium. Furthermore, oxyPAHs are interesting molecules for the study of the origin of life for their prebiotic potential. However, their stability and transformation pathways under astrophysically relevant conditions have remained largely unexplored. Herein we report the photochemical behavior of 1-naphthol (1-HN) and 1,6- and 1,8-dihydroxynaphthalene (DHN) either as pure powdered solids or adsorbed on forsterite or anatase surface. All the compounds showed an extensive decrease of main vibrational bands, accompanied in the case of DHNs by the formation of new molecular species. Irradiation of 1,8-DHN at 80 K resulted in the IR-detectable generation of CO2 (2340 cm–1), a process reported by other authors following irradiation of PAHs in water–ice analogues at 14 K. These results, when compared to model autoxidation experiments, indicated a high susceptibility of hydroxylated naphthalene derivatives to UV radiation leading to free radical and carbonyl-containing extended quinone intermediates (preliminary DFT calculations) with partial degradation and decarboxylation. On the basis of these results, oxyPAH formation and photoprocessing on minerals is proposed as a plausible pathway of PAHs transformation under astrochemical conditions of prebiotic relevance.

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Section: Resultsmentioning

confidence: 99%

Solid State Photochemistry of Hydroxylated Naphthalenes on Minerals: Probing Polycyclic Aromatic Hydrocarbon Transformation Pathways under Astrochemically-Relevant Conditions

Potenti

Manini

Fornaro

et al. 2018

ACS Earth Space Chem.

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“…They are related to the dehydration, melting, and decomposition of the compound. The melting range of PyrHem×H 2 O is between 393 and 443 K. The formation of gas bubbles was noted when the sample was heated above 420 K. It seems most likely that decarboxylation of anion moiety proceeds [ 23 ]. The salt has a different and more complex decomposition profile compared to pure acid (Hem×H 2 O) and pyrazole (Pyr).…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic and Structural Study of a New Conducting Pyrazolium Salt

et al. 2021

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The increase in conductivity with temperature in 1H-pyrazol-2-ium 2,6-dicarboxybenzoate monohydrate was analyzed, and the influence of the mobility of the water was discussed in this study. The electric properties of the salt were studied using the impedance spectroscopy method. WB97XD/6-311++G(d,p) calculations were performed, and the quantum theory of atoms in molecules (QTAiM) approach and the Hirshfeld surface method were applied to analyze the hydrogen bond interaction. It was found that temperature influences the spectroscopic properties of pyrazolium salt, particularly the carbonyl and hydroxyl frequencies. The influence of water molecules, connected by three-center hydrogen bonds with co-planar tetrameters, on the formation of structural defects is also discussed in this report.

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“…Calculations of intrinsic reaction coordinates (IRC) were employed to confirm the located transition states which connect with the expected minima. All initial states, stable intermediates and final products were confirmed to have only real harmonic frequencies and each transition state was confirmed to have one single imaginary vibrational [49]. The energy barrier of the reaction was obtained from the energy difference between the transition states and the corresponding reactants with the zero-point correction.…”

Section: Methodsmentioning

confidence: 99%

“…When there is no water in vacuum, the proton is transferred through a C(2)-H( 13 22) gets a proton from water). Lu Gao et al [49] found that when a water molecule facilitate H transfer from carboxyl group to the a-C of benzene ring, energy barrier was lowered by 14.2kcal/mol. In this study, the energy barrier of step 6 with the two water molecules mediated proton transfer in the solvent of water is 12.98kcal/mol(shown in Figure 11(a)), which is 44.82kcal/mol lower than that in vacuum.…”

Section: Water Mediated Proton Transfer In Theoximation Reactionmentioning

confidence: 99%

DFT study on the mechanism of simultaneous trifluoromethylation and oximation of aryl-substituted ethylene.

Wang

Meng

et al. 2021

Preprint

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The effects of different substituents located at the para position of the aromatic ring and β carbon atom of the styrene on the reaction were investigated. The results showed that the reaction steps with higher energy barriers changed a little with the substituents of the reactants, which indicates that the reaction has a good adaptability to reactants containing different substituents. It was found the proton transfer in the final tautomerism step of nitroso intermediate to oxime is the rate limiting step under anhydrous conditions. Although the solvent effect did not influence the the rate limiting step significantly, the water mediated proton transfer significantly decreased the energy barrier of final tautomerism step. Compared with the direct proton transfer in vacuum, the energy barrier of the final tautomerism step decreased from 57.80kcal/mol in vacuum to 12.98kcal/mol with the water mediated proton transfer in water, which declined by 77.5%. When water participates in rate-limiting steps in organic solvents, the energy barrier also decreases significantly, which indicates that a small amount of water in the organic solvent is conducive to the reaction. This study is of great significance for the application of bifunctionalized reaction in the synthesis of organic fluoride compounds with different substituents.

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DFT computational study on decarboxylation mechanism of salicylic acid and its derivatives in the anionic state

Cited by 14 publications

References 16 publications

Solid State Photochemistry of Hydroxylated Naphthalenes on Minerals: Probing Polycyclic Aromatic Hydrocarbon Transformation Pathways under Astrochemically-Relevant Conditions

Solid State Photochemistry of Hydroxylated Naphthalenes on Minerals: Probing Polycyclic Aromatic Hydrocarbon Transformation Pathways under Astrochemically-Relevant Conditions

Spectroscopic and Structural Study of a New Conducting Pyrazolium Salt

DFT study on the mechanism of simultaneous trifluoromethylation and oximation of aryl-substituted ethylene.

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