AROMATIC SUBSTITUTION

REACTIONS
NOMENCLATURE
 Learn Nomeclature Either on Your Own
or Use the Organic Nomeclature Software

CH3 Br
methylbenzene 1-bromo-3-nitrobenzene
(toluene)
NO2

CH3
CH3
1-chloro-3-methylbenzene

Cl
CH3

1,4-dimethylbenzene
 SOME SPECIAL NAMES
CH3 NH2 O CH3 OH

toluene aniline anisole phenol

CH3 CH3 CH3 COOH

CH3

CH3

o-xylene m-xylene CH3

benzoic
acid
p-xylene
 ortho, meta and para Positions
CH3

m-nitrotoluene
R ipso NO2
3-nitrotoluene

1
o- 6 2 ortho
1-methyl-3-nitrobenzene

meta Cl
m-
5 3
4
para p-dichlorobenzene
p-
1,4-dichlorobenzene
Cl
REVIEW OF BENZENE PROPERTIES
 BENZENE RESONANCE
Review Sections 6.8 - 6.14

KEKULE
STRUCTURES

Resonance Energy = 36 Kcal / mole

All bonds are equivalent

The ring is symmetric.
Bond lengths are between a single and a double bond.
Very Stable
Less reactive than other groupings of atoms.
 H . . H
. .
H . . H

H H

All 2p orbitals overlap equally.

 BENZENE
Isodensity surfaces - electron potential mapped in color.
(van der Waal’s)

Highest Color adjusted

electron density to enhance the
is red. pi system.

Note the symmetry.

BENZENE - DETERMINATION OF RESONANCE ENERGY
cyclohexatriene
(hypothetical)

+ 3 H2

benzene

RESONANCE
cyclohexene + 3 H2 ENERGY
36 kcal/mol
+ H2
-49.8 kcal/mol
-85.8 kcal/mol
(calculated)
-28.6 kcal/mol

cyclohexane
REACTIVITY
 The “Double Bonds” in a Benzene Ring Do Not React Like Others

Alkene Benzene

R R Cl no
+ HCl + HCl reaction
H

R R Cl no
+ Cl2 + Cl2 reaction
Cl

R R Br no
+ Br2 + Br2 reaction
Br

R R O
no
+ RCO3H + RCO3H reaction
 Benzene is a Weak Base and Poor Nucleophile

Stronger + Readily donates electrons

base H to an electrophile.

alkene

Weaker + Donation of electrons would

base
H interrupt ring resonance
(36 kcal / mole).

A strong electrophile is
benzene required - and often a
catalyst.
 Benzene Reactivity
Benzene requires a strong electrophile and a catalyst
…..and then it undergoes substitution reactions, not addition.

Cl
FeCl3
+ Cl2 + HCl

catalyst
substitution
compare:

Cl
+ Cl2
Cl
no catalyst
addition
 Some Substitution Reactions of Benzene
Cl
AlCl3
Halogenation + Cl2

CH3
AlCl3
Friedel-Crafts + CH3Cl
Alkylation O
O AlCl3 C CH
3
Friedel-Crafts + CH C Cl
Acylation 3
O
N O
O H2SO4
Nitration
+ + -
+ HO N
O O
-
O S OH
Sulfonation SO3
O
+ HO S OH
O
 MECHANISM
All of the reactions follow the same pattern of mechanism.

The reagents combine to form a strong electrophile E+ ,and

its partner (:X ), which react as follows:

ELECTROPHILIC AROMATIC SUBSTITUTION

(+) E
H E
E+ H + HX
slow (+) +
:X
intermediate
benzenium ion* restores
ring resonance
resonance structures are shown
by the (+) symbols

* also called a benzenonium ion

ENERGY PROFILE FOR AROMATIC SUBSTITUTION
(+) E
Transition benzenium
H
state 1 + intermediate
(+)

Transition
state 2

intermediate

Ea
activation
H energy
E
E+ +
H

slow fast
STEP 1 STEP 2
HALOGENATION
 Formation of the Chloronium Ion Complex

.. ..
: Cl : : Cl :
.. .. .. ..d+ .. d- ..
: Cl
..
Cl :
.. Al Cl : : Cl Cl Al Cl :
.. .. .. ..
: Cl : : Cl :
.. ..

