An AM1 study of the effect of substituents on the bond dissociation energies of anilines, phenols, and α-substituted toluenes

Bean, Gerritt P.

doi:10.1016/s0040-4020(02)01327-3

Cited by 18 publications

(13 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Several previous studies addressed the change of BDEs of the C α H bond in toluene upon the presence of para substituents . It was found that the benzyl radical is stabilized upon introduction of a substituent group, irrespective of whether the Z group is an electron donor or acceptor.…”

Section: Resultsmentioning

confidence: 99%

“…Several previous studies addressed the change of BDEs of the C a AH bond in toluene upon the presence of para substituents. [92][93][94][95][96] It was found that the benzyl radical is stabilized upon introduction of a substituent group, irrespective of whether the Z group is an electron donor or acceptor. The present findings confirm these conclusions since all para-Z-C 6 H 4 CH 2 AH bonds are weaker than that in toluene.…”

Section: Bde Analysis Of Mahsmentioning

confidence: 99%

See 1 more Smart Citation

Group additive modeling of substituent effects in monocyclic aromatic hydrocarbon radicals

et al. 2016

View full text Add to dashboard Cite

The thermodynamic properties of the unsubstituted and substituted phenyl, phenoxy, anisyl, benzoyl, styryl and benzyl radicals with six substituents (hydroxy, methoxy, formyl, vinyl, methyl, and ethyl) are calculated with the bond additivity corrected (BAC) post‐Hartree‐Fock G4 method. Bond dissociation energies of monocyclic aromatic hydrocarbons are calculated and used to identify substituent interactions in these radicals. Benson's Group Additivity (GA) scheme is extended to aromatic radicals by defining 6 GAV and 29 NNI parameters through least squares regression to a database of thermodynamic properties of 369 radicals. Comparison between G4/BAC and GA calculated thermodynamic values shows that the standard enthalpies of formation generally agree within 4 kJ mol−1, whereas the entropies and the heat capacities deviate less than 4 J mol−1 K−1. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2089–2106, 2017

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Bde Analysis Of Mahsmentioning

confidence: 99%

Group additive modeling of substituent effects in monocyclic aromatic hydrocarbon radicals

et al. 2016

View full text Add to dashboard Cite

show abstract

“…1 kcal/mol [35] [36]. The present study reveals that two EtOCO groups reduce the BDE value of CÀH bonds by as much as 10 kcal/mol, indicating that resonance effects are much stronger in this case than electronic effects in lowering the dissociation enthalpy.…”

Section: Roomentioning

confidence: 49%

DFT Calculations Indicate that 1,4‐Dihydropyridine Is a Promising Lead Antioxidant

Wang

Zhang

Kong

et al. 2004

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…18 Previously, we have shown that olefins of the 1-acetyl vinyl carboxylate type 1 (Figure 1) proved to be highly reactive and regioselective as dienophiles and dipolarophiles in Diels−Alder and 1,3-dipolar cycloadditions with unsymmetrically substituted dienes 19,20 and diverse 1,3-dipoles. 21,22 Even though these dienophiles or dipolarophiles are structurally related to captodative radicals, we have found no experimental or computational evidence that the captodative effect significantly enhances their reactivity and selectivity compared with dienophiles or dipolarophiles bearing a single electron-withdrawing group, such as methyl vinyl ketone (2). 23,24 Because the electron-releasing effect of the aroyloxy group (OCOC 6 H 4 p-NO 2 ) would be expected to deplete their reactivity under normal electron demand (NED) conditions, their behavior is rather unexpected.…”

Section: ■ Introductionmentioning

confidence: 78%

Thermochemical Study of 1-Acetyl Vinyl p-Nitrobenzoate: Vinyl Bond Enthalpy in Captodative Olefins

et al. 2015

View full text Add to dashboard Cite

Captodative olefins are highly reactive and selective substrates in Diels-Alder and 1,3-dipolar cycloadditions. Seeking an explanation of this fact based on molecular energetics, the thermochemical analysis of 1-acetyl vinyl p-nitrobenzoate, a captodative olefin, has been performed using semi-micro-combustion calorimetry, effusion measurements through a quartz crystal microbalance, and differential scanning calorimetry. The molar standard combustion energy and enthalpy as well as the molar standard formation enthalpy are reported along with sublimation and melting enthalpies. From these data, experimental formation enthalpy of the gas-phase is derived and compared with the theoretical value calculated through the density functional theory procedure. The olefinic bond enthalpy is also computed from experimental data, and the relevance of the results is discussed.

show abstract

An AM1 study of the effect of substituents on the bond dissociation energies of anilines, phenols, and α-substituted toluenes

Cited by 18 publications

References 23 publications

Group additive modeling of substituent effects in monocyclic aromatic hydrocarbon radicals

Group additive modeling of substituent effects in monocyclic aromatic hydrocarbon radicals

DFT Calculations Indicate that 1,4‐Dihydropyridine Is a Promising Lead Antioxidant

Thermochemical Study of 1-Acetyl Vinyl p-Nitrobenzoate: Vinyl Bond Enthalpy in Captodative Olefins

Contact Info

Product

Resources

About