AROMATIC COMPOUNDS

Aromaticity

hydrocarbons

aliphatic aromatic

alkanes alkenes alkynes

Aliphatic vs. Aromatic Compunds
 Aliphatic compounds: open-chain
compounds and ring compounds that are
chemically similar to open-chain compounds.
Alkanes, alkenes, alkynes, dienes, alicyclics,
etc.
 Aromatic compounds: unsaturated ring
compounds that are far more stable than they
should be and resist the addition reactions
typical of unsaturated aliphatic compounds.
Benzene and related compounds.
 Aromatic compounds
 Arene: A compound containing one or more
H benzene rings.
H C H
C C
C C
H C H Naphthalene Anthracene Phenanth
H
Aryl group:
ekulé structure A KekuléWhen we remove a
structure H atom from
an arene (Ar-).
wing all atoms as a line-angle formula

H
H C H
C C Phenyl C6H5-
C C
H C H
Common Aromatic Compounds
Aromatic hydrocarbons
 Simplest and most important member:
Benzene – C6H6.
 In the nineteenth century, many other compounds
having properties similar to those of benzene were
isolated from natural sources.

 Since these compounds possessed strong and

characteristic odors, they were called aromatic
compounds. It should be noted, however, that it is
their chemical properties, and not their odor, that
make them special.
History of benzene
 Since 1834, MF of benzene has been known
to be C6H6.

 A possible structure might be hexatetraene:

 This structure would have two possible

isomeric forms of C6H5Cl.
 Only one form of chlorobenzene has ever
been isolated.

 August Kekule proposed a ring structure in

1865:
◦ Called the Kekule or cyclohexatriene structure.
 AugustKekulé proposed that benzene was a
rapidly equilibrating mixture of two
compounds, each containing a six-
membered ring with three alternating 
bonds.

 In
the Kekulé description, the bond between
any two carbon atoms is sometimes a single
bond and sometimes a double bond.
Resonance Hybrid
H H
H C H H C H
Resonance: stable
C C C C
C C C C
H C H H C H
H H
 In
reality there is no equilibrium between the
two different kinds of benzene molecules.

 Current descriptions of benzene are based

on resonance and electron delocalization
due to orbital overlap.
 Any structure for benzene must account for
the following facts:

1. It contains a six-membered ring and three

additional degrees of unsaturation.

2. It is planar.

3. All C—C bond lengths are equal.

 The Kekulé structures satisfy the first two
criteria but not the third, because having
three alternating  bonds means that
benzene should have three short double
bonds alternating with three longer single
bonds.
 The resonance description of benzene
consists of two equivalent Lewis structures,
each with three double bonds that alternate
with three single bonds.

 Thetrue structure of benzene is a resonance

hybrid of the two Lewis structures, with the
dashed lines of the hybrid indicating the
position of the  bonds.
 We will use one of the two Lewis structures and not
the hybrid in drawing benzene. This will make it
easier to keep track of the electron pairs in the 
bonds (the  electrons).

 Because each  bond has two electrons, benzene

has six  electrons.
 In benzene, the actual bond length (1.39 Å) is
intermediate between the carbon—carbon
single bond (1.53 Å) and the carbon—carbon
double bond (1.34 Å).
18
Nomenclature of Benzene Derivatives
Monosubstituted derivatives
 Aromatic compounds are named:
◦ With benzene as the parent chain.
◦ Name of substituent comes in front of the
“benzene”.

methylbenzene chlorobenzene ethylbenzene

CH CH2 CH3
Cl CH=CHCHCH
CH -CH
CH33 CH=CHC
CH 3 2 CH3 CH3 2 3 22 2

Ethylbenzene Ethylbenzene
Toluene Toluene
Ethylbenzene Styrene
Styrene Tolu
 Nomenclature of Benzene Derivatives
Monosubstituted derivatives
Some substituted benzenes have common names. O
CH3
OH OCH OH NHOCH NH
3 2 3 C-H
2

