Chapter 4.

Aromatic Compounds
Aromatic compounds --- a special class of cyclic compounds related in structure to
benzene (parent of this type of hydrocarbon)

4.1 Some Facts about Benzene

--- Molecular formula of benzene: C6H6
--- a highly unsaturated hydrocarbons
--- more stable than the other unsaturated hydrocarbons: alkenes and alkynes
--- can’t be oxidized by KMnO4 to change color like alkenes
--- does not undergo the typical addition reactions of alkenes or alkynes
--- reacts mainly by substitution like alkanes
--- all six hydrogen atoms in benzene are chemically equivalent.
4.2 The Structure of Benzene
1. The Kekulé Structure H H
H H H H
rapidly

H H H H
H H

1
 Cl Cl
Cl H Cl H
and are the Kekulé structures of ortho-dichlorobenzene
H H H H
H H

molecule. Are they same if we don’t take into account the equilibrium between the two
structures?
They are different in the arrangement of the electrons. In chapter 1. we reviewed the
resonance structures. So instead of the rapid exchange structures in an equilibrium,
the Kekulé structures represent two contributing structures to a single resonance
hybrid structure of benzene.
2. The Resonance Model for Benzene
In stead of “ “, write the double-headed arrow “ ” for resonance structures.
H H
H H H H
Benzene is a resonance hybrid of
these two contributing structures.
H H H H
H H
2
(1) Being a resonance hybrid, benzene is more stable than its Kekulé structures.
There are no single or double bonds in benzene --- only one type of carbon-carbon
bond, which is the intermediate of C-C and C=C.
(2) Experimental measurement: benzene is planar, each carbon atom is at the corner
of a regular hexagon. All carbon-carbon bonds are identical with a bond length
1.39Ǻ (C-C single bond is 1.54Ǻ and C=C double bond is 1.34Ǻ). These support
the resonance model for benzene structure.
(3) So benzene doesn’t react chemically like alkenes (not addition but substitution).
(4) Physical properties of benzene: colorless liquid, bp is 80ºC and mp is 5.5ºC
3. Orbital Model of Benzene
All carbons of benzene are sp2 hybridized. Each carbon has a p orbital left, which
is perpendicular to the plane of 3 sp2 hybridized orbitals. Each carbon uses two sp2
hybridized orbitals to form C-C  bonds with the other two carbons’ sp2 hybridized
orbitals, and uses one sp2 hybridized orbital to form C-H  bond with a hydrogen’s
1s orbital. In this way the 6 carbons of benzene form a hexagon carbon frame. The
p orbitals on all six carbons can overlap laterally to form a big  bond which is a
ring with cloud of electrons above or below the plane of the ring. All the H-C-C and
C-C-C bond angles are 120º. See Figure 4.2 on pg.120 of your textbook.
4. Symbols for Benzene
Conventionally, so far Kekulé structure is still used.
A hexagon a circle inscribed for delocalized  cloud is also used.
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4.3 Nomenclature of Aromatic Compounds
1. Common names are accepted by IUPAC.
CH3 CH3CHCH3 CH CH2 OH

benzene toluene cumene styrene phenol

OCH3 CH O CH3C O CO2H NH2

anisole benzaldehyde acetophenone benzoic acid aniline

2. Monosubstituted benzenes are named as derivatives of benzene.
CH3
CH2CH2CH2CH3 CCH3 t-butylbenzene

butylbenzene CH3
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3. If two substituents are present in benzene, three isomeric structures are possible.
X X
o o
designated by the prefix ortho- X
abbreviated as o-
designated by the prefix para-
X X abbreviated as p-

designated by the prefix meta- p

abbreviated as m-
m m

H3C CH3
Example:
H3C H3C H3C CH3

o-xylene m-xylene p-xylene

The prefixes ortho-, meta-, and para- are used even when the two substituents are
not identical. Br H2C CH
Example:
Br SO3H Cl O2N

p-bromobenzenesulfonic acid m-bromochlorobenzene o-nitrostyrene

5
4. When more than two substituents are present, their positions are designated by
numbering the ring.
CH CH2 Br
2 3 5 6

1 4 4 1
H2C CH Br OH
2
6 5 3
CH CH2 Br
1,3,5-trivinylbenzene 2,4,6-tribromophenol
5. Aromatic hydrocarbons --- arenes. The symbol Ar- is for aryl group.
phenyl group C6H5- Ph-
Common aryl groups
benzyl group C6H5CH2-
CH2
ArR --- arylalkane
Examples:
Problem 4.9 a. b. CH2Br

c. CH CH2d. CH2 CH2

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Problem 4.10 a. cyclohexylbenzene or phenylcyclohexane b. o-benzylphenol
4.4 The Resonance Energy of Benzene
1,3,5-hexatriene

