BENZENE &

DERIVATIVES
Prepared by:
Jean H. Pontillas
INTRODUCTION
• BENZENE - colorless liquid first isolated
by Michael Faraday in 1825
• Its molecular formula (C6H6), suggests a
high degree of unsaturation
• Remarkably unreactive
INTRODUCTION
• AROMATIC
• Originally used to classify benzene and its derivatives because
many of them have distinctive odors
• Now used to refer to compounds (benzene and its derivatives)
that are highly unsaturated and are unexpectedly stable toward
reagents that react with alkenes

• Aryl group (Ar–) - derived from an aromatic compound (an arene)

by the removal of a H
STRUCTURE OF BENZENE
A. KEKULÉ’S MODEL
• First structure for benzene was
proposed by August Kekulé in
1872
• It consisted of a six-membered
ring with alternating single and
double bonds and with one
hydrogen bonded to each
carbon
STRUCTURE OF BENZENE
B. RESONANCE MODEL
• Represented as a hybrid of two equivalent contributing structures,
often referred to as Kekulé structures
• Each Kekulé structure makes an equal contribution to the hybrid
Aromaticity
AROMATICITY
• Many other types of molecules besides
benzene and its derivatives show aromatic
character
• In 1930s, German chemical physicist Erich
Hückel solved this problem by providing a
set of criteria
AROMATICITY
To be aromatic, a ring must:
1. Have one 2p orbital on each of its atoms;
2. Be planar or nearly planar, so that there is continuous overlap or
nearly continuous overlap of all 2p orbitals of the ring; and
3. Have 2, 6, 10, 14, 18, and so forth pi electrons in the cyclic
arrangement of 2p orbitals.
AROMATICITY
• Pyridine and pyrimidine are heterocyclic analogs of benzene
• In pyridine, one CH group of benzene is replaced by a nitrogen
atom, and in pyrimidine, two CH groups are replaced by nitrogen
atoms
AROMATICITY
• The five-membered-ring compounds furan, pyrrole, and imidazole
are also aromatic
AROMATICITY
• Nature abounds with compounds having a heterocyclic aromatic ring
fused to one or more other rings
• Two such compounds especially important in the biological world
are indole and purine
Monosubstituted
Benzenes
MONOSUBSTITUTED BENZENES
• Monosubstituted alkylbenzenes are named as derivatives of benzene
(e.g., ethylbenzene)
• IUPAC system retains certain common names for several of the
simpler monosubstituted alkylbenzenes
• Examples are toluene (rather than methylbenzene) and styrene
(rather than phenylethylene)
MONOSUBSTITUTED BENZENES
• Monosubstituted benzene derivatives are named by prefixing
benzene with the name of the substituent
• The whole name is written as one word
MONOSUBSTITUTED BENZENES
• Certain monosubstituted benzene derivatives are given special
names (e.g., methylbenzene as toluene, hydroxybenzene as phenol)
MONOSUBSTITUTED BENZENES
• Substituent group derived by the loss of H from benzene is a phenyl
group (Ph)
• That derived by the loss of H from the methyl group of toluene is a
benzyl group (Bn)
NOMENCLATURE
• If the substituent is larger than the benzene ring (has more than six
carbon atoms), then the benzene ring is treated as a substituent and
is called a phenyl group
NOMENCLATURE
• Presence of phenyl groups is often indicated with the letters Ph or
with the Greek letter phi (ᵩ)
MONOSUBSTITUTED BENZENES
PHYSICAL PROPERTIES
• Physical properties vary depending on the nature of the substituent
• Alkylbenzenes are nonpolar and have lower boiling points than
benzenes with polar substituents such as phenol, aniline, and
benzoic acid
• Melting points depend on whether or not their molecules can be
packed close together
• Benzene, which has no substituents can pack its molecules very
closely, giving it a considerably higher melting point than many
substituted benzenes
PHYSICAL PROPERTIES
PHYSICAL PROPERTIES
Disubstituted
Benzenes
DISUBSTITUTED BENZENES
• When two substituents occur on a benzene ring, three constitutional
isomers are possible
• We locate substituents either by numbering the atoms of the ring or
by using the locators ortho, meta, and para
• The numbers 1,2- are equivalent to ortho (Greek: straight); 1,3- to
meta (Greek: after); and 1,4- to para (Greek: beyond)
DISUBSTITUTED BENZENES
• Dimethyl derivatives of benzene are called xylene, and there are
three constitutionally isomeric xylene
DISUBSTITUTED BENZENES
DISUBSTITUTED BENZENES
NOMENCLATURE
• If two or more substituents are different, then the substituent that is
treated as a high priority group, is given the number 1 position in the
benzene ring
• The order of priority of the groups (left to right):
— COOH, — CN, — CHO, — COCH3, — OH, — NH, — OR, — R
• Other groups are numbered by counting from position 1 in the
manner which gives them the lowest number
NOMENCLATURE
NOMENCLATURE
• If the two substituents are different and they are not present in
priority order list, they are named in alphabetical order
• The last named substituent will be at position 1
NOMENCLATURE
• If there is a substituent on the ring which gives a special name to the
molecule, then special name is used as parent name to the molecule
• Special substituent occupies ring position number 1
NOMENCLATURE
• If there is a substituent on the ring which gives a special name to the
molecule, then special name is used as parent name to the molecule
• Special substituent occupies ring position number 1

