Weaving a web of reliable thermochemistry around lignin building blocks: phenol, benzaldehyde, and anisole

Verevkin, Sergey P.

doi:10.1007/s10973-021-10924-x

Cited by 9 publications

(6 citation statements)

References 61 publications

(154 reference statements)

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“…We note that van der Spoel c.s. [19] have reported a G4 value of −229.4 kJ/mol for 2-methoxybenzene, which is significantly off the experimental value and also differs significantly from the G4 result of −209.4 kJ/mol reported by Verevkin [44]. Regarding our GC model, when introducing a GC value for the methoxy Group of −152 kJ/mol, all GC values agree within chemical accuracy with the experimental values, except a larger deviation for 1,2-dimethoxybenzene.…”

Section: Methoxybenzenescontrasting

confidence: 64%

“…Regarding the three methylphenols, the experimental heats of formation, as presented in Table 10. [44]; all other data are from Pedley c.s. [34].…”

Section: Anilinesmentioning

confidence: 99%

“…Thus, the GC model does not account properly for 1,2-dimethoxybenzene, and consequently also not for the trimethoxybenzenes with adjacent methoxy groups. [44] except for the experimental values for methoxybenzene and 1-methoxy-3-methylbenzene (Pedley [34]) and the G4 value for methoxybenzene [19]. Experimental and G4 results in the lower part of the table were taken from Verevkin c.s.…”

Section: Methoxybenzenesmentioning

confidence: 99%

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Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V

Meier,

Rablen

2024

Applied Sciences

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Group Contribution (GC) methods to predict thermochemical properties are eminently important in chemical process design. Following our earlier work in which a Group Contribution (GC) model was presented to account for the gas-phase heat of formation of organic molecules which, for the first time, revealed chemical accuracy (1 kcal/mol or 4 kJ/mol), we here present Group Contribution parameters for a range of additional series of molecules allowing the application to a wider range of molecules whilst, mostly, retaining chemical accuracy. The new classes of molecules include amines, alkylesters, and various substituted benzenes, including t-butyl-benzenes, phenols, methoxybenzenes, anilines, benzaldehydes, and acetophenones, and finally furans and indoles/indolines. As in our previous works on this theme, again the critical selection of experimental data was crucial. Not meeting the criterion for chemical accuracy occurred when steric interactions such as nearest neighbour substituents on a benzene ring were present, something which does not fit with the characteristics of the Group Contribution method. We also report some cases for which the experimental value does not seem correct, but where both the G4 and GC model values agree well. In general, in line with accounts in the literature, the G4 method performs really well. Contrary to other related works, we have applied conformational averaging to obtain a slightly more realistic G4 result. Although the difference is generally only a few kJ/mol, this may still be relevant when attempting the development of a model with chemical accuracy, e.g., 4.2 kJ/mol.

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Section: Methoxybenzenescontrasting

confidence: 64%

“…Regarding the three methylphenols, the experimental heats of formation, as presented in Table 10. [44]; all other data are from Pedley c.s. [34].…”

Section: Anilinesmentioning

confidence: 99%

Section: Methoxybenzenesmentioning

confidence: 99%

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Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V

Meier,

Rablen

2024

Applied Sciences

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“…The conversion of glucose, derived from biomass, to chemical intermediates and fuel is the challenging task. The efficient transformation of these chemicals required design of new catalyst with better efficiency, understanding of the molecular pathways, their kinetics and thermochemistry of these chemicals [11,12] . The thermochemistry of the reactions involved in glucose transformation to varied chemicals and fuels can be studied by employing computational chemistry with high molecular orbital theory.…”

Section: Introductionmentioning

confidence: 99%

Thermochemical property predictions in biomass transformation to fuel components and value-added chemicals

Parveen

Upadhyayula

2022

new n.a. exploit. and appl.

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Biomass transformation to fuel and platform chemicals is of an immense interest in the world. The thermochemical data for various reactions involved during biomass transformations to fuel components, fuels and platform chemicals has been investigated using highly accurate Gaussian-4 (G-4) method. Glucose to 5-hydroxymethyl furfural (5-HMF) conversion is a two-step pathway, where first step, glucose isomerization to fructose is highly endothermic with high activation energies. 5-HMF upgradation can be carried through hydrogenation, oxidation, condensation and rehydration. Upgradation of HMF to fuel and value-added chemicals (VAC) is industrially important process that can reduce the demand of petrochemical based products. Thermochemical calculations predict the hydrogenation of 5-HMF to 2,5 dimethyl furan (2,5 DMF) is feasible and follow either pathways with dihydroxy methyl furan (DHMF) and methyl furan (MF) as intermediates. The total Gibb’s Free energy difference for the 5-HMF transformation to 2,5 DMF is highly exothermic. The condensation, rehydration and oxidation reactions of 5- HMF also predicted to be feasible and highly exothermic in nature, that can have potential application in industrial processes. Ethanol is mixed with petrol to run the vehicle on reduced fuel. Ethanol can be obtained from glucose following glycolysis pathway, breaking C-6 sugar to two C-3 sugars. Glyceraldehyde and pyruvic acid are the intermediates in the glycolysis cycle with positive Gibbs free energy change, hence require high temperature.

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“…Determination of the intra-molecular hydrogen bonding strength in substituted benzophenone using the “well-balanced reaction” method; Enthalpy of fusion measurements. References [ 7 , 8 , 9 , 10 , 20 , 31 , 32 , 46 , 55 , 58 , 59 , 60 , 61 , 62 , 63 , 64 ] are cited in the Supplementary Materials.…”

mentioning

confidence: 99%

Nearest-Neighbour and Non-Nearest-Neighbour Non-Covalent Interactions between Substituents in the Aromatic Systems: Experimental and Theoretical Investigation of Functionally Substituted Benzophenones

2022

Self Cite

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Benzophenone derivatives exhibit not only biological activity but also act as photo initiator and UV blocker. We carried out experimental and theoretical thermochemical studies of hydroxy- and methoxy-substituted benzophenones. Standard molar enthalpies of vaporisation were obtained from the temperature dependence of vapour pressures measured by the transpiration method. The thermodynamic data on phase transitions available in the literature (crystal–gas, crystal–liquid, and liquid–gas) were also collected and evaluated. High-level quantum chemical methods G3MP2 and G4 were used to estimate the standard molar enthalpies of formation of substituted benzophenones in the gas phase and establish agreement between experimental and theoretical results. The application of the “centrepiece” group-contribution approach to hydroxy- and methoxy-substituted benzophenones was demonstrated. A quantitative assessment of the hydrogen bond was carried out using various approaches based on experimental data and quantum chemical calculations.

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Weaving a web of reliable thermochemistry around lignin building blocks: phenol, benzaldehyde, and anisole

Cited by 9 publications

References 61 publications

Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V

Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V

Thermochemical property predictions in biomass transformation to fuel components and value-added chemicals

Nearest-Neighbour and Non-Nearest-Neighbour Non-Covalent Interactions between Substituents in the Aromatic Systems: Experimental and Theoretical Investigation of Functionally Substituted Benzophenones

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