AROMATIC

COMPOUNDS
By: Group 1
INTRODUCTION

In the early days of organic chemistry, the word aromatic

was used to describe fragrant substances such as
benzaldehyde (from cherries, peaches and almonds), toluene
(from tolu balsam), and benzene (from coal distillate).
A quick inspection of these molecules reveals that they each
contain a benzene- like ring- a six- membered ring with
alternating double and single bonds.
PROPERTIES
• Benzene
– Does not undergo electrophilic addition reactions
– All carbon-carbon bonds in benzene have the same length, intermediate between
a typical single bond a typical double bond.
– Most C-C single bonds have lengths near 154 pm
– Most C-C double bonds have lengths about 134 pm long
– All C-C bonds in benzene are 139 pm long
– Benzene is a flat, symmetrical molecule with a shape of a regular hexagon.
– All C-C-C bond angles are 120 degrees
NOMENCLATURE
Aromatic substances, more than any other class of
organic compounds, have acquired a large number of
common name. Although the use of such names is
discouraged, IUPAC rules allow for some common names
to be retained.
e.g. methylbenzene is commonly known as toluene
• Monosubstituted benzenes are systemically
named in the same manner as other
hydrocarbons, with –benzene used as the
parent name. Thus,
C6H5Br bromobenzene
• The name phenyl (fen-nil) is used for the –
C6H5 unit when the benzene ring is
considered as a substituent.
• The name benzyl is used for the C6H5CH2-
group.
• Disubstituted benzenes are named using one of the
prefixes
ortho- (o) has its two substituents in a 1,2 relationship
meta- (m) has its two substituents in a 1,3 relationship
para- (p) has its two substituents in a 1,4 relationship
 1

ortho-Dichlorobenzene meta-Xylene
1,2 disubstituted 1,3 disubstituted

para-Chlorobenzaldehyde
1,4 disubstituted
• Benzenes with more than two substituents
are named by numbering the position of
each substituent on the ring so that the
lowest possible numbers are used.
• The substituents are listed alphabetically
when writing the name.

4-Bromo-1,2-dimethylbenzene
• Note that - toluene is used as the parent name rather
than –benzene.

2,4,6-Trinitrotoluene (TNT)
• Any of the monosubstituted aromatic compounds shown earlier
(Common Names of Some Aromatic Compounds) can serve as a parent
name, with the principal substituent (-CH3, in toluene, for
example) assumed to be on carbon 1.

6 2

5 3

2,6-Dibromophenol m-Chlorobenzoic acid

REACTIONS
ELECTROPHILIC AROMATIC
SUBSTITUTION
– The most common reaction of aromatic compounds.
– That is, an electron-poor reagent (an electrophile, E+) reacts with
the electron-rich aromatic ring (a nucleophile) and substitutes for
one of the ring hydrogens.
• Many different substituents can be introduced onto the
aromatic ring by electrophilic substitution. By carrying
out the right reactions, it is possible to
– halogenate the aromatic ring (substitute a halogen: -F, -Cl, -Br,
or –I)
– nitrate it (substitute a nitro group: -NO2)
– sulfonate it (substitute a sulfonic acid group: -SO3H)
– alkylate it (substitute an alkyl group: -R)
– acylate it (substitute an acyl group: -COR)
BROMINATION
• Benzene reacts with Br2 in the presence of FeBr3 as catalyst to yield the
substitution product bromobenzene:

Or simply,

Benzene Bromobenzene
OTHER ELECTROPHILIC
AROMATIC SUBSTITUTION
REACTIONS
 CHLORINATION
• Aromatic rings are chlorinated by reaction with Cl2 in the presence of FeCl3
catalyst. This kind of reaction is used in the synthesis of numerous
pharmaceutical agents, including the tranquilizer diazepam (Valium).

Benzene Chlorobenzene (86%)

Diazepam
NITRATION
• Aromatic rings are nitrated by reaction with a mixture of concentrated nitric
and sulfuric acids. The electrophile is the nitronium ion, NO2+, which is formed
by reaction of HNO3 with H+, followed by loss of water, and which reacts with
benzene in much the same way Br+ does.
• Nitration of aromatic rings is a key step in the synthesis of explosives such as TNT
(2,4,6-trinitrotoluene), dyes, and many pharmaceutical agents.

