HYDROCARBONS. METHANE. ALKANES.

120o

C
H C

120o

H C

C H
C H

C
H

What might be the structural formula of this

compound?

C6H6
benzene

From the number of carbon and hydrogen atoms it could be

assumed this compound is unsaturated i.e it has double bonds
between two carbon atoms
BUT it does not discolor the solution of KMnO4 and Br2 AND it
undergoes more easily Substitution reactions than Addition!

Kekule suggested a formula according to which benzene had six

Carbon atoms bonded in a ring with alternating single and double
Bonds between the carbon atoms -> BUT in that case since we
Would have at least three double bonds within the ring it is to be
Benzene the expected that ADDITION reactions will be typical for benzene and
structural
That it will discolor KMnO4 solution and Bromine water which
Formula
Was not the case.
suggested by
Kekule
Later on, with the advance of technology, it was discovered the
molecule of benzene is flat (planer) all six carbon atoms lie in
The same plain and form a regular hexagon

Structure of Benzene

120o

C
H C

120o

H C

C H
C H

C
H

The distances between all 6 carbon atoms are

equal, all bond angles are 120o.
Each carbon atom in benzene is bonded to two other
carbon atoms and to one hydrogen atom with single
(sigma) bonds, which leaves 1 single valent electron
at each carbon atom -> in total 6 single electrons.
Those six electrons are completely
delocalized (That means they do not belong to
neither of the six carbon atoms but instead move
freely inside the benzene ring) over the six carbon
atoms. This bond is called a delocalized pi-bond. So
in the molecule of benzene we have six sigma bonds
between the six carbon atoms (each of those sigma
bonds belongs only to two neighboring carbon
atoms in the ring) and 1 delocalized pi-bond which
belongs simultaneously to All six carbon atoms in
the ring. This configuration is known as a benzene or
aromatic ring, and it is characterized by equalized
lengths and strengths of the C-C bonds, low energy
and high stability

Physical properties of Benzene

120o

C
H C

120o

H C

C H
C H

C
H

Colorless, volatile liquid with a characteristic

Odor, only slightly soluble in water, but highly
Soluble in organic compounds. Its vapors are
toxic and it is carcinogenic

Chemical properties of Benzene

Because of the high stability of the aromatic ring (which defines the Aromatic
(character of benzene) the majority of the chemical interactions of benzene do
not affect the benzene ring (the delocalized pi-bond). Therefore, benzene mainly
Participates in SUBSTITUTION reactions (which affect the sigma bonds between
the carbon and hydrogen atoms)
Halogenation
H

FeBr3

Br Br

Br

+
bromobenzene

HBr

Chemical properties of Benzene

Nitration
H

C. H2SO4

NO2

+ HO NO2

H2O

nitrobenzene
Sulfonation
H

+ HO SO3H

SO3H

+
Benzenesulfonic acid

H2O

Chemical properties of Benzene

Although with difficulties, benzene can take part in ADDITION reactions. It can
ADD chlorine and hydrogen.

Addition of Hydrogen

+ 3H2

Catalyst
Pressure,
heating

cyclohexane
Cl
Cl

Addition of Chlorine

+ 3Cl2

Catalyst
Pressure,
heating

Cl

Cl
Cl
Cl hexachlorocyclohexane

AlkylBenzene
Hydrocarbons that can be considered as obtained from benzene, in the
molecule of which one or more hydrogen atoms were replaced by an alkyl
group, are called monocyclic arenes or alkylbenzenes.
CH3

CH3

CH3
CH3

CH3
1,2 - dimethylbenzene
CH3

Methylbenzene (toluene)

1,3 - dimethylbenzene

CH3
1,4- dimethylbenzene

Properties of AlkylBenzene
Physical properties liquids with characteristic odor, insoluble in water, very
good solvents of organic substances.
Chemical properties Substitution reactions just like benzene. Alkylbenzenes
orientate the subsequent substituents to positions 2, 4, 6 within the benzene
ring.
CH3

CH3
C. H2SO4

O2N

NO2

+ 3HO NO2
Methylbenzene
(toluene)

NO2

2,4,6 - trinitrotoluene

H2O

Properties of AlkylBenzene
Halogination
CH3
Br
CH3

HBr
+
FeBr3

+ Br2
Methylbenzene
(toluene)

2 - bromotoluene
CH2 CH2 CH2 CH3
CH2CH2CH3
HBr

Br

Properties of AlkylBenzene
Sulfonation
CH3
SO3H
CH3

H2O

+ HO-SO3H
Methylbenzene
(toluene)

CH3

+
SO3H

H2O

Properties of AlkylBenzene
Oxidation
CH3

COOH
KMnO4, H+
H2O

Methylbenzene
(toluene)

BENZOIC ACID

Preparation by the method of Wurtz-Fittig

CH3

Cl

+ 2Na + ClCH3

+ 2NaCl

CH3

CH3
FeCl3

+ Cl2

HCl

Cl

CH3

CH3
FeCl3

+ Cl2
Methylbenzene
(toluene)

+
Cl

HCl

NO2
Cl

2,4,6

4-

SO3H

1
9

2
6

Cl

CH3
3

CH

CH3

+C
l2

10
4

?*
?
?
CH

8
2,4,6