AROMATIC SUBSTITUTION REACTIONS

NOMENCLATURE

Learn Nomeclature Either on Your Own or Use the Organic Nomeclature Software
CH3
methylbenzene (toluene)
Br

1-bromo-3-nitrobenzene
NO2

CH3

CH3
1-chloro-3-methylbenzene

Cl

CH3
1,4-dimethylbenzene

SOME SPECIAL NAMES

CH3 NH2
O CH3

OH

toluene

aniline
CH3

anisole

phenol

CH3 CH3

CH3

COOH

CH3

o-xylene

m-xylene

CH3

p-xylene

benzoic acid

ortho, meta and para Positions

CH3

m-nitrotoluene

R
o1 6 2

ipso ortho meta

3-nitrotoluene
NO2

1-methyl-3-nitrobenzene

m-

Cl

5 4

p-

para
Cl

p-dichlorobenzene
1,4-dichlorobenzene

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

All 2p orbitals overlap equally.

BENZENE
Isodensity surfaces - electron potential mapped in color. (van der Waals)

Highest electron density is red. Note the symmetry.

Color adjusted to enhance the pi system.

BENZENE - DETERMINATION OF RESONANCE ENERGY

cyclohexatriene
(hypothetical)

+ 3H2

benzene cyclohexene
+ H2
+ 3H2

RESONANCE ENERGY 36 kcal/mol

-49.8 kcal/mol -28.6 kcal/mol -85.8 kcal/mol (calculated)

cyclohexane

REACTIVITY

The Double Bonds in a Benzene Ring Do Not React Like Others Alkene
R R Cl

Benzene no reaction no reaction

+ HCl
H

+ HCl
R Cl

Cl2 Cl

+ Cl2
R Br

Br2 Br

Br2

no reaction

+ RCO3H

+ RCO3H

no reaction

Benzene is a Weak Base and Poor Nucleophile

Stronger base alkene

Readily donates electrons to an electrophile.

Weaker base

H
benzene

Donation of electrons would interrupt ring resonance (36 kcal / mole). A strong electrophile is required - and often a catalyst.

Benzene Reactivity
Benzene requires a strong electrophile and a catalyst ..and then it undergoes substitution reactions, not addition.

Cl
+

Cl2

FeCl3
catalyst

+ HCl
substitution

compare:

Cl2
no catalyst

Cl Cl
addition

Reaksi substitusi Nukleofilik

Reaksi Sandmeyer

Substitusi Langsung Pada cincin Aromatik Teraktivasi

Zat Antara Benzine

O N C H C C H C F

NO2 group to reduce electron density in the system

H C C H

area of low electron density F atom to act as a leaving group

4-fluoronitrobenzene

Example 1-

NO2 C

NO2

HC HC C F

CH CH

..O CH3 /CH 3 OH .. ..F ..

C HC HC C OCH 3 CH CH

reactants tetrahedral intermediate products Draw all possible resonance structures for the intermediate Meisenheimer complex formed in Example 1.

Comparison of leaving group reactivities (in polar protic solvents) Nucleophilic aliphatic substitution F- < Cl- < Br- < INucleophilic aromatic substitution F- > Cl- < Br- > I-

..

.. ..

Some Substitution Reactions of Benzene

Halogenation + Cl2
AlCl3 Cl

Friedel-Crafts Alkylation

+ CH3Cl
O

AlCl3

CH3 O

Friedel-Crafts Acylation
Nitration

AlCl3

+ CH C Cl 3 +
O OH2SO4

C CH 3 O

+ HO N
O

N O O

S OH SO3 O

Sulfonation

+ 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

H E+
slow

(+) E (+) +

E H
:X

+ HX

intermediate benzenium ion* resonance structures are shown by the (+) symbols

restores ring resonance

* also called a benzenonium ion

ENERGY PROFILE FOR AROMATIC SUBSTITUTION

(+) E Transition state 1 (+) +
H

benzenium intermediate

Transition state 2
intermediate Ea activation energy
E+

H slow STEP 1 fast STEP 2

HALOGENATION

Formation of the Chloronium Ion Complex

..

.. .. Cl : ..
..d+ .. Cl : Cl .. .. : Cl : .. dAl Cl : .. : Cl : ..

.. : Cl ..

.. Cl : ..

: Cl :
Al

: Cl : ..

