Aromatic Hydrocarbons

• Aromatic hydrocarbons are one of the

three classes of compounds found in
petroleum.
• They are less abundant than
the alkanes and cycloalkanes, amounting
to only a few percent of the total, but they
are quite important commercially.
• Most aromatic hydrocarbons contain
a benzene ring
• The benzene ring is usually indicated by
• In the latter structure the lines represent
C—C bonds, but carbon and hydrogen
atoms, as well as C—H bonds, have been
omitted.
• The benzene ring is very stable, surviving
unchanged in most chemical reactions.
• It is very different in reactivity and shape
from the puckered six-membered rings
found in cycloalkanes. Below are.
 3D models of both cyclohexane and
benzene

Figure 8.8.18.8.1: Examples of aromatic hydrocarbons found in crude oil

• Note that the three xylenes are also
isomers.
• Compounds containing two benzene rings
joined together, such as naphthalene, are
also found in crude oil, though they are
much rarer than benzene-related
compounds.
• Aromatic hydrocarbons are much more common in coal
than in petroleum, though in the United States they are
mostly manufactured from the latter.
• In addition to their use in motor fuel, they may be made
into dyes, plastics, explosives, detergents, insecticides,
medicines, and many other products.
• In 2000, a total of 6.74 × 1012 liters of benzene were
produced in the US, after compensation for exportation and
importation.
• Some aromatic compounds, benzene among
them, are toxic. The compound 1,2-
benzopyrene was the cause of the first
demonstrated case of occupational disease.
• During the eighteenth century chimney
sweeps in London were found to have
extremely high rates of skin cancer relative to
the average person. This was eventually traced
to the carcinogenic (cancer-causing)
properties of 1,2-benzopyrene in the soot
which coated the insides of the chimneys they
cleaned.
• Small quantities of the compound were
produced by inefficient combustion of coal in
the fireplaces used to heat London houses.
• Properties of Aromatic Compounds
• Aromatic compounds, originally named because
of their fragrant properties, are unsaturated
hydrocarbon ring structures that exhibit special
properties, including unusual stability, due to their
aromaticity.
• They are often represented as resonance
structures containing single and double bonds.
However, the bonding is stronger than expected
for a conjugated structure, and it is more
accurately depicted as delocalized electron density
shared between all the atoms in the ring.
Benzene can only be fully depicted with all of its resonance structures, which show
how its pi-electrons are delocalized throughout its six-carbon ring. This delocalization
leads to a lower overall energy for the molecule, giving it greater stability.
• Structure of Aromatic Compounds
• Aromatic compounds are cyclic structures
in which each ring atom is a participant in
aππ bond, resulting in
delocalized ππ electron density on both
sides of the ring.
• Due to this connected network of ππ bonds,
the rings are planar, unlike the boat or table
structures typical of cycloalkanes.
• Physical Properties of Aromatic
Compounds
• Aromatic compounds are generally
nonpolar and immiscible with water.
• As they are often unreactive, they are
useful as solvents for other nonpolar
compounds.
• Due to their high ratio of carbon to
hydrogen, aromatic compounds are
characterized by a sooty yellow flame.
• Sources of Aromatic Compounds

• Aromatic compounds are produced from a

variety of sources, including petroleum and
coal tar. Poly-aromatic hydrocarbons are
components of atmospheric pollution and are
known carcinogens.
• Aromatic compounds are also interesting
because of their presumed role in the origin of
life as precursors to nucleotides and amino
acids.
• Reactions of Aromatic Compounds
1. Aromatic Substitution Reactions
These reactions involve the replacement of
one substituent on the ring of an aromatic
hydrocarbon, commonly a hydrogen atom, by a
different substituent group.
• The common types of aromatic substitution
reactions include:
– Nucleophilic aromatic substitution reactions
– Electrophilic aromatic substitution reactions
– Radical nucleophilic aromatic substitution reactions
• An example of an aromatic substitution reaction is the
electrophilic substitution observed in the nitration reaction
of salicylic acid.
• 1. Nucleophilic Substitution Reaction:
(a) What are nucleophiles?
– Nucleophiles are those species in the form of an
ion or a molecule which are strongly attached to the
region of a positive charge. These are said to be fully
charged or have negative ions present on a molecule.
The common examples of nucleophiles are cyanide
ions, water, hydroxide ions, and ammonia.
(b) What is Nucleophilic substitution reaction?
– A Nucleophilic substitution reaction in organic
chemistry is a type of reaction where a nucleophile
gets attached to the positive charged atoms or
molecules of the other substance.
(c) Mechanism of Nucleophilic substitution reaction:
– Two mechanisms of nucleophilic substitution reaction
are SN1 reaction and the SN2 reaction,
where S represents chemical substitution, N represents
nucleophilic, and the number stands for the kinetic
order of a reaction.
• Example of Nucleophilic Substitution
Reaction:
– A good example of a nucleophilic substitution
reaction is the hydrolysis of alkyl bromide (R-Br),
under the basic conditions, wherein the
nucleophile is nothing but the base OH−,
whereas the leaving group is the Br−. The
reaction for the following is as given below