Toluene
Phenol Phenol Aniline
Anisole AnisoleBenzaldehyde
Aniline Ben

O O
OH OCH3 NH2 C-H C-OH

enol Anisole Aniline Benzaldehyde Benzoic acid

21
 Nomenclature of Benzene Derivatives
Disubstituted derivatives
 When two groups are attached to benzene,
the ring is numbered to give the lower
numbers to the substituents.
◦ Start numbering from a special name (if we have).
◦ If we do not have, number them to get the
smallest set of numbers.
◦ List them by alphabetical order.
COOH CH3 CH2 CH3
4
1
2 Br 1
3
2

3 2
CH3 1
3-methyltoluene Cl
2-Bromobenzoic acid 1,3-Dimethylbenzene 1-Chloro-4-ethylbenzene
(o-Bromobenzoic acid) (m-Xylene) (p-Chloroethylbenzene)
Nomenclature of Benzene Derivatives
Disubstituted derivatives
 Relative positions on a benzene ring
◦ ortho- (o) on adjacent carbons (1,2)
◦ meta- (m) separated by one carbon (1,3)
◦ para- (p) separated by two carbons (1,4)
 Describes reaction patterns (“occurs at the para position”)

23
 Nomenclature of Benzene Derivatives
Polysubstituted derivatives
 If we have three or more substituents:
◦ Start numbering from a special name (if we have).
◦ If we do not have, number them to get the
smallest set of numbers.
◦ List them by alphabetical order.

CH3 OH NO2
1
2 NO2 Br 6
1
2 Br 4
3

2
3 5 3
4 4
1
Br
Cl Br CH2 CH3
4-Chloro-2- 2,4,6-Tribromophenol 2-Bromo-1-ethyl-4-
nitrotoluene nitrobenzene
Nomenclature of Benzene Derivatives
Polysubstituted derivatives

25
 Nomenclature of Benzene Derivatives
Phenyl Groups
 Aryl group: When we remove a H atom from
an arene (Ar-).
H
H C H
C C
Phenyl C6H5-
C C
H C H
H
Kekulé structure A Kekulé structure
owing all atoms as a line-angle formula
4 2
1 3 1
C6 H5
Phenyl group 1-Phenylcyclohexene 4-Phenyl-1-butene
Nomenclature of Benzene Derivatives
Phenyl Groups
 When a benzene ring is a substituent, the term
phenyl is used (for C6H5_)
◦ You may also see “Ph” or “f” in place of “C6H5”

 “Benzyl” refers to “C6H5CH2_”

27
Phenol
 Phenol is the name for benzene with a
OH
hydroxyl group. CH2 CH3

Phenol
Ethylbenzene
OH OH OH
OH OH OH OH OH
1
OH
1 NO2 OH
2

3 3 Cl OH
OH
Phenol 3-Chloro-2-nitrophenol
3-Methylphenol
Phenol 3-Methylphenol 1,2-Benzenediol 1,2-Benzenediol
1,3-Benzenediol 1,3-B
1,4-Benzenedio
(m-Cresol)
(m-Cresol) (Catechol) (m-Cresol)
(Resorcinol) (Catechol)
(Hydroquinone(R
Phenol
 Many are used as antiseptics and
disinfectants.
 Phenols are found widely in nature.

 Phenols are weak acids (pKa~10).

 Phenols are insoluble in water.

H2 O
OH + NaOH O- Na + + H2 O

Phenol Sodium phenoxide

(a water-soluble salt)
Chemical Properties of Benzene
 Benzene has four degrees of unsaturation,
making it a highly unsaturated hydrocarbon.

 Whereas unsaturated hydrocarbons such as

alkenes, alkynes and dienes readily undergo
addition reactions, benzene does not.
 Benzene does react with bromine, but only
in the presence of FeBr3 (a Lewis acid), and
the reaction is a substitution, not an
addition.

 Proposed structures of benzene must

account for its high degree of unsaturation
and its lack of reactivity towards
electrophilic addition.
Aromatic substitution
 One of the H atoms are replaced by some
groups:

 Halogenation
 Nitration
 Sulfonation
Halogenation
 Cl and Br react rapidly with benzene in the
presence of an iron catalyst.