Benzene Nitrobenzene (85%)

Trinitrotoluene (TNT)
SULFONATION
• Aromatic rings are sulfonated by reaction with so-called fuming sulfuric acid, a
mixture of SO3 and H2SO4. The reactive electrophile is HSO3+, and substitution
occurs by the usual two-step mechanism seen for bromination.
• Aromatic sulfonation is a key step in the synthesis of such compounds as the
sulfa drug family of antibiotics.
FRIEDEL-CRAFTS
ALKYLATION AND
ACYLATION REACTIONS
FRIEDREL-CRAFTS ALKYLATION
REACTION
– A process where an alkyl group is attached to an aromatic ring on a
reaction with an alkyl chloride, RCl, in the presence of AlCl3 catalyst.
– It is an aromatic substitution in which the electrophile is a
carbocation, R+. Aluminum chloride catalyzes the reaction by
helping the alkyl chloride ionize, in much the same way that FeBr3
helps Br2 ionize.

Benzene 2-Chloropropane Cumene (85%)

Isopropylbenzene
• Although useful, the Friedrel-Crafts alkylation reaction
has several limitations. Some of it are,
– Only alkyl halides can be used; aryl halides such as
chlorobenzene don’t react.
– Friedrel-Crafts reactions don’t succeed on aromatic rings that
are already substituted by the groups -NO2, -C≡N, -SO3H, or –
COR.
Such aromatic rings are much less reactive than benzene.
FRIEDREL-CRAFTS ACYLATION
REACTION
• Closely related to the Friedrel-Crafts alkylation reaction.
• When an aromatic compound is treated with a carboxylic acid
chloride, RCOCl, in the presence of AlCl3, an acyl (a-sil) group, -
COR is introduced onto the ring.

Benzene Acetyl chloride Acetophenone (95%)

SUBSTITUENT EFFECTS IN ELECTROPHILIC
AROMATIC SUBSTITUTION
• Substituents affect the reactivity of the aromatic ring. Some groups activate the
ring for further electrophilic substitution, and some deactivate it.
– An –OH group activates the ring, for instance, making phenol (hydroxybenzene) 1000
times more reactive than benzene toward nitration.
– An –NO2 group deactivates the ring, however, making nitrobenzene 20 million times
less reactive than benzene.
• Substituents affect the orientation of the reaction. The three possible disubstituted
products –ortho, meta, and para- are usually not formed in equal amounts.
Instead, the nature of the substituent already present on the ring determines the
position of the second substitution.
– An –OH group directs further substitution toward the ortho and para positions, for
instance, while a –CN group directs further substitution primarily toward the meta
position.
• Substituents can be classified into three groups based on site of
reaction and reactivity:
– Ortho- and para-directing activators: Groups like –OH and –NH3 present on
a ring direct an electrophile, E+, to ortho or para positions, and they react
faster than benzene.
– Ortho- and para-directing deactivators: Halogens present on a ring direct
an electrophile, E+, to ortho or para positions, and they react slower than
benzene.
– Meta-directing deactivators: Groups containing a carbonyl (C=O) or a –CN
group direct an electrophile, E+, to the meta positions, but they react
slower than benzene.
OXIDATION AND REDUCTION OF
AROMATIC COMPOUNDS
• Despite its unsaturation, a benzene ring does not usually react with strong
oxidizing agents such as KMnO4. Alkyl groups attached to the aromatic ring
are readily attacked by oxidizing agents, however, and are converted into
carboxyl groups (-CO2H).
For example, butylbenzene is oxidized by KMnO4 to five benzoic acid. The
mechanism of this reaction is complex and involves attack on the side-chain C-H
bonds at the position next to the aromatic ring (the benzylic position) to give
radical intermediates.
AROMATICITY IN NONBENZENE RINGS
AND POLYCYCLIC COMPOUNDS
• Extending the concept of aromaticity beyond simple monocyclic
compounds to include polycyclic aromatic compounds.
– Napthalene, familiar for its use in mothballs, has two benzene-like rings
fused together and is the simplest and best-known polycyclic aromatic
compound.
– Benz[a]pyrene is found in chimney soot, cigarette smoke, and charcoal-
broiled meat. Once in the body, it is oxidized and becomes carcinogenic.

