On the ortho : para ratio in activation of nucleophilic aromatic substitution by the nitro-group

1970 ◽  
pp. 769
Author(s):  
Francesco Pietra ◽  
Francesco Del Cima
Keyword(s):  
Nitro Group ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution

Synthesis and Structural Investigation of Some Electron-Rich Nitroaromatics

2019 ◽  
Vol 72 (4) ◽  
pp. 311
Author(s):  
Jonathan M. White ◽  
Colin E. Skene ◽  
John Deadman ◽  
Ruwan Epa ◽  
Sarah Foenander ◽  
...  
Keyword(s):  
Nitro Group ◽  
Bond Distance ◽  
Lone Pair ◽  
Crystal Structure Analysis ◽  
Nucleophilic Aromatic Substitution ◽  
Anomeric Effect ◽  
Aromatic Substitution ◽  
Nitrogen Lone Pair ◽  
Lone Pair Electrons ◽  
Electron Donation

2,4-Difluoro-, 2,4,6-trifluoro-, and 2,3,4,6,tetrafluoronitrobenzenes undergo nucleophilic aromatic substitution, once, twice, and three times with a variety of amine substituents with a high degree of regiochemical control to provide a range of electron-rich nitrobenzene derivatives. In these structures the nitro group proves a useful structural probe to reveal the varying extents of electron donation from the varying number of amino substituents onto the nitro group as revealed by accurate low temperature X-ray crystal structure analysis, thus increasing electron donation manifests in a decrease in the Ar–NO2 distance consistent with increased double bond character, while the N–O bond distance increases as the oxygens accept the electron density. The effect of delocalization of the aniline nitrogen lone pair onto the nitro group impacts on the geometry and hybridization of the nitrogen substituent and also impacts on the ability of the nitrogen lone pair electrons to participate in other competing electronic interactions, such as the nN–σ*C–S anomeric effect as demonstrated by the thiazolidine substituted derivatives 3c, 4c, and 6c.

Redox condensation of o-halonitrobenzene with 1,2,3,4-tetrahydroisoquinoline: involvement of an unexpected auto-catalyzed redox cascade

2016 ◽  
Vol 52 (27) ◽  
pp. 4914-4917 ◽  
Author(s):  
T. B. Nguyen ◽  
L. Ermolenko ◽  
A. Al-Mourabit
Keyword(s):  
Nitro Group ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Methylene Group

An uncatalyzed cascade of nucleophilic aromatic substitution, reduction of the nitro group, oxidation of the α-methylene group and condensation.

scholarly journals Machine learning meets mechanistic modelling for accurate prediction of experimental activation energies

2021 ◽  
Author(s):  
Kjell Jorner ◽  
Tore Brinck ◽  
Per-Ola Norrby ◽  
David Buttar
Keyword(s):  
Machine Learning ◽  
Activation Energies ◽  
Accurate Prediction ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Mechanistic Modelling

Hybrid reactivity models, combining mechanistic calculations and machine learning with descriptors, are used to predict barriers for nucleophilic aromatic substitution.

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