Benzene and

Aromatic
Compounds
 Discovery of Benzene
• Benzene was isolated in 1825 by Michael Faraday, who
determined C:H ratio to be 1:1. He named it “bicarburet
of hydrogen.”
• It was synthesized in 1834 by Eilhard Mitscherlich, who
determined its molecular formula to be C6H6. He named
it benzin.
• Other related compounds with low C:H ratios had a
pleasant smell, so they were classified as aromatic
 Kekulé Structure
This structure was
proposed in 1866 by
Friedrich Kekulé, shortly
after multiple bonds were
suggested.
It failed to explain
the existence of
only one isomer of
1,2-dichlorobenzene.
 Resonance Structures of Benzene

Benzene is actually a resonance hybrid between the two Kekulé structures.

The C—C bond lengths in benzene are shorter than typical single-bond lengths,
yet longer than typical double-bond lengths (bond order 1.5).
Benzene’s resonance can be represented by drawing a circle inside the six-
membered ring as a combined representation.
There are delocalized electrons above and
below the plane of the ring, which
makes benzene particularly stable

Chapter 15 5
Common Names of
Benzene Derivatives
 Disubstituted Benzenes

• Numbers can also be used to identify the

relationship between the groups; ortho- is 1,2-
disubstituted, meta- is 1,3, and para- is 1,4.
 Three or More Substituents
Use the smallest possible numbers, but
the carbon with a functional group is number 1.
 Common Names for
Disubstituted Benzenes
 Phenyl and Benzyl

Phenyl indicates the benzene ring attachment. The

benzyl group has an additional carbon.
Electrophilic Aromatic Substitution
Arene (Ar-H) is the generic term for an aromatic
hydrocarbon
The aryl group (Ar) is derived by removal of a
hydrogen atom from an arene
Benzene compounds undergo electrophilic
aromatic substitution
The electrophile has a full or partial positive
charge

Chapter 15 11
Chapter 15 12
•A General Mechanism for Electrophilic
Aromatic Substitution: Arenium Ion
Intermediates
• Benzene reacts with an electrophile using two of its p electrons
• Electrophile must be generated first before reaction occur.

Chapter 15 13
• Nitration
HO-NO2 + H2SO4 HSO4 + HH2O-NO2 NO2 + H2O
H

• Sulfonation

SO3 + H2SO4 SO3H + HSO4-

• Alkylation

R H + AlCl3 R + AlCl4

Chapter 15 14
 Acylation

O
O
R C Cl + AlCl3 R C

Halogenation

FeBr3 Br Br FeBr3 Br + FeBr4

Br Br

Chapter 15 15
In step 1 of the mechanism, the electrophile reacts with two p
electrons from the aromatic ring to form an arenium ion

The arenium ion is stabilized by resonance which delocalizes the

charge

In step 2, a proton is removed and the aromatic system is

regenerated

Chapter 15 16
•Halogenation of Benzene
• Halogenation of benzene requires the presence of a Lewis acid

Chapter 15 17
 Nitration of Benzene

• Sulfuric acid acts as a catalyst, allowing the reaction to be

faster and at lower temperatures.
• HNO3 and H2SO4 react together to form the electrophile of
the reaction: nitronium ion (NO2+).
 Reduction of the Nitro Group

• Treatment with zinc, tin, or iron in dilute

acid will reduce the nitro to an amino group.
• This is the best method for adding an amino
group to the ring.
•Friedel-Crafts Alkylation
• An aromatic ring can be alkylated by an alkyl halide in
the presence of a Lewis acid
• The Lewis acid serves to generate a carbocation electrophile

Chapter 15 20
 Sulfonation of Benzene

• Sulfur trioxide (SO3) is the electrophile in the

reaction.
• A 7% mixture of SO3 and H2SO4 is commonly referred
to as “fuming sulfuric acid.”
• The —SO3H group is called a sulfonic acid.
 Desulfonation Reaction

• Sulfonation is reversible.
• The sulfonic acid group may be removed from an
aromatic ring by heating in dilute sulfuric acid.
•Friedel-Crafts Acylation
• An acyl group has a carbonyl attached to some R group

• Friedel-Crafts acylation requires reaction of an acid

chloride or acid anhydride with a Lewis acid such as
aluminium chloride

Chapter 15 23
Chapter 15 24
•Synthetic Applications of Friedel-Crafts
Acylations: The Clemmensen Reduction
• Primary alkyl halides often yield rearranged
products in Friedel-Crafts alkylation which is a
major limitation of this reaction
• Unbranched alkylbenzenes can be obtained in
good yield by acylation followed by Clemmensen
reduction
• Clemmensen reduction reduces phenyl ketones to the
methylene (CH2) group