36 kcal/mol 

1,3-cyclohexadiene benzene
Energy
84 ~ 86 kcal/mol
cyclohexene
55.4 kcal/mol
49.8 kcal/mol
28.6 kcal/mol

cyclohexane

Here,  is the stabilization energy, or resonance energy, which is the difference

between the energy of the real molecule (the resonance hybrid) and the calculated
energy of the most contributing structure.
Benzene and other aromatic compounds usually react in such as way as to
preserve their aromatic structure and therefore retain their resonance energy.
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4.8 Electrophilic Substitution of Benzene
Electrophilic substitution of benzene --- the substitution reaction in which the electron
poor reactant) substitutes the proton(s) of benzene.
1. Halogenation
catalyst
H   X
  FeX3
X X HX

X = Cl, Br
2. Nitration
catalyst
H NO2
  H SO
HO NO2 2 4 H2O
(HNO3)

3. Sulfonation
catalyst
H   SO3H
  SO3
HO SO3H H 2O
heat
(H2SO4)
8
4. Alkylation
catalyst
H   R
  AlCl3
R Cl HCl

R = an alkyl group such as CH3 and CH3CH2

This is also called Friedel-Crafts Alkylation.
catalyst
H CH2CH3
H2SO4
CH2 CH2

5. Acylation O
H O C R
AlCl3
R C Cl HCl

R = any alkyl group

This
9 is also called Friedel-Crafts Acylation.
4.10 Ring-Activating and Ring-Deactivating Substituents
1. Ring-activating substituents:
If the substituent(s) on a benzene is (are) more electron donating than H, the
electron density of the benzene ring is increased, so the speed of the electrophilic
substitution is faster. e.g. –OH and –CH3
These electron donating substituents are called ring-activating substituents.
2. Ring-deactivating substituents:
If the substituents on benzene ring are more electron withdrawing, the electron
density of the benzene ring is decreased, so the speed of the electrophilic
substitution is slower. e.g. –Cl and –NO2
These electron withdrawing substituents are called ring-deactivating substituents.
OH CH3 H Cl NO2

1000 24.5 1 .0 0.033 0.0000001

nitration rate
(relative) decreasing rate

4.11 Ortho, Para-Directing and Meta-Directing Groups

Substituents already present on an aromatic ring determine the position taken by
the new substituent.
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 ortho-, para- Directing and meta-Directing
Group

CH3 CH3 CH3

NO2
HONO2
+ + (4% metaisomer)

NO2
orthoisomer paraisomer
59% 37%

NO2 NO2

HONO2 + orthoisomer
7%
NO2
11 (93% metaisomer)
 Ortho,para attack
CH3 CH3 CH3
ortho H H H
NO2 NO2 NO2
CH3

CH3 CH3 CH3

para

O2N H O2N H O2N H

12
 Meta attack

CH3 CH3 CH3 CH3

meta
H H H

NO2 NO2 NO2

13
 Ortho,para attack
OH OH OH OH
H H H H
ortho Br Br Br Br

OH

para OH OH OH OH

Br H H Br H
Br Br H
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 Meta attack
O O– O O– O +
O–
N +
N+ N
H H H
ortho
NO2 NO2 NO2
–
O O
N+

–
O O– O O O O–
para N+ N+ N +

O2N H O2N H O2N H

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 Meta attack

O O– O –
O – O O–
O O N+
N+ N +
N +

meta

H H H

NO2 NO2
NO2

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 OH OH OH
NO2
HONO2 very few
meta isomer

OH is a ortho-, para-directing group NO2

COOH COOH

HONO2 very few ortho

and para isomers
NO2
COOH is meta-directing group.

Table 4.1 (on pg. 133) shows the directing and activating effects of common
functional groups. From the table, we can see:
(1) All groups with unshared electron pair(s) on the atom attached to the ring are
ortho, para-directing groups. Alkyl groups are ortho, para-directing groups.
(2) All groups in which the atoms directly attached to the ring is positively charged or
is part of a multiple bond to a more electronegative element are meta-directing.
(3) Ortho, para-directing groups normally activate the aromatic ring. Meta-directing
groups are deactivate the aromatic ring. But halo groups are ortho, para-directing
groups but deactivate the aromatic ring.
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 Directing
and
Activating
Effects of
Common
Functional
Groups

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4.12 The Importance of Directing Effects in Synthesis
Based on the directing effect of substituents on the benzene ring, we can design a
Route to synthesize specific di- or multi- substituted benzene.
Synthesize m-bromobenzenesulfinic acid and p-bromobenzenesulfinic acid
starting with benzene.
SO3H SO3H

H2SO4 Br2
heat FeBr3
Br
Br Br

Br2 H2SO4
FeBr3 heat

SO3H
4.13. Polycyclic Aromatic Hydrocarbons (section 4.13 read on your own)
Homework: 4.20 a-f; 4.21 b,d,g; 4.23a; 4.28a; 4.35a,c,e,g.

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 Polycyclic Aromatic Hydrocarbons

Naphthalene Anthracene Phenanthrene

Pyrene

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