The origin of August Kekulé’s view of benzene structure:

“There I sat and wrote my

textbook, but things did not
go well; my mind was
occupied
with other matters, I turned
the
chair towards the fireplace
and
began to doze.
“Once again the atoms danced
before my eyes. This time
smaller groups modestly
remained in the background.
My mental eye, sharpened by
repeated apparitions of similar
kind, now distinguished larger
units of various shapes.”

“Long rows, frequently joined

more densely; everything in
motion, twisting and turning
like snakes. And behold, what
was that? One of the snakes
caught hold of its own tail and
mockingly whirled around my
eyes.
“1 awoke, as if by lightening;
this time, too, I spent the rest of
the night working out the
consequences of this
hypothesis”
“Let us learn to dream, gentlemen,
then perhaps we shall find the truth”
AUGUST KEKULÉ
Edison, Einstein and many others have used the
subconscious mind to give them the insight and the
“know-how” to bring about their great achievements.

August Kekulé
“In variably, my device works
as I imagined it should.
In twenty years there has not been
single exception.”
NIKOLA TESLA
“Imagination is more important
than knowledge.”
ALBERT EINSTEIN
 AROMATIC COMPOUNDS

Introduction to
14.1
aromatic Compounds

Arenes = aromatic compounds:

the word aromatic has nothing to do with odour.
 KEYWORDS

aromatic Kekulé structure

ortho meta para

resonance structure

Friedel-Craft acylation
electrophilic substitution

oxidation of
activating and alkylbenzene
deactivating group

substitution of
ortho-para and meta director toluene
 DISCOVERY OF BENZENE

1825 Michael Faraday

(British)

Isolated a pure compound of

boiling point 80oC

Empirical formula = CH

Named “bicarburet of hydrogen”

1834 Eilhard Mitscherlich (German)

Prepared benzene from benzoic acid

heat
C6H5CO2H + CaO  C6H6 + CaCO3

Molar mass = 78, molecular formula = C6H6

named “benzin”

benzene benzin benzoin

benjoin Luban Jawi

gum benzoin
(French) (Arabic)
1866 Friedrich August Kekulé (German)
Proposed a cyclic structure for benzene.
 AROMATIC COMPOUNDS
In earlier time, compounds are called
aromatic because of their pleasant odours.

Benzene has strong

pleasant odour.

Today, we use the word aromatic to refer to

benzene and its structural relatives.
 AROMATIC COMPOUNDS

Aromatic compound is a cyclic conjugated

molecule or ion that is stabilized by ∏ electron
delocalisation.

it is characterised by substitution reactions.

 KEKULÉ’S STRUCTURE

 Kekule was the first to formulate a

reasonable representation of benzene
H

H C H
C C
or
C C
H C H
H

The Kekule structure suggests alternating double

and single carbon-carbon bonds
 RESONANCE STRUCTURE
Benzene is actually a resonance hybrid of the
two Kekulé structures.

equivalent to

resonance hybrid

All C–C bond length equal = 139 pm

Shorter than typical C–C (148 pm)

Longer than typical C=C (134 pm)

The six π electrons completely delocalized around the ring
 The circle represents the six
π electrons, distributed over
the six atoms of the ring!

All six C atoms and six p orbitals are equivalent

 THE CRITERIA FOR AROMATICITY

4 structural criteria must be satisfied for

compound to be aromatic

Cyclic Planar

Conta
in par
numb ticula
er of r
m p l etely electr ∏
Co ed on
j ug a t  ob
con eys H
RuleÜckel’s
 THE CRITERIA FOR AROMATICITY

HÜckel’s Rule
* cyclic, planar and completely
conjugated compounds that
contain [4n+2] ∏ electron
(n=0,1,2…..) are said to be
aromatic

Erich HÜckel
(1896-1980)

 planar monocyclic rings with 2,6,10,14 and so forth

∏ electrons are aromatic
 THE CRITERIA FOR AROMATICITY

EXAMPLE OF AROMATIC COMPOUNDS

1. Aromatic compounds with a single ring

Benzene
aromatic
Benzene is aromatic because:
 contains 6∏ electrons
(obeys HÜckels Rule)
[4n+2] ∏ = [4(1) + 2]∏
 cyclic, planar and has double
= 6 ∏ electrons
bond in the ring
 THE CRITERIA FOR AROMATICITY