Fe Cl3
H + Cl2 Cl + HCl

Benzene Chlorobenzene
Nitration
 In presence of concentrated nitric acid and
sulfuric acid, one of the H atoms is replaced
by a nitro (-NO2) group.

H2 S O4
H + HNO3 NO2 + H2 O

Nitrobenzene
Sulfonation
 In presence of concentrated sulfuric acid
and heat, one of the H atoms is replaced by
sufonic acid (-SO3H) group.

Heat
H + H2 S O4 SO3 H + H2 O

Benzenesulfonic acid
 Effects of substituents on the benzene ring

 Substituents on the benzene ring affect:

1. The reactivity of the electrophilic substitutions.

2. The orientation in electrophilic substitutions.

The reactivity of the electrophilic
substitutions
 Groups that make the benzene ring more
reactive are called activating groups.
◦ OH, R, NH2

 Those that make the ring less reactive are

called deactivating groups.
◦ X, COOH, NO2, SO3H.
The orientation in electrophilic
substitutions
 These groups influence the orientation of
attack by an incoming electrophile. They are
of two types:

1. The ortho-para (o-p) directors e.g. OH, NH 2, X, R.

2. The meta (m) directors e.g. COOH, NO 2, SO3H.

 The Criteria for Aromaticity
Hückel’s Rule
 Four structural criteria must be satisfied for a
compound to be aromatic.
1. A molecule must be cyclic.

2. A molecule must be planar.

3. A molecule must be completely conjugated.

4. A molecule must satisfy Hückel’s rule, and

contain a particular number of  electrons.
Range and scope of aromatic
chemistry
 Pharmaceutical compounds, e.g. Morphine

 Herbicides, e.g. Diuron

 Detergents, e.g. Sodium

dodecylbenzenesulfonate

 Dyes, e.g. Martius Yellow

Aromatic compounds and cancer
 Some aromatic compounds are carcinogenic,
e.g. Benzene

 However, not all aromatic compounds are

carcinogenic; aspirin is an example
Reactions of Aromatic
Compounds
Electrophilic Aromatic Substitution
Electrophile substitutes for a hydrogen on
the benzene ring.

E
E
H E
H :base
+ H-base

43
Mechanism

=>
44
EAS Reactions of Benzene
NO 2

CHO Cl

O
CR Br

R I

SO 3H
Bromination / Chlorination

H Br
Br2, FeBr3
+ HBr

H Cl
Cl2, FeCl3
+ HCl
 Bromination of Benzene
 Requires a stronger electrophile than Br2.
 Use a strong Lewis acid catalyst, FeBr3.
Br Br FeBr3 Br Br FeBr3
H
H H
H
H H _
Br
Br Br FeBr3 + + FeBr4
H H
H H
H
H

Br
+ HBr

47
Bromination Mechanism
Nitration

NO2
HNO3, H2SO4
+ H 2O

Formation of electrophile
+ -
HNO3 + H2SO4 NO2 + H2O + HSO4
Nitration Mechanism
Nitration of Toluene
Chlorination
and Iodination

 Chlorination is similar to bromination. Use

AlCl3 as the Lewis acid catalyst.
 Iodination requires an acidic oxidizing
agent, like nitric acid, which oxidizes the
iodine to an iodonium ion.

+ +
H + HNO3 + 1/2 I2 I + NO2 + H2O

=>

Chapter 17 52
Nitration of Benzene
Use sulfuric acid with nitric acid to form
the nitronium ion electrophile.

O O H O
_
H O S O H H O N H O N + HSO4
+
O O O

H O O NO2+ then forms a

H O N H2O + N+ sigma complex with
+ benzene, loses H+ to
O O form nitrobenzene. =>

Chapter 17 53
 Nitration of Toluene
 Toluene reacts 25 times faster than benzene.
The methyl group is an activator.
 The product mix contains mostly ortho and para

substituted molecules.