Chapter 15 25
Chapter 15 26
• This method can be used to add a ring to an aromatic ring
starting with a cyclic anhydride
• Note that the Clemmensen reagents do not reduce the carboxylic
acid

Chapter 15 27
 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.
29
•Effects of Substituents on Reactivity
and Orientation
•The nature of groups already on an
aromatic ring affect both the reactivity and
orientation of future substitution
•Alkyl groups and heteroatom with one or
more unshared electron pairs directly
bonded to the aromatic ring will be ortho-
para directors

Chapter 15 30
•Classification of Substitutents

Chapter 15 31
Example of ortho para directors

Chapter 15 32
 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.
 Alkyl Group Stabilization

• Alkyl groups are activating substituents and ortho,

para-directors.
• This effect is called the inductive effect because alkyl
groups can donate electron density to the ring through the
sigma bond, making them more active.
 Anisole

• Anisole undergoes nitration about 10,000 times faster than

benzene and about 400 times faster than toluene.
• This result seems curious because oxygen is a strongly
electronegative group, yet it donates electron density to
stabilize the transition state and the sigma complex.
Example of meta directors

Chapter 15 36
 Nitration of Nitrobenzene

• Electrophilic substitution reactions for nitrobenzene are

100,000 times slower than for benzene.
• The product mix contains mostly the meta isomer and
only small amounts of the ortho and para isomers.
•Theory of Substituent Effects on
Electrophilic Substitution
•Reactivity: The Effect of Electron-Releasing
and Electron-Withdrawing Groups
• Electron-releasing groups activate the ring
toward further reaction
• Electron-withdrawing groups deactivate the
ring toward further reaction

Chapter 15 38
39
•Meta-directing Groups
• All meta-directing groups have either a partial
or full positive charge on the atom directly
attached to the aromatic ring
• The trifluoromethyl group destabilizes the
arenium ion intermediate in ortho and para
substitution pathways
• The arenium ion resulting from meta substitution is
not so destabilized and therefore meta substitution
is favored

40
41
• Ortho-Para Directing Groups
• Many ortho-para directors are groups that have a lone
pair of electrons on the atom directly attached to the ring

Chapter 15 42
Chapter 15 43
• Halo groups are ortho-para directors but are also
deactivating
• The electron-withdrawing inductive effect of the halide is the
primary influence that deactivates haloaromatic compounds
toward electrophilic aromatic substitution
• The electron-donating resonance effect of the halogen’s unshared
electron pairs is the primary ortho-para directing influence

Chapter 15 44
Chapter 15 45
• Ortho-Para Direction and Reactivity of Alkylbenzenes
• Alkyl groups activate aromatic rings by inductively stabilizing the
transition state leading to the arenium ion
• Alkyl groups are ortho-para directors because they inductively
stabilize one of the resonance forms of the arenium ion in ortho
and para substitution

Chapter 15 46
• Reactions of the Side Chain of Alkylbenzenes
• Benzylic Radicals and Cations
• When toluene undergoes hydrogen abstraction from its methyl group
it produces a benzyl radical
• A benzylic radical is a radical in which the carbon bearing the unpaired
electron is directly bonded to an aromatic ring

• Departure of a leaving group by an SN1 process from a benzylic

position leads to formation of a benzylic cation

Chapter 15 47
• Halogenation of the Side Chain: Benzylic Radicals
• Benzylic halogenation takes place under conditions which favor
radical reactions
• Reaction of N-bromosuccinamide with toluene in the presence of
light leads to allylic bromination
• Recall N-bromosuccinamide produces a low concentration of bromine
which favors radical reaction

• Reaction of toluene with excess chlorine can produce multiple benzylic

chlorinations

Chapter 15 48
• Oxidation of the Side Chain
• Alkyl and unsaturated side chains of aromatic rings can be
oxidized to the carboxylic acid using hot KMnO4

49
•Synthetic Applications
• When designing a synthesis of substituted benzenes, the
order in which the substituents are introduced is crucial
• Example: Synthesize ortho-, meta-, and para-nitrobenzoic
acid from toluene

50
51
52
•Orientation in Disubstituted Benzenes
•When two substituents are present on the
ring initially, the more powerful activating
group generally determines the orientation
of subsequent substitution
• Ortho-para directors determine orientation
over meta directors
• Substitution does not occur between meta
substituents due to steric hindrance

Chapter 15 53
Chapter 15 54