2. Aromatic compounds with more than one ring

EXAMPLE

Aromatic

naphthalene
4n+2= 4(2)+ 2
10 ∏ electrons

* Two benzene rings joined together forms naphthalene

 AROMATIC COMPOUNDS

Nomenclature of benzene
14.2
and its derivatives

Arenes = aromatic compounds:

the word aromatic has nothing to do with odour.
 NAMING BENZENE DERIVATIVES
Many organic molecules contain a benzene
ring with one or more substituents.

Many common name are

recognized by the IUPAC
system

EXAMPLE:

CH3
Common: toluene
IUPAC: methylbenzene
 MONO SUBSTITUTED BENZENE
Benzene is the parent name and the substituent
is indicated by a prefix.
F Cl Br

fluorobenzene chlorobenzene bromobenzene

NO2 CH2CH3

nitrobenzene ethylbenzene
 IUPAC rules allow some common names
to be retained.

CH3 OH NH2

toluene phenol aniline

COOH CHO

benzoic acid benzaldehyde

 DISUBSTITUTED BENZENE
Two Same Substituents
Relative position of subsituents are indicated by
prefixes ortho, meta, and para ( o–, m–, and p–)
or by the use of number.
Br
Br 1
1 Br 2
2 Br
1
2 3
4
3
Br Br
1,2–dibromobenzene 1,4–dibromobenzene
or 1,3–dibromobenzene or
o–dibromobenzene or p–dibromobenzene
m–dibromobenzene
 NO2 NO2
1 NO2 1
2
2
3
NO2

1,2–dinitrobenzene 1,3–dinitrobenzene
or or
o–dinitrobenzene m–dinitrobenzene
NO2
1
2

3
4
NO2
1,4–dinitrobenzene
or
p–dinitrobenzene
 DISUBSTITUTED BENZENE
Two Different Substituents

Select one of the substituent that give

new parent name and numbered as C1.
COOH
COOH 1
1 2
2 NO2 COOH
1
2 3
4
3
NO2
NO2
2–nitrobenzoic acid 4–nitrobenzoic acid
or 3–nitrobenzoic acid or
o–nitrobenzoic acid or p–nitrobenzoic acid
m–nitrobenzoic acid
 THREE OR MORE SUBSTITUENTS
Position of substituents must be indicated by
numbers.

The substituents are listed alphabetically when

writing the name.

Cl
Br
1 2 Br Br
3 I
4
2–bromo–1–chloro–3–iodobenzene
Br
1,2,4–tribromobenzene
C atom bearing the subtituent that define the
new parent name is numbered as C1.
OH
COOH
1
2 NO2 1
6 2
3 5 3
4 OH
HO 4
NO2
3,5–dihydroxybenzoic acid
2,4–dinitrophenol

3
Br 4 2 CH3

1 CH3
4–bromo–1,2–dimethylbenzene
 3
Br 4 2 CH3

1 CH3

4–bromo–1,2–dimethylbenzene correct

4–bromo–o–dimethylbenzene

o–, m– and p– naming system is used

for arenes with 2 substituents only!
 14.2-11
PHENYL GROUP
Benzene ring as substituent.
If alkyl substituent is larger than the ring
(more than 6 C), the compound is named as
phenyl-substituted alkane.

1 CH2
3 4 5 6 7
2 CH–CH –CH2–CH2–CH2–CH3
2

2–phenylheptane

Phenyl = C6H5– = Ph
 14.2-12

If the chain is unsaturated (have C═C or C≡C)

or contains important functional group, the
benzene ring is considered as
phenyl substituent.

