SCH 2304 CHEMISTRY OF

AROMATIC COMPOUNDS
LECTURE 3
Objectives
After completing this section, you should be able to
1. draw the resonance contributors for the carbocation
intermediate formed during the reaction of a given
monosubstituted benzene derivative with any of the
electrophiles discussed in this section
2. classify each of the substituents as being either meta or
ortho/para directing.
3. classify each of the substituents as being ortho/para
directing activators,
4. ortho/para directing deactivators, or meta directing
deactivators.
Introduction
Nomenclature of Benzene Disubstituted benzenes are commonly named using

Derivatives Aromatic compounds have been widely ortho, meta and para prefixes. These are often

used for the last hundred years, and most are referred shorted to o-, m- and p-. However, these are non-

to almost exclusively by their common names. IUPAC, and numbers have to be given to the

For example, substituents. E.g.

In certain cases, the functional group defines the

Some are referred to as simple derivatives of benzene
base name, and this also defines C-1. E.g.

When the benzene group is simply a
substituent, it is called a Phenyl or Ph
group,
Note the difference between benzyl
group with the phenyl group. aryl
(aromatic) group is represented by
Ar−
Benzene reactions
Since a mono-substituted benzene ring has two equivalent
ortho-sites, two equivalent meta-sites and a unique para-
site, three possible constitutional isomers may be formed in
such a substitution. If reaction occurs equally well at all
available sites, the expected statistical mixture of isomeric
products would be 40% ortho, 40% meta and 20% para.
Bromination of methoxybenzene (anisole) is very fast and
gives mainly the para-bromo isomer, accompanied by 10%
of the ortho-isomer and only a trace of the meta-isomer.
Bromination of nitrobenzene requires strong heating and
produces the meta-bromo isomer as the chief product.
Benzene reactions. In the following diagram we see that electron donating
Nitro substituent decreases the ring's substituents (blue dipoles) activate the benzene ring
reactivity by roughly a million. toward electrophilic attack, and electron withdrawing
This activation or deactivation of the substituents (red dipoles) deactivate the ring (make it less
benzene ring toward electrophilic reactive to electrophilic attack)
substitution may be correlated with the
electron donating or electron withdrawing
influence of the substituents, as measured
by molecular dipole moments.
Inductive effect of the substituent .
In cases where the subtituents is esters or amides,
Most elements other than metals and carbon have a
they are less activating because they form resonance
greater electronegativity than hydrogen.
structure that pull the electron density away from
Consequently, substituents in which nitrogen,
the ring.
oxygen and halogen atoms form sigma-bonds to the
aromatic ring exert an inductive electron The mechanism above, shows how electron donating
withdrawal, which deactivates the ring. groups direct electrophilic substitution to the ortho
and para positions. Since the extra electron density is
When substituents such as -OH have an unshared pair
localized on the ortho and para carbons, these
of electrons, the resonance effect is stronger than the
carbons are more likely to react with the electrophile.
inductive effect which make these substituents
Inductive effects of alkyl groups activate the
stronger activators, since this resonance effect direct
direction of the ortho or para substitution, which is
the electron toward the ring.
when s electrons gets pushed toward the ring.
Deactivating group (meta directors) The
deactivating groups deactivate the ring by the
inductive effect in the presence of an
electronegative atom that withdraws electron
density away from the ring.
The mechanism above shows that when electron density
is withdrawn from the ring, that leaves the carbons at the
ortho, para positions with a parital positive charge which
is unfavorable for the electrophile, so the electrophile
attacks the carbon at the meta positions. Halogens are an
exception of the deactivating group that directs to the
ortho or para substitution. The halogens deactivate the
ring by inductive effect not by the resonance even though
they have an unpaired pair of electrons. The unpaired pair
of electrons gets donated to the ring, but the inductive
effect pulls away the s electrons from the ring by the
electronegativity of the halogens.
The reaction of a substituted ring with an On the other hand, deactivating groups withdraw
activating group is faster than the same electron density away from the carbocation formed
reaction with benzene. On the other hand, a in the intermediate step, increasing the activation
substituted ring with a deactivated group energy, which slows down the reaction.
reacts slower than benzene. Activating groups
speed up reaction with electrophiles due to
increased electron density on the ring. This
stabilizes the intermediate carbocation, which
decreases the activa ti o n en ergy f o r th e
reaction.
Alkyl groups are inductively donating, therefore are activators. This resulsts in o/p attack to form a tertiary
arenium carbocation which speeds up the reaction.
The methoxy group is an example of groups that are ortho, para directors by
having and oxygen or nitrogen adjacent to the aromatic ring. This same activation
is present with alcohols, amines, esters and amides (with the oxygen or nitrogen
attached to the ring, not the carbonyl). Groups with an oxygen or nitrogen attached
to the aromatic ring are ortho and para directors since the O or N can push
electrons into the ring, making the ortho and para positions more reactive and
stabilizing the arenium ion that forms. This causes the ortho and para products to
form faster than meta. Generally, the para product is preferred because of steric
effects.
Ketones are an example of groups that deactivate an aromatic ring through resonance.
Similar deactivation also occurs with ammonium ions, nitro groups, aldehydes, nitriles,
sulfonic acids, and groups with a carbonyl attached to the ring (amides, esters,
carboxylic acids, and anhydrides). Acyl groups are resonance deactivators. Ortho and
para attack produces a resonance structure which places the arenium cation next to an
additional cation. This destabilizes the arenium cation and slows down ortho and para
reaction. By default the meta product forms faster because it lacks this destabilizing
resonance structure.
Acyl groups are meta directors
Halogens are an interesting hybrid case. They are
ortho, para directors, but deactivators. Overall, they The nitrobenzene reactant in the third example is very
remove electron density from the ring, making it unreactive, so rather harsh reaction conditions must be
less reactive. However, due to their resonance used to accomplish that reaction.
donation to the ring, if it does react, it reacts
primarily at ortho and para positions

More examples of product isomer distribution in

other electrophilic substitutions are given in the
table below. The reaction conditions for these
substitution reactions are not the same, and must be
adjusted to fit the reactivity of the reactant C6H5-Y.
The high reactivity of anisole, for example, requires
that the first two reactions be conducted under very
mild conditions (low temperature and little or no
catalyst).
In alkyl substituents, charge stabilization is
Halogen ( X ), OR and NR 2 substituents all exert a
greatest when the alkyl group is bonded to one of
destabilizing inductive effect on an adjacent positive
the positively charged carbons of the
charge, due to the high electronegativity of the
benzenonium intermediate. This happens only for
substituent atoms. By itself, this would favor meta-
ortho and para electrophilic attack, so such
substitution; however, these substituent atoms all have
substituents favor formation of those products.
non-bonding valence electron pairs which serve to
Primary alkyl substituents, eg methyl, provide
stabilize an adjacent positive charge by pi-bonding, with
greater stabilization of an adjacent charge.
resulting delocalization of charge. Consequently, all
Nitro (NO 2 ), sulfonic acid (SO 3 H) and carbonyl
these substituents direct substitution to ortho and para
(C=O) substituents have a full or partial positive
sites. The balance between inductive electron
charge on the atom bonded to the aromatic ring.
withdrawal and p-π conjugation is such that the
Structures in which like-charges are close to each
nitrogen and oxygen substituents have an overall
other are destabilized by charge repulsion, so
stabilizing influence on the benzenonium intermediate
these substituents inhibit ortho and para
and increase the rate of substitution markedly; whereas
substitution more than meta substitution.. halogen substituents have an overall destabilizing
influence