1) Each H atom of an acceptor-substituted aromatic compound should be

substituted more slowly by an electrophile than an H atom in benzene.

2) The substitution product should primarily be the meta-disubstituted aromatic
compound.Among the by-products, the ortho-disubstituted benzene should
predominate, while practically no para product is expected.

Substitution
Reactions
on Aromatic
Advanced Organic
Compounds
Chemistry, 2002,
Pages 169-219
Reinhard Bruckner
 Journal of Molecular Structure (Theochem) 507 (2000)
239-244

Electrophilic aromatic substitution

regioselectivity for benzene derivatives
in terms of cationic localization energies
from semiempirical quantum chemical
computations
Alexei N. Pankratov, Department of Chemistry,
N. G. Chernyshevskii Saratov State University,
83 Astrakhanskaya Street, Saratov 410026,
Russian Federation, Received 22 January 1999;
received in revised form 1 November 1999;
accepted 1 November 1999
 Journal of Molecular Structure: THEOCHEM 811 (2007)
1926
Loss of aromaticity and pi-electron delocalization in the first step of
the electrophilic aromatic nitration of benzene, phenol and
benzonitrile
Ana Arrieta, Fernando P. Cosso
From the results reported in the present work, the following
conclusions can be drawn: (i) The transition structures
and the sigma-complexes associated with the nitration
of aryl compounds reflect an almost complete destruction
of the aromaticity of the starting arenes as well as a strong
pi-electron delocalization. (ii) The meta-sigma-complexes show
the most important diamagnetic shielding both in the
presence of a hydroxy and cyano groups as model
electron-releasing and electron-withdrawing groups,
respectively. (iii) In the nitration of phenol, the relative stabilities
of the regioisomeric sigma-complexes are in agreement
with the experimentally observed formation of ortho- and
para-nitrophenol. (iv) In the case of benzonitrile, the
meta-sigma-complex is found not to be the most stable one.
This result has been confirmed at high levels of theory
(up to G3B3) or taking into account solvent effects. We
think that this unexpected result deserves further investigations
in order to assess the validity of the classical model
developed to explain the preferential formation of meta
disubstituted nitroarenes when electron-withdrawing
groups are present