Cl sp2 ..
: Cl :
Al Cl .. + .. - ..
: Cl : Cl
..
Al Cl :
..
..
: Cl
..
:
Cl
chloronium
ion complex
Chlorination of Benzene
-
AlCl4
H
Cl2 + AlCl3
Cl
+ - +
[ Cl AlCl4 ]
benzenium
ion

chloronium
ion complex Cl
+ HAlCl4

HCl + AlCl3
FRIEDEL-CRAFTS REACTIONS
FRIEDEL-CRAFTS ALKYLATION
 Formation of a Carbocation Complex

.. ..
: Cl : d+ : Cl :
.. .. .. d- ..
CH3 Cl : Al Cl: CH3 Cl Al Cl :
.. .. .. ..
: Cl : : Cl :
.. ..

Other aliphatic
R-Cl may be used ..
: Cl :
+ .. - ..
CH3 : Cl Al Cl :
.. ..
: Cl
..
:
carbocation
Friedel-Crafts Alkylation
-
AlCl4
H
CH3Cl + AlCl3
CH3
[ CH+3 AlCl4- ] +

CH3
+ HAlCl4

HCl + AlCl3
REARRANGEMENTS ARE COMMON IN
FRIEDEL-CRAFTS ALKYLATION

AlCl3 + -
CH3CH2CH2 Cl CH3CH2CH2 Cl AlCl3

H3C + -
CH Cl AlCl3
H3C
carbocation rearrangement

CH3

AlCl3 CH
+ CH3CH2CH2 Cl CH3
FRIEDEL-CRAFTS ACYLATION
 Formation of an Acylonium Complex

O .. ..
: Cl : O : Cl :
.. .. d+ .. d- ..
CH3 C Cl : Al Cl : CH3 C Cl Al Cl :
.. .. .. ..
: Cl : : Cl :
.. ..

Other acid chlorides ..

(RCOCl) may be used O : Cl :
.. - ..
CH3 C : Cl
..
Al Cl :
..
+
: Cl
..
:
acylium ion
(acylonium ion)

Rearrangements DO NOT occur

Friedel-Crafts Acylation
-
AlCl4
O H
CH3 C Cl + AlCl
3
C CH3
AlCl4- ]
+
[ CH3 C +
O
O

C CH3
O
+ HAlCl4

HCl + AlCl3
LINEAR CHAINS ARE MADE VIA ACYLATION
(no rearrangement) AND REMOVAL OF C=O

AlCl3 C CH2CH3
CH3CH2 C Cl O
O
Zn / HCl
Clemmensen
CH3CH2CH2Cl
X CH2 CH2CH3
AlCl3
doesn’t work
- rearranges
NITRATION
 Formation of Nitronium Ion

.. .. ..
O: O: O:
.. + H2SO4 .. + + ..
H O N H O N H O: N+
..
: O: H :O: H O:
.. - .. - ..
nitronium ion

..
:O
Powerful
N+ Electrophile

Reacts with benzene.

:O
..
Nitration of Benzene
H

H :O.. H
..
:O HNO3 + ..
N O:
N+ +
H2SO4 :O
..: -
: O..

..
:O
N ..
.. :
+ O
-
SULFONATION
 Fuming Sulfuric Acid
H2SO4 . SO3

.. ..
O: H2SO4 O:
.. - ..
+ S O: +S O H
.. ..
O: O:
.. ..
sulfur
trioxide
Sulfonation of Benzene
-
HSO4
H
O
H2SO4 . SO3
O
S OH
+S OH O
O

H3O+
can be D O
reversed
in boiling water S OH
or steam (acidic) O
+ H2SO4
REMOVAL OF THE SULFONATE GROUP

O O H O
S OH H S O-
+
O O H O H
heat or steam
H
excess H2O

H
H O
O
S O -
+S O-
O
O

H2O

H2SO4
Benzoic Acid Syntheses
Synthesis of Benzoic Acids and Benzoate Esters

CH3 COOH COOCH3

CH3Cl
AlCl3 KMnO4 CH3OH

1 Li
2 CO2
Br2 +
Br 3 H3O
AlBr3
 AROMATIC ?

WHERE DID THE TERM

ORIGINALLY COME FROM ?
 A LOT OF NICE-SMELLING COMPOUNDS
(SPICES IN PARTICULAR) HAVE BENZENE RINGS
CHO HC CH CHO thymol
anisaldehyde (thyme)
cinnamaldehyde
(anise)
(cinnamon)
OH

OMe OH CHO
OMe
eugenol cuminaldehyde
(cloves) (cumin)
CH2 CH CH2

Hence, compounds having benzene rings eventually came

to be know as “AROMATIC COMPOUNDS.

Today chemists have a different definition of “AROMATIC”

which we will discuss later in the chapter.