Napthalene Benz[a]pyrene
• Pyridine and pyrrole are examples of nitrogen-containing
aromatic compounds.
• Chemists can rapidly determine whether a molecule is aromatic
by applying the 4n+2 𝜋 electron rule. If the number of 𝜋 electrons
in a flat, cyclic, conjugated molecule is an equal to 4n+2 (where
n is an integer), the molecule is aromatic.
• Let’s look back at benzene. Benzene has 6 𝜋 electrons and fits the
4n+2 rule, where n=1.

Why is pyrrole
aromatic?
Pyrrole
 Why is pyrrole aromatic?

• The lone pair of electrons on nitrogen leads

to a total of 6 𝜋 electrons and completes
the ring.
ORGANIC SYNTHESIS
• The only trick to devising an organic synthesis is to work backward,
a process called retrosynthesis. Look at the product and ask
yourself, “What is the immediate precursor of that product?”
Having found an immediate precursor, work backward again,
one step at a time, until a suitable
𝜋 starting material is found.
PRACTICE PROBLEM
• “What is an immediate precursor of m-chloronitrobenzene?”

?
m-Chloronitrobenzene
• There are two substituents on the ring, a –Cl group, which is ortho- and para-
directing, and an –NO2 group, which is meta-directing. We can’t nitrate
chlorobenzene because the wrong isomers (o- and p-chloronitrobenzenes)
would result, but chlorination of nitrobenzene should give the desired product.
• “What is an immediate precursor of nitrobenzene?” Benzene, which can be
nitrated.

Chlorobenzene

m-Chloronitrobenzene

Nitrobenzene
PRACTICE PROBLEM
• Solution
We’ve solved the problem in two steps:

HNO3, H2SO4 Cl2, FeCl3

Benzene Nitrobenzene m-Chloronitrobenzene

SUMMARY OF REACTIONS
I. Electrophilic aromatic substitution
a. Bromination
b. Chlorination
c. Nitration
d. Sulfonation
e. Friedel-Crafts alkylation
f. Friedel-Crafts acylation
II. Oxidation of aromatic side chains
III. Hydrogenation of aromatic rings
SUMMARY
Aromatic compounds are named according to IUPAC rules, with
disubstituted benzenes referred to as either ortho, meta or para.
Benzene is a resonance hybrid of two equivalent forms, neither of which
is correct by itself. The true structure of benzene is intermediate between
the two.
Electrophilic aromatic substitution is a two-step polar reaction where
the 𝜋 electrons of the aromatic ring first attack the electrophile to yield a
resonance-stabilized carbocation intermediate, which then loses H+ to
give a substituted aromatic product. Bromination, chlorination,
iodination, nitration, sulfonation, Friedrel-Crafts alkylation, and Friedel-
Crafts acylation can all be carried out. Friedrel-Crafts alkylation is
particularly useful for preparing a variety of alkylbenzenes but is limited
because only alkyl halides can be used and strongly deactivated rings
do not react.
 Substituents on the benzene ring affect both the reactivity of
the ring toward further substitution and the orientation of that
further substitution. Substituents can be classified either as
activators or deactivators, and either as ortho and para
directors or as meta directors.
The side chains of alkylbenzenes have unique reactivity
because of the neighboring aromatic ring. Thus, an alkyl group
attached to the aromatic ring can be degraded to a carboxyl
group (-CO2H) by ocidation with aqueous KMnO4. In addition,
aromatic rings can be reduced to yield cyclohexanes on
catalytic hydrogenation at high pressure.
KEY WORDS
• Aromatic- refers to the class of compounds structurally related to
benzene.
• ortho- 1,2 disubstituted
• meta- 1,3 disubstituted
• para- 1,4 disubstituted
• Electrophilic Aromatic Substitution- most common reaction of
aromatic compounds.
 GROUP 1

CENIZA, ROMEN KHYLE

ESPINOSA, JOSE PATRICK EDWARD

OSUGAY, JOHANN ETHAN JADE

MALAZARTE, JANELLE

MAPANG, ROSHEN NOVIAN

RAMA, JERACHEL

TORRENUEVA, LINDY MOORE

VILLARIAZA, ALLIANAH MAE

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