3-nitrobenzoic acid 2-nitrobenzaldehyde

NOMENCLATURE
• When neither group imparts a special name, we locate the two
substituents and list them in alphabetical order before the ending
-benzene

1-bromo-2-ethylbenzene 1-bromo-2-nitrobenzene
Polysubstituted
Benzenes
POLYSUBSTITUTED BENZENES
• When three or more substituents are present on a ring, we specify
their locations by numbers
• If one of the substituents imparts a special name, then the molecule
is named as a derivative of that parent molecule
• If none of the substituents imparts a special name, we number them
to give the smallest set of numbers and list them in alphabetical
order before the ending –benzene
POLYSUBSTITUTED BENZENES
POLYSUBSTITUTED BENZENES

5-bromo-2-chlorophenol
EXERCISE
Provide the IUPAC name of the following compounds:

3-iodotoluene or m-iodotoluene 3,5-dibromobenzoic acid

EXERCISE
Provide the IUPAC name of the following compounds:

1-chloro-2,4-dinitrobenzene 1-bromo-3-chlorobenzene
EXERCISE
Provide the IUPAC name of the following compounds:

3-isopropylbenzaldehyde 2-bromotoluene
EXERCISE
Provide the IUPAC name of the following compounds:

2,4-dinitrophenol 1-ethyl-2,5-diisopropylbenzene
Reactions for
Benzenes
HALOGENATION

• Chlorine alone does not react with benzene, in contrast to its

instantaneous addition to cyclohexene
• In the presence of an acid catalyst, such as ferric chloride or
aluminum chloride, chlorine reacts to give chlorobenzene and HCl
HALOGENATION

• Treatment of benzene with bromine in the presence of ferric

chloride or aluminum chloride gives bromobenzene and HBr
NITRATION AND SULFONATION
FRIEDEL-CRAFTS ALKYLATION

• Discovered in 1877 by the French chemist Charles Friedel and

American chemist, James Crafts
• Discovered that mixing benzene, a haloalkane, and AlCl3 results in
the formation of an alkylbenzene and HX
• Friedel–Crafts alkylation forms a new carbon–carbon bond between
benzene and an alkyl group
FRIEDEL-CRAFTS ACYLATION

• Treating an aromatic hydrocarbon with an acyl halide in the

presence of aluminum chloride gives a ketone
• Acyl/acid halide – derivative of a carboxylic acid in which the -OH
of the carboxyl group is replaced by a halogen, most commonly
chlorine
Thank you!