Benzene and

Its Derivatives

Peppers of the Capsicum family

 What Is the Structure of Benzene?
• Because these hydrocarbons have pleasant
odors, they were called aromatic compounds

A more appropriate
definition of an aromatic
compound is any
compound that has one or
more benzene-like rings.
Arene
• A compound containing one or more benzene-
like ring

Aryl group
• A group derived from an arene by removal of
a H atom from an arene and given the symbol
Ar-
• Benzene, the simplest aromatic hydrocarbon, was
discovered in 1825 by Michael Faraday (1791–
1867).

• Benzene has the molecular formula C6H6, and a

compound with so few hydrogens for its six
carbons (compare hexane, C6H14,and cyclohexane
C6H12), chemists argued, should be unsaturated.
But benzene does not behave like an alkene (the
only class of unsaturated hydrocarbons known at
that time).
• Benzene is an important
compound in both the
chemical industry and the
laboratory, but it must be
handled carefully. Not only
is it poisonous if ingested
in liquid form, but its
vapor is also toxic and can
be absorbed either by
breathing or through the
skin. Long-term inhalation
can cause liver damage
and cancer.
 A. Kekulé’s Structure of Benzene
• The first structure for benzene was proposed by
Friedrich August Kekulé in 1872 and consisted of
a six-membered ring with alternating single and
double bonds, with one hydrogen bonded to
each carbon.
 B. Resonance Structure of Benzene
• The concept of resonance, developed by Linus
Pauling in the 1930s, provided the first
adequate description of the structure of
benzene.

Resonance hybrid
A molecule best described
as a composite of two or
more Lewis structures

• Each individual Lewis structure is called a

contributing structure or Kekule’ structure.
 How Do We Name
Aromatic Compounds?
• A. One Substituent

The IUPAC system also retains common names for the following
compounds:
• Phenyl group C6H5- the aryl group derived by
removing a hydrogen atom from benzene, the
common symbol for which is Ph-

B. Two Substituents
• When one of the two substituents on the ring imparts
a special name to the compound (for example, -CH3, -
OH, -NH2, or -COOH), we name the compound as a
derivative of that parent molecule and assume that the
substituent occupies ring position number 1.
 C. Three or More Substituents
• When three or more substituents are present on a
benzene ring, specify their locations by numbers. If one
of the substituents imparts a special name, then name
the molecule as a derivative of that parent molecule. If
none of the substituents imparts a special name, then
locate the substituents, number them to give the
smallest set of numbers, and list them in alphabetical
order before the ending “benzene.”
 Example: Naming Aromatic
Compounds
• Write names for these compounds.

Solution
(a) The parent is toluene, and the compound is
3-iodotoluene or m-iodotoluene.
(b) The parent is benzoic acid, and the compound is
3,5-dibromobenzoic acid.
(c) The parent is aniline, and the compound is
4-chloroaniline or p-chloroaniline.
 Problem 4.1
• Write names for these compounds.
 D. Polynuclear Aromatic Hydrocarbons
(PAH)
• A hydrocarbon containing two or more
benzene rings, each of which shares two
carbon atoms with another benzene ring

At one time, naphthalene was used as mothballs and an insecticide in

preserving woolens and furs, but its use decreased after the introduction of
chlorinated hydrocarbons such as p-dichlorobenzene.
 What Are the Characteristic Reactions
of Benzene and Its Derivatives?
• By far the most characteristic reaction of aromatic
compounds is substitution at a ring carbon, which we
give the name aromatic substitution. Groups we can
introduce directly on the ring include the halogens, the
nitro (-NO2) group, and the sulfonic acid (-SO3H) group.

A. Halogenation
 • B. Nitration

A particular value of nitration is that we can reduce the

resulting –NO2 group to a primary amino group, -NH2, by
catalytic reduction using hydrogen in the presence of a
transition-metal catalyst. In the following example, neither the
benzene ring nor the carboxyl group is affected by these
experimental conditions:
• C. Sulfonation

A major use of sulfonation is in the preparation

of synthetic detergents, an important example of
which is sodium 4-dodecybenzenesulfonate.
 What Are Phenols?
• A. Structure and Nomenclature
The functional group of a phenol is a hydroxyl group
bonded to a benzene ring. Substituted phenols are
named either as derivatives of phenol or by common
names.
Urushiol is the main
component of the
irritating oil of poison
ivy. It can cause severe
contact dermatitis in
sensitive individuals.
• B. Acidity of Phenols
Phenols are weak acids, with pKa values of
approximately 10. Most phenols are insoluble in
water, but they react with strong bases, such as NaOH
and KOH, to form water-soluble salts.

Most phenols are such weak acids that they do not react with
weak bases such as sodium bicarbonate; that is, they do not
dissolve in aqueous sodium bicarbonate.
C. Phenols as Antioxidants
• An important reaction for living systems,
foods, and other materials that contain
carbon–carbon double bonds is
autoxidation—that is, oxidation requiring
oxygen and no other reactant.
• Autoxidation is a radical-chain process that
converts an R-H group to an R-O-O-H group,
called a hydroperoxide.

• An atom or molecule with an unpaired

electron is called a radical.
 Mechanism of Autoxidation
Step 1: Chain Initiation—Formation of a Radical from a
Nonradical Compound

Step 2a: Chain Propagation—Reaction of a Radical to Form

a New Radical
Step 2b: Chain Propagation—Reaction of a Radical
to Form a New Radical

This cycle of propagation steps repeats over and over in a

chain reaction. Thus, once a radical is generated in Step 1,
the cycle of propagation steps repeats many thousands of
times and, in so doing, generates thousands of
hydroperoxide molecules. The number of times the cycle of
chain propagation steps repeats is called the chain length.
• Hydroperoxides themselves are unstable and,
under biological conditions, degrade to short-
chain aldehydes and carboxylic acids with
unpleasant “rancid” smells.

• Similar formation of hydroperoxides in the

low-density lipoproteins deposited on the
walls of arteries leads to cardiovascular
disease in humans. In addition, many effects
of aging are thought to result from the
formation and subsequent degradation of
hydroperoxides.
• Fortunately, nature has developed a series of
defenses against the formation of these and
other destructive hydroperoxides, including
the phenol vitamin E. This compound is one of
“nature’s scavengers.”
• Unfortunately, vitamin E is removed in the
processing of many foods and food products.
• To make up for this loss, phenols such as BHT
and BHA are added to foods to “retard
spoilage” (as they say on the packages) by
autoxidation.
• Likewise, similar compounds are added to
other materials, such as plastics and rubber, to
protect them against autoxidation.
 END OF
CHAPTER