Theoretical and conceptual density functional theory (DFT) study on selectivity of 4-hydroxyquinazoline electrophilic aromatic nitration

Makhloufi, A.; Belhadad, O.; Ghemit, R.; Baitiche, Milad; Merbah, M.; Benachour, Djafer

doi:10.1016/j.molstruc.2017.09.001

Cited by 13 publications

(6 citation statements)

References 26 publications

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“…329 Quantitative linear relationships between the experimental rate constants and the global and local electrophilicity indices are obtained for nucleophilic addition involving the C C double bond, 328 Friedel-Crafts reactions, 182 and aminolysis of thiolcarbonates and dithiocarbonates. 190 The reactivity patterns associated with formaldehyde decomposition, 315,330 intermolecular ligand exchange in alkyltin trihalides, 315,330 hydride ion transfer, 331 selectivity of 4-hydroxyquinazoline electrophilic aromatic nitration, 332 and so forth have been properly analyzed in terms of the electrophilicity index or its variants.…”

Section: Chemical Reactivity and Cdft Based Chemoinformaticsmentioning

confidence: 99%

Electrophilicity index revisited

Pal

Chattaraj

2022

J Comput Chem

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This review aims to be a comprehensive, authoritative, critical, and accessible review of general interest to the chemistry community; because the electrophilicity index is a very useful global reactivity descriptor defined within a conceptual density functional theory framework. Our group has also introduced electrophilicity based new global and local reactivity descriptors and also new associated electronic structure principles, which are important indicators of structure, stability, bonding, reactivity, interactions, and dynamics in a wide variety of physico‐chemical systems and processes. This index along with its local counterpart augmented by the associated electronic structure principles could properly explain molecular vibrations, internal rotations and various types of chemical reactions. The concept of the electrophilicity index has been extended to dynamical processes, excited states, confined environment, spin‐dependent and temperature‐dependent situations, biological activity, site selectivity, aromaticity, charge removal and acceptance, presence of external perturbation through solvents, external electric and magnetic fields, and so forth. Although electrophilicity and its local variant can adequately interpret the behavior of a wide variety of systems and different physico‐chemical processes involving them, their predictive potential remains to be explored. An exhaustive review on all these aspects will set the tone of the future research in that direction.

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Section: Chemical Reactivity and Cdft Based Chemoinformaticsmentioning

confidence: 99%

Electrophilicity index revisited

Pal

Chattaraj

2022

J Comput Chem

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“…This molecule is accepted as the quasi-stable intermediate species in the kinetics of the bromination of nitrobenzene, and the site selectivity of halogenations of aryl species is largely dictated by this intermediate. 32,40,41,47 However, recent experimental and theoretical explorations have demonstrated that other pathways, such as an addition−elimination route, maybe more favored under certain conditions. 42,48,49 Outside the cavity, the meta intermediate is the most stable for nitrobenzene and provides nearly 100% selectivity due to a favorable set of possible resonance structures.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In this work, we focus on the cavity modification of the energies of these positively charged reaction intermediates PhNO 2 –Br + . This molecule is accepted as the quasi-stable intermediate species in the kinetics of the bromination of nitrobenzene, and the site selectivity of halogenations of aryl species is largely dictated by this intermediate. ,,, However, recent experimental and theoretical explorations have demonstrated that other pathways, such as an addition–elimination route, maybe more favored under certain conditions. ,, …”

Section: Resultsmentioning

confidence: 99%

Cavity Quantum Electrodynamics Enables para- and ortho-Selective Electrophilic Bromination of Nitrobenzene

Weight,

Weix,

Tonzetich

et al. 2024

J. Am. Chem. Soc.

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Coupling molecules to a quantized radiation field inside an optical cavity has shown great promise to modify chemical reactivity. In this work, we show that the ground-state selectivity of the electrophilic bromination of nitrobenzene can be fundamentally changed by strongly coupling the reaction to the cavity, generating ortho-or para-substituted products instead of the meta product. Importantly, these are products that are not obtained from the same reaction outside the cavity. A recently developed ab initio approach was used to theoretically compute the relative energies of the cationic Wheland intermediates, which indicate the kinetically preferred bromination site for all products. Performing an analysis of the ground-state electron density for the Wheland intermediates inside and outside the cavity, we demonstrate how strong coupling induces reorganization of the molecular charge distribution, which in turn leads to different bromination sites directly dependent on the cavity conditions. Overall, the results presented here can be used to understand cavity induced changes to ground-state chemical reactivity from a mechanistic perspective as well as to directly connect frontier theoretical simulations to state-of-the-art, but realistic, experimental cavity conditions.

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“…The global nucleophilicity (N) is calculated based on the HOMO energies: N = E HOMO − E HOMO ( TCE ) ; here, tetracyanoethylene (TCE) was chosen as reference because it presents the lower HOMO energy (−9.12 eV). Noteworthy, from the nucleophilicity index (N), it may be seen that studied derivative can act as moderate nucleophile in polar organic reactions, since it shows nucleophilicity power value (2.527 eV) in the range 2.0 to 3.0 eV . Electrophilic and nucleophilic reactive sites of title compound have been assessed based on electrophilic

P_{k}^{+}

and nucleophilic

P_{k}^{-}

Parr functions, considering atomic spin densities coming from the Mulliken population analysis.…”

Section: Resultsmentioning

confidence: 99%

A newly synthesized nitrogen‐rich derivative of bicyclic quinoxaline—Structural and conceptual DFT reactivity study

Abad¹,

Hajji

Ramli

et al. 2020

J of Physical Organic Chem

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Novel nitrogen-rich compound featured bicyclic quinoxaline as a basic core structure has been synthesized, 1-{[1-(3-azido-2-hydroxypropyl)-1H-1,-2,3-triazol-4-yl]methyl}-3-methyl-1,2-dihydroquinoxalin-2-one with formula C 15 H 16 N 8 O 2 , and their structural and chemical reactivity aspects have been comprehensively discussed. Nature, role, and relative contribution of weak noncovalent interactions in supramolecular assembly have been assessed through single-crystal analysis and computational approaches. Useful information about the global and local reactivity were obtained from Conceptual Density Functional Theory at wB97X-D/cc-pVDZ level. Studied system could act as strong electrophile and/or moderate nucleophile in polar organic reactions. We hope this study will provide deeper insight in the knowledge of the synthesis and chemistry of the quinoxaline and quinoxaline derivatives. K E Y W O R D SDFT, chemical reactivity theory, Hirshfeld surfaces, NCI topological analysis, quinoxaline derivatives, weak noncovalent interactions

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Theoretical and conceptual density functional theory (DFT) study on selectivity of 4-hydroxyquinazoline electrophilic aromatic nitration

Cited by 13 publications

References 26 publications

Electrophilicity index revisited

Electrophilicity index revisited

Cavity Quantum Electrodynamics Enables para- and ortho-Selective Electrophilic Bromination of Nitrobenzene

A newly synthesized nitrogen‐rich derivative of bicyclic quinoxaline—Structural and conceptual DFT reactivity study

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