1 2 3 4 2 1
CH2–C C–CH3 CH2–CH2–OH

1–phenyl–2–butene 2–phenylethanol
 14.2-13
BENZYL GROUP

CH2—

phenyl group benzyl group

CH2Br CH2OH

benzyl bromide benzyl alcohol

 AROMATIC COMPOUNDS

Chemical properties of benzene

14.3
and its derivatives

Arenes = aromatic compounds:

the word aromatic has nothing to do with odour.
 14.3-01
UNUSUAL REACTIONS OF BENZENE

Br2 / CCl4
no addition of Br2
(no decolorization)

BENZENE KMnO4 / H2O

no oxidation
(no decolorization)
H2 / Ni
slow addition at high
temperature and pressure

Alkenes readily undergo addition

reaction, benzene does not!
 14.3-03
REACTION OF ARENES
Involves the benzene ring itself
Electrophilic aromatic substitution

Br
FeBr3
+ Br2

benzene bromobenzene

Involves substituents attached to the ring

CH3CH2CH2CH3 KMnO COOH
4

H2O
butylbenzene benzoic acid
 14.3-04
ELECTROPHILIC SUBSTITUTION
Most characteristic reaction of benzene.
A H atom is replaced by an electrophile.

H E
+ E+ + H+
electrophile
 14.3-05
X2, FeX3 X halogenatio
(X = Cl Br) + HX n

HONO2
NO2
nitratio
+ H2O n
H2SO4

RCl , AlCl3 R Friedel-

+ HCl Crafts
(R can rearrange) Alkylation

O
O
RCCl , AlCl3 Friedel-
C–R Crafts
+ HCl Acylation
 14.3-07
GENERAL MECHANISM

STEP 1 Formation of arenium ion

H
H H E+

H H
H

H H H
E E E
H H H
+ H H H
+ +
H H H H H H
H H arenium ion H
 14.3-08
ARENIUM ION

+
E+ E
H

benzene ring arenium ion

Electrophile takes two electrons of six–electrons

π system to form σ bond.

This interrupts of cyclic system of π electrons.

Benzene ring  arenium ion

(aromatic) (nonaromatic)
The four π electrons delocalized through these
the five C atom (p orbitals)
 14.3-09
STEP 2 Loss of H +

H H
E
H H E
+ H

H H H H
H H

Substitution reaction allow

aromatic six π electrons
to
be regenerated.
+
E+ E – H+
H E

6 π electrons 4 π electrons 6 π electrons

 14.3-10

Kekulé structures are more appropriate for writing

mechanisms.
For simplicity, however, we can show the mechanism
in the following way:
E
STEP 1
H
+ E+ +
arenium ion

STEP 2 E
E
H + H+
+
 14.3-11
HALOGENATION
Reactants: benzene and halogens (Cl2 or Br2).
Conditions:
Lewis acid such as FeCl3 and FeBr3

+ Br2 no reaction
(decolorization not observed)

Br
FeBr3
+ Br2 + HBr

bromobenzene
 14.2-13
MECHANISM
STEP 1 Formation of Br+
δ + δ –
Br–Br + FeBr3 Br—Br–FeBr3 Br+ + FeBr4–
complex

STEP 2 Formation of arenium ion Br

H
+
+ Br+

STEP 3 Loss of H+
Br FeBr4– Br
H + HBr + FeBr3
+
 14.3-14
FUNCTION OF LEWIS ACIDS

Increase polarity of halogen molecules.

Produce positive halogen ions (Br+ or Cl+).
 14.3-15
NITRATION
Reactants: benzene and concd. HNO3.
Conditions:
Concd. H2SO4

HNO3 NO2

H2SO4
nitrobenzene

+ H+ + HSO4–
 12.5-49
MECHANISM

STEP 1 Formation of nitronium ion (NO2+)

H
..+-NO2 + HSO4–
..
H-O-NO2 +
.. H-OSO3H H-O

H2O + NO2+
nitronium ion
STEP 2 Formation of arenium ion
NO2
H
+ NO2+ +

STEP 3 Loss of H+
NO2 HSO 4
–

NO2
H + H2SO4
+
 12.5-51
FRIEDEL–CRAFT ALKYLATION
Reactants: benzene and haloalkane.
Conditions:
Catalyst: Lewis acid such as AlCl3.