=>

Chapter 17 54
The Amino Group

Aniline reacts with bromine water (without a

catalyst) to yield the tribromide. Sodium
bicarbonate is added to neutralize the HBr
that’s also formed.

NH2
NH2
Br Br
3 Br2
H2O, NaHCO3
Br =>

Chapter 17 55
Summary of
Activators

=>
56
Chapter 17
Deactivating Meta-
Directing Substituents
 Electrophilic substitution reactions for
nitrobenzene are 100,000 times slower
than for benzene.
 The product mix contains mostly the meta
isomer, only small amounts of the ortho
and para isomers.
 Meta-directors deactivate all positions on
the ring, but the meta position is less
deactivated.
=>

Chapter 17 57
Halobenzenes
 Halogens are deactivating toward
electrophilic substitution, but are ortho,
para-directing!
 Since halogens are very electronegative, they

withdraw electron density from the ring

inductively along the sigma bond.
 But halogens have lone pairs of electrons

that can stabilize the sigma complex by

resonance. =>

Chapter 17 58
Summary of
Directing Effects

=>
Chapter 17 59
Friedel-Crafts Alkylation

 Synthesis of alkyl benzenes from alkyl

halides and a Lewis acid, usually AlCl3.

 Reactions of alkyl halide with Lewis acid

produces a carbocation which is the
electrophile.

=>

Chapter 17 60
Limitations of
Friedel-Crafts
 Reaction fails if benzene has a substituent
that is more deactivating than halogen.

 Carbocations rearrange. Reaction of benzene

with n-propyl chloride and AlCl3 produces
isopropylbenzene.

 The alkylbenzene product is more reactive

than benzene, so polyalkylation occurs.
=>

Chapter 17 61
Friedel-Crafts
Acylation
 Acyl chloride is used in place of alkyl
chloride.

 The acylium ion intermediate is resonance

stabilized and does not rearrange like a
carbocation.

 The product is a phenyl ketone that is less

reactive than benzene.
=>

Chapter 17 62
 Catalytic Hydrogenation
 Elevated heat and pressure is required.
 Possible catalysts: Pt, Pd, Ni, Ru, Rh.
 Reduction cannot be stopped at an

intermediate stage.

CH3 CH3

3 H2, 1000 psi

Ru, 100°C =>
CH3 CH3

Chapter 17 63
Side-Chain Oxidation
Alkylbenzenes are oxidized to benzoic acid
by hot KMnO4 or Na2Cr2O7/H2SO4.

_
CH(CH3)2 COO
-
KMnO4, OH
_
H2O, heat COO
CH CH2

=>
Chapter 17 64
2) Oxidation of Alkyl Substituents
O
CH3 COH
KMnO4, H2O

CO2H
KMnO4
H2O

CH3 CO2H
KMnO4, H2O

CH(CH3)2 CO 2H
 Side-Chain Halogenation
 Benzylic position is the most reactive.

 Chlorination is not as selective as

bromination, results in mixtures.

 Br2 reacts only at the benzylic position.

Br
CH2CH2CH3 CHCH2CH3
Br2, h

=>
Chapter 17 66
Friedel-Crafts Acylation

O
O C
RCCl, AlCl3 R
+ HCl
 An Acylation

CH3 CH3 O
O
CH3CH2CH2CH2CCl CCH2CH2CH2CH3

TiCl 4 in CH2Cl2 + HCl

CH3 CH3
Friedel-Crafts Alkylation
many more limitations

R
RX, AlCl3
+ HCl
Benzylic Bromination with NBS
benzylic hydrogen
H Br

NBS, CCl4, h

NBS NBr

O
Reduction of Nitro Groups

NO2 1) SnCl2, HCl NH2

2) NaOH
or H2 on Pt
Reactions of Rings With
Two or More Substituents

Activating Group Controls Reaction

OCH3 OCH3
Cl
Cl2, FeCl3

NO2 NO2
Mixtures with Conflicting Directing
Effects