R-Br + OH− ————– R-OH + Br−

– Nucleophilic reactions are as important in the

field of organic chemistry, and these reactions
are broadly classified as to occur at the place of
a carbon atom of a saturated aliphatic carbon
compound.
2. Electrophilic Substitution Reactions:

(a) What are electrophiles?

– The electrophilic substitution reaction involves the electrophiles.
Electrophiles are those which donate a pair of electrons in the
formation of a covalent bond. The Electrophilic reactions occur
mostly with the aromatic compounds. These compounds have about
an excess of electrons that can be shared throughout the system of
reaction.

(b) What is Electrophilic substitution reaction?

– The Electrophilic substitution reactions are basically defined as
those chemical reactions where the electrophile replaces
the functional group in a compound but not the hydrogen atom.
Some of the examples of species of electrophiles include hydronium
ion (H3O+), halides of hydrogen such as HCl, HBr, HI, sulfur trioxide
(SO3), the nitronium ion (NO2+), etc.

(c) Types of Electrophilic substitution reaction:

– Two types of electrophilic substitution reaction are discussed here.
Aromatic electrophilic substitution reaction and aliphatic electrophilic
substitution reaction.
• Electrophilic Aromatic Substitution (EAS):
– In this type of electrophilic substitution, an
atom attached to the aromatic ring which is
mostly hydrogen is substituted by an
electrophile. The reactions that occur
are aromatic halogenation, alkylating Friedel-
Crafts reactions, aromatic nitration, and
aromatic sulfonation and acylation. It further
comprises acylation and alkylation.
Electrophilic aromatic substitution (EAS): This reaction mechanism takes
place from bottom to top. EAS occurs ortho or para to electron donating groups,
such as amines, due to the stabilization of the intermediate positive charge. The
four structures drawn in the middle of the diagram are all resonance structures.
Due to the electrons provided by the NH2 group, this intermediate is stabilized,
and the para-substitution is favored. As an exercise, draw out the stabilization of
the positive charge when ortho substitution occurs.
• 2. Coupling Reactions
– In these types of reactions, the coupling of two
fragments which have a radical nature is achieved
with the help of a metal catalyst. When aromatic
hydrocarbons undergo coupling reactions, the
following type of bonds can be formed.
– A. Carbon-carbon bonds can be formed from
the coupling reactions of arenes and products
such as vinyl arenes, alkyl arenes, etc. are formed.
– B. The formation of carbon-oxygen bonds can
occur in these reactions, forming aryloxy
compounds.
– C. Carbon-nitrogen bonds can form in coupling
reactions, giving products such as aniline.
• An example of a coupling reaction involving aromatic
hydrocarbons can be observed in the arylation of
perfluorobenzenes, as illustrated below.