Cl Al Cl

sp2

Cl
chloronium ion complex

:Cl : .. .. + .. Al Cl : :Cl :Cl .. .. .. : :Cl ..

..

Chlorination of Benzene
H AlCl4 Cl

Cl2 + AlCl3

+ [ Cl AlCl4 ]

benzenium ion

chloronium ion complex

Cl

+ HAlCl4
HCl + AlCl3

FRIEDEL-CRAFTS REACTIONS

FRIEDEL-CRAFTS ALKYLATION

Formation of a Carbocation Complex

..

.. .. Cl: ..
d+
CH3

.. CH3 Cl : ..

: Cl :
Al

: Cl : ..
Other aliphatic R-Cl may be used

: Cl : .. d.. Cl Al Cl : .. .. : Cl : ..

carbocation

: Cl : .. .. + CH3 : Cl Al Cl : .. .. : : Cl ..

..

Friedel-Crafts Alkylation
H AlCl4 CH3

CH3Cl + AlCl3

-] [ CH+ AlCl 3 4

CH3

+ HAlCl4
HCl + AlCl3

REARRANGEMENTS ARE COMMON IN FRIEDEL-CRAFTS ALKYLATION

AlCl3
+

CH3CH2CH2

Cl

CH3CH2CH2 Cl H3C H3C

+

AlCl3
-

CH

Cl

AlCl3

carbocation rearrangement
CH3
+ CH3CH2CH2

Cl

AlCl3

CH CH3

FRIEDEL-CRAFTS ACYLATION

Formation of an Acylonium Complex

O CH3 C

.. Cl : ..

: Cl :
Al

..

.. .. Cl : ..
CH3 C

d+

: Cl : ..

: Cl : .. d.. Cl Al Cl : .. .. : Cl : ..

Other acid chlorides (RCOCl) may be used

O CH3 C
+

acylium ion
(acylonium ion)

: Cl : .. .. Al Cl : : Cl .. .. : : Cl ..

..

Rearrangements DO NOT occur

Friedel-Crafts Acylation
O CH3 C Cl + AlCl 3

AlCl4 C CH3 O

+ -] [ CH3 C AlCl4
O

C CH3 O

+ HAlCl4 HCl + AlCl3

LINEAR CHAINS ARE MADE VIA ACYLATION (no rearrangement) AND REMOVAL OF C=O
AlCl3 CH3CH2 C Cl O Zn / HCl CH3CH2CH2Cl AlCl3
Clemmensen

C CH2CH3 O

CH2 CH2CH3

doesnt work - rearranges

NITRATION

Formation of Nitronium Ion

.. + H2SO4 H O N .. : O: .. .. O: : ..+ + O H O N O: H : .. .. ..
H O: H

..

O: N+ O

.. :
nitronium ion

:O
N+
Powerful Electrophile
Reacts with benzene.

..

: .. O

Nitration of Benzene
H

:O

..

HNO3 H2SO4

N+

:O .. H + .. N O: + :O ..:
H

:O .. :O ..
-

N .. + O .. :

SULFONATION

Fuming Sulfuric Acid

H2SO4. SO3

sulfur trioxide

.. + S O: .. O: ..

O:

..

H2SO4

.. +S O H .. O: ..

O:

..

Sulfonation of Benzene
HSO4 O
+S H2SO4. SO3

O S OH O

OH

O
H3O+ D

can be reversed in boiling water or steam (acidic)

O S OH O
+ H2SO4

REMOVAL OF THE SULFONATE GROUP

O S OH O O H H
heat or steam

S O+ H O H O H

excess H2O
H H O O S O O

+S
O

O-

H2O H2SO4

Benzoic Acid Syntheses

Synthesis of Benzoic Acids and Benzoate Esters

CH3Cl AlCl3

CH3
KMnO4

COOH
CH3OH

COOCH3

Br2 AlBr3

Br

1 Li 2 CO2 3 H3O+

AROMATIC ?
WHERE DID THE TERM ORIGINALLY COME FROM ?

A LOT OF NICE-SMELLING COMPOUNDS (SPICES IN PARTICULAR) HAVE BENZENE RINGS

CHO
anisaldehyde (anise)

HC CH CHO
cinnamaldehyde (cinnamon)

thymol (thyme)

OH

OMe

OH OMe
eugenol (cloves)

CHO
cuminaldehyde (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.