R
AlCl3
+ R–X + HCl

alkylbenzene

Alkylation = transfer an
alkyl group to benzene
12.5-52
 12.5-53
EXAMPLE:

Cl
CH(CH3)2
AlCl3
+ CH3CHCH3 + HCl
2–chloropropane
isopropylbenzene

C(CH3)3
AlCl3
+ (CH3)3C–Cl + HCl
2–chloro–2–methylpropane
tert–butylbenzene
 12.5-54
MECHANISM
STEP 1 Formation of carbocation

+ -

: :
: :
(CH3)2CHCl: + AlCl3 (CH3)2CH–Cl–AlCl3

(CH3)2CH+ + AlCl4–
carbocation
STEP 2 Formation of arenium ion
CH(CH3)2
H
+ +
CH(CH3)2 +

STEP 3 Loss of H+
AlCl4–
CH(CH3)2
CH(CH3)2
H
+ + HCl
 OTHER FACTS ABOUT 12.5-55

FRIEDEL–CRAFT ALKYLATION
Rearrangement can occur, especially when
1o haloalkanes are used.
CH2CH2CH2CH3
EXAMPLE: 35
%
CH3CH2CH2CH2Cl butylbenzene
CH3
AlCl3 +
CHCH2CH3 65
%
Rearrangement: sec–butylbenzene

H
+ +
CH3—CH2—CH—CH2 CH3—CH2—CH—CH3
1o carbocation 2o carbocation
 12.5-56
FRIEDEL–CRAFT ACYLATION
Reactants: benzene and acid chloride.
Product: ketone.
Conditions:
Catalyst: Lewis acid such as AlCl3.

EXAMPLE:
O
O
AlCl3 CCH3
+ CH3C—Cl + HCl
acetyl chloride
acetophenone
 12.5-57
ACYL GROUP

O
RC—
acyl group

EXAMPLE:
O
O
–C—
CH3C—
acetyl group benzoyl group

Acylation = transfer an
acyl group to benzene
 12.5-59
MECHANISM
STEP 1 Formation of acylium ion

:O: :O:
R–C–Cl + AlCl3 R–C–Cl–AlCl3

: :
R–C+═O R–C≡O+ + AlCl4–

acylium ion
 Formation of arenium ion R
STEP 2
C=O

+ R–C+═O H
+

STEP 3 Loss of H+
R AlCl4– R
C=O
C═O
H
+ + HCl
 12.5-61
SUBSTITUENT EFFECT

But, what would happen if we were to carry out a reaction

on aromatic ring that already has a substituent?
 12.5-62
EFFECT ON REACTIVITY
Activating groups:
Substituents that activate the ring,
making it more reactive than benzene.
Deactivating groups:
Substituents that deactivate the ring,
making it less reactive than benzene.

EXAMPLE:
NO2 Cl H OH

relative rate
6 x 10–8 0.033 1 1000
of nitration
reactivity
 12.5-63
EFFECT ON ORIENTATION
Ortho–para directors
Tend to direct the incoming group into
ortho and para positions.
Meta directors
Tend to direct the incoming group into
meta position.
EXAMPLE: ortho-para director
CH3 CH3 CH3 CH3

HNO3 NO2
+ +
H2SO4 NO2
(59 (37 (4
%)
NO2
%) %)
 12.5-64

CLASSIFICATION OF SUBSTITUENTS

ortho– , para– directing

activators

ortho– , para– directing

deactivators

meta– directing deactivators

 ORTHO– , PARA– 12.5-65

DIRECTING ACTIVATORS
Increasing activation
●● ●● ●●
—NH2 —NHR —NR2

●●
—OH
●●
●● General
—OR structure: ●
●●
—R or —Z●
●●
—NHCOR
Alkyl groups or have
nonbonded electron pair
—R on the atom bonded to
benzene ring
 12.5-66

EXAMPLE:

CH2CH3 CH2CH3 CH2CH3

Br
Br2
+
FeBr3
(38 (62
ethylbenzene %) Br
%)
ORTHO– , PARA– 12.5-67

DIRECTING DEACTIVATORS

●● ●●
—F ●
● —Cl●
●
●● ●●

●● ●●
—Br●● — I●
●
●● ●●

General structure
●●
—X ●
● (halogens)
●●
 12.5-68

EXAMPLE:

Cl Cl Cl
NO2
HNO3
+
H2SO4
(35 (64
chlorobenzene %) %) NO2
 12.5-69
META– DIRECTING ACTIVATORS
—CHO

—COR
General
—COOR
structure:
—COOH —Y (δ + or δ –)

—CN
Have a full or partial
—SO3H positive charge on the
atom bonded to
—NO2 benzene ring
+
—NR3
Increasing deactivation
 12.5-69
EXAMPLE:

NO2
NO2
HNO3
H2SO4
NO2
nitrobenzene (93
%)
 12.5-70
INDUCTIVE EFFECT
Due to:
Electronegativity of the atoms in the
substituent.
Polarisability of the substituent.

EXAMPLE:

Cl CH3

Cl— CH3—
electron–withdrawing electron–donating
 12.5-71

Activating Groups
CH3
Release electrons to the ring NO2

Stabilise arenium ion +

Form faster

Deactivating Groups
Cl
Withdraw electrons from the ring NO2

Destabilise arenium ion +

Form slower
 12.5-72
EXAMPLE:
CF3 CH3

(trifluoromethyl)benzene benzene toluene

increasing rate of nitration

CF3 CH3
NO2 NO2
NO2

+ +
+

CF3 withdraws e-, CH3 releases e-,

 arenium ion less stable  arenium ion more stable
 ring less reactive  ring more reactive
 12.5-75
OXIDATION OF SIDE CHAIN

Reactants: arene with benzylic H.

Conditions:
Strong oxidizing agent such as KMnO4
and Na2Cr2O7.
Heat.

benzylic H

CH3

CH3 CH(CH3)2
 EXAMPLE: 12.5-76

CH3 COOH
KMnO4
heat
toluene benzoic acid

Na2Cr2O7
O2 N CH3 O2 N COOH
heat
p–nitrotoluene p–nitrobenzoic acid

KMnO4
CH3 CH(CH3)2 HOOC COOH
heat
isopropyl toluene terepththalic acid
 12.5-77

KMnO4
CH3 CH(CH3)2 HOOC COOH
heat

Alkyl group, regardless their chain length are

converted to –COOH.

Compounds without a benzylic H are inert to oxidation.

KMnO4
CH3 C(CH3)3 HOOC C(CH3)3
heat
 12.5-78
HALOGENATION OF TOLUENE

Free radical substitution reaction

Take place at high temperature or in the
presence of uv light.
Mechanism: free–radical substitution
Cl or Br replaces H atom of alkyl group

EXAMPLE: (dichloromethyl)benzene
CH3 CH2Cl CHCl2 CCl3
Cl2 Cl2 Cl2
heat or heat or heat or
light light light
toluene benzyl chloride (trichloromethyl)benzene
 HALOGENATION OF TOLUENE

Electrophilic aromatic substitution reaction

CH3
CH3
CH3
Br2 Br2 +
FeBr3

toluene Br2
 ●
CH2 12.5-79

benzylic
radical

Benzylic radicals are even more stable than 3o radicals!

 12.5-34
CARCINOGENIC EFFECT
CH3

benzene toluene

Many aromatic compounds are carcinorgenic

and toxic.

Example: benzene, benzo[a]pyrene.

 12.5-35

At one time, benzene was widely used as solvent.

Studies revealed benzene is carcinorgenic
(can cause cancer).
Replaced by toluene.
 12.5-36

benzo[a]pyrene

Benzo[a]pyrene is found in cigarette smoke, automobile

exhaust, and the fumes from charcoal grills.

When ingested or inhaled, it oxidised to carcinogenic

products.
12.5-21
 12.5-20

Benzoic acid, the simplest organic acid, prevent the

growth of many organism.
 12.5-22

widely used as a food preservative.

 12.5-19

Fresh wild berries

 END OF
SLIDE SHOW