The catalyst used in this reaction is Palladium(II) acetate. It can also be noted
that DMA is the abbreviation of Dimethylacetamide.
• 3. Hydrogenation Reactions
– The hydrogenation reactions involving arenes
generally lead to the formation of saturated
rings. An example of such a reaction is the
reduction of 1-naphthol into a mixture
containing different isomers of decalin-ol.
– Another example of such a reaction is the
hydrogenation reaction of resorcinol with the
help of spongy nickel (also referred to as
Raney nickel) and aqueous NaOH. This
reaction proceeds via the formation of an
enolate, and the successive alkylation of this
enolate (with methyl iodide) to yield 2-methyl-
1,3-cyclohexanedione.
• Uses of Aromatic Hydrocarbons
The use of aromatic hydrocarbons is common in both biological
and synthetic processes. Some of the numerous uses of aromatic
hydrocarbons are listed below.
– The green pigment found in plants, more commonly
known as chlorophyll, consists of aromatic
hydrocarbons and is very important in the process of food
production in plants.
– The nucleic acids and amino acids in the human body also
consist of these aromatic hydrocarbons.
– Methylbenzene which is an aromatic hydrocarbon is used as a
solvent in model glues
– Naphthalene is an important item in the production of
mothballs
– For the synthesis of drugs, dyes, and explosives, an aryl
hydrocarbon known as Phenanthrene is used
– Trinitrotoluene or TNT is a very important aromatic
hydrocarbon which is widely used for explosive purposes.
– Plastic industry and petrochemical industries make use of
aromatic hydrocarbons extensively.
• Polycyclic Aromatic Hydrocarbons
– These are the hydrocarbons which comprise
of aromatic rings in fused form. These are
found in coal, tar, oil and some of the cooked
foods such as smoked fish, burnt toast, etc.
– One common example of these polycyclic
hydrocarbons is naphthalene. These
compounds are said to be pollutants.
– Some of the examples of aromatic
hydrocarbons are Methylbenzene,
Naphthalene, Phenanthrene,
Trinitrotoluene, and o-dihydroxybenzene.
• Structure and Nomenclature of
Aromatic Compounds
• Historically, benzene-like substances
were called aromatic hydrocarbons
because they had distinctive aromas.
• Today, an aromatic compound is any
compound that contains a benzene
ring or has certain benzene-like
properties (but not necessarily a
strong aroma).
• In the International Union of Pure
and Applied Chemistry (IUPAC)
system, aromatic hydrocarbons are
named as derivatives of benzene.
• four examples are shown below . In
these structures, it is immaterial whether
the single substituent is written at the
top, side, or bottom of the ring: a
hexagon is symmetrical, and therefore all
positions are equivalent.
Some Benzene Derivatives. These compounds are named in the usual
way with the group that replaces a hydrogen atom named as a
substituent group: Cl as chloro, Br as bromo, I as iodo, NO2 as nitro, and
CH3CH2 as ethyl.
• Although some compounds are referred
to exclusively by IUPAC names, some are
more frequently denoted by common
names, as is indicated in the following:
• When there is more than one substituent,
the corners of the hexagon are no longer
equivalent, so we must designate the relative
positions.
• There are three possible disubstituted
benzenes, and we can use numbers to
distinguish them.
• We start numbering at the carbon atom to
which one of the groups is attached and count
toward the carbon atom that bears the other
substituent group by the shortest path.
The Three Isomeric Dichlorobenzenes
• common names are also used: the
prefix ortho (o-) for 1,2-
disubstitution, meta (m-) for 1,3-
disubstitution, and para (p-) for 1,4-
disubstitution.
• The substituent names are listed in
alphabetical order. The first substituent is
given the lowest number. When a common
name is used, the carbon atom that bears
the group responsible for the name is given
the number 1:
•
• Polycyclic Aromatic Hydrocarbons
Some common aromatic hydrocarbons consist of fused benzene rings—
rings that share a common side. These compounds are called polycyclic
aromatic hydrocarbons (PAHs).

The three examples shown here are colorless, crystalline solids

generally obtained from coal tar. Naphthalene has a pungent odor
and is used in mothballs. Anthracene is used in the manufacture of certain
dyes. Steroids, a large group of naturally occurring substances, contain the
phenanthrene structure.
• Biologically Important Compounds with
Benzene Rings
– Substances containing the benzene ring are
common in both animals and plants, although
they are more abundant in the latter.
– Plants can synthesize the benzene ring from
carbon dioxide, water, and inorganic materials.
– Animals cannot synthesize it, but they are
dependent on certain aromatic compounds for
survival and therefore must obtain them from
food.
– Phenylalanine, tyrosine, and tryptophan
(essential amino acids) and vitamins K,
B2 (riboflavin), and B9 (folic acid) all contain the
benzene ring. Many important drugs, also feature
a benzene ring.