AROMATIC HYDROCARBONS However, because all the hydrogen atoms in
benzene are equivalent, it does not matter at
An aromatic hydrocarbon is an unsaturated
which carbon of the ring the substituted group
cyclic hydrocarbon that does not readily
is located. Each of the following formulas
undergo addition reactions.
represents chlorobenzene.
This reaction behavior, which is very different
from that of alkenes and alkynes, explains the
separate classification for aromatic
hydrocarbons.
Benzene
In this reversed approach, the benzene ring
The simplest aromatic hydrocarbon
attachment is called a phenyl group, and the
There are two equivalent structures that can be
compound is named according to the rules for
drawn for benzene that differ only in the
naming alkanes, alkenes, and alkynes.
locations of the double bonds
Each carbon atom in the ring can be considered
to participate in three conventional (localized)
bonds (two C— C bonds and one C—H bond)
and in one delocalized bond (the circle) that
involves all six carbon atoms
A delocalized bond is a covalent bond in which Benzene Derivatives with Two Substituents
electrons are shared among more than two When two substituents, either the same or
atoms different, are attached to a benzene ring, three
isomeric structures are possible.
To distinguish among these three isomers, we
must specify the positions of the substituents
Aromatic Ring System relative to one another.
An aromatic ring system is a highly unsaturated This can be done in either of two ways: by using
carbon ring system in which both localized and numbers or by using nonnumerical prefixes
delocalized bonds are present.
Nomenclature of Aromatic Compounds
Benzene Derivatives with One Substituent The prefix system uses the prefixes ortho-,
The IUPAC system of naming monosubstituted meta-, and para- (abbreviated o-, m-, and p-).
benzene derivatives uses the name of the Ortho- means 1,2 disubstitution; the
substituent as a prefix to the name benzene substituents are on adjacent carbon atoms.
Meta- means 1,3 disubstitution; the
substituents are one carbon removed from each
other.
Para- means 1,4 disubstitution; the substituents
are two carbons removed from each other (on
opposite sides of the ring).
A few monosubstituted benzenes have names
wherein the substituent and the benzene ring
taken together constitute a new parent name
When one of the two substituents in a Physical Properties
disubstituted benzene imparts a special name
They are insoluble in water, are good solvents
to the compound, the compound is named as a
for other nonpolar materials, and are less dense
derivative of that parent molecule. The special
than water.
substituent is assumed to be at ring position 1.
Benzene, monosubstituted benzenes, and many
disubstituted benzenes are liquids at room
temperature. Benzene itself is a colorless,
flammable liquid that burns with a sooty flame
because of incomplete combustion
Benzene was once widely used as an organic
solvent. Such use has been discontinued
When neither substituent group imparts a because benzene’s short- and long-term toxic
special name, the substituents are cited in effects are now recognized. Benzene inhalation
alphabetical order before the ending -benzene. can cause nausea and respiratory problems.
The carbon of the benzene ring bearing the CHEMICAL REACTIONS OF AROMATIC HYDROCARBONS
substituent with alphabetical priority becomes
carbon 1 Substitution - are characterized by different
atoms or groups of atoms replacing hydrogen
atoms in a hydrocarbon molecule
Alkylation and Halogenation
ALKYLATION
1. Alkylation: an alkyl group (R-) from an alkyl
chloride (R---Cl) substitutes for hydrogen atom
A benzene ring bearing two methyl groups is a on the benzene ring. A catalyst, AlCl3, is needed
situation that generates a new special base for alkylation
name. Such compounds (there are three
isomers) are not named as dimethylbenzenes or
as methyl toluenes. They are called xylenes.
In general terms, the alkylation of benzene can
be written as
Benzene Derivatives with Three or More Substituents
The ring is numbered in such a way as to obtain 2. Halogenation (bromination or chlorination): a
the lowest possible numbers for the carbon hydrogen atom on a benzene ring can be
atoms that have substituents. replaced by bromine or chlorine if benzene is
If there is a choice of numbering systems (two treated with Br2 or Cl2 in the presence of a
systems give the same lowest set), then the catalyst. The Catalyst is usually FeBr3 for
group that comes first alphabetically is given Bromination and FeCl3 for Chlorination
the lower number
SAMPLE:
FUSED-RING AROMATIC HYDROCARBONS
A fused-ring aromatic hydrocarbon is an
aromatic hydrocarbon whose structure contains
two or more rings fused together. Two carbon
rings that share a pair of carbon atoms are said
to be fused.
The three simplest fused-ring aromatic
compounds are naphthalene, anthracene, and
phenanthrene. All three are solids at room
temperature.
Fused-Ring Aromatic Hydrocarbons and Cancer
Carcinogenic fused-ring aromatic hydrocarbons
share some structural features. They all contain
four or more fused rings, and they all have the
same “angle” in the series of rings
Fused-ring aromatic hydrocarbons are often
formed when hydrocarbon materials are heated
to high temperatures. These resultant
compounds are present in low concentrations in
tobacco smoke, in automobile exhaust, and
sometimes in burned (charred) food
Angular, fused-ring hydrocarbon systems are
believed to be partially responsible for the high
incidence of lung and lip cancer among cigarette
smokers because tobacco smoke contains 3,4-
benzpyrene.
We now know that the high incidence of lung
cancer in British chimney sweeps (documented
over 200 years ago) was caused by fused-ring
hydrocarbon compounds present in the
chimney soot that the sweeps inhaled regularly.
