01 Aromatic Hydrocarbons Benzene

Organic compds divided into:
1) Aliphatic compds (Alkane,Alkenes and Alkynes in

addition to dienes and cycloalkanes. (studied in 2nd
year).The simplest aliphatic HC is methane
2) The aromatic hydrocarbon are benzene and compds
resemble benzene in the chemical behaviour. Benzene
is the simplest aromatic HC.
Aromatic compounds named referring to the aromas
like odour shown by some members of this group of
compounds.
Dr Elrashied A E Garelnabi
Structure of Benzene:
The facts upon which the structure of benzene based

included:
1. From the elemental analysis and the molecular weight
determination the molecular formula of benzene was
found to be C6H6 .
2. now the, question how these 6C and 6H are arranged to
form benzene.
3. Benzene can be hydrogenated to cyclohexane, this can
confirm that the 6C are in a ring form.
H2 / Catalyst H H
C 6H 6
High temp
4. All the hydrogen in benzene are equivalent since
only one monobrominated, mononitrated
benzene are obtained.
Fe HBr
C6H6 + Br2 C6H5Br +
4. Only one hydrogen is attached to each carbon

since dehydrogenation of 1,3-cyclohexadiene
give benzene.
H
H Pd
C6H6
H
Then the skeleton of benzene is
H
H H
H H
H
Each carbon attached itself to one hydrogen and two

adjacent carbon atoms by sp2 hybrid orbitals.
Then each carbon is left with a p-orbital having a single

e. The p-orbital consists of two lobes, one above and
one below the plane of the 6 carbon atoms.
H
. .
. . H H
. .
H H
H
As in the case of ethylene, the p-orbital of one
carbon can overlap the p-orbital of the adjacent
carbon atom to form a bond
H
H H
H H
H
The over lapping of the p-orbitals in the case of the

benzene ring is not limited to a pair of p-orbitals as in
the case of ethylene but any one of carbon atom can
overlap equally one of the two adjacent carbon atoms
the result is a continuous e cloud above and below
the plane of the carbon atoms.
The plane of benzene with the above and
below es clouds
Electroststic potential
map that shows that
es density is identical
at all 6 c-c bonds
Because the 6-carbon atoms of benzene use the
sp2 hybrid orbitals, then the 6 carbon Atoms were
in the same plane that is benzene:
Is a flat molecule with hexagon shape.
The C-C bonds angles are 120.
Electron density identical at all 6-carbon atoms.
The es in the cloud are delocalized, whereas in
the case of ethylene are localized.
Each e is attached by 6 C nuclei.
Each carbon is attached by 6 e.
The delocalization lead to stabilization of
benzene, ring therefore benzene is unusually
stable unsaturated compds.
Resonance theory:
Many structures were proposed for benzene. The
most widely accepted representation of benzene
was that suggested by the Kekule in 1865.
H
H H
H H
H
From this structure it would appear that those pair of

carbon atoms that joined by C=C should be of 1.34
apart, the normal distance between double bonded
carbon atoms, and that the single bonded carbon
atoms have the distance 1.54 between them.
However all of the bonds in benzene are found to be
equal and have the length 1.39. Thus the structure
Suggested by Kekule does not fit that of benzene very
Well. Hence Kekule to solve this problem suggested
That benzene found into 2 structures
H H
H H rapid oscillation H H
OR
H H H H
H H
In one structure C1& C2 are joined by a double bond

while in the other C1&C2 are joined by a single bond.
The actual molecule of benzene is not represented by

either of these formula but by a 3rd formula.
This formula was obtained by combining the two
formula and divide them by 2.
In the combined formula, the bonds neither
single 1.54 nor double bond 1.34 something in
between and its length is 1.39 .
Then the actual structure of benzene is said to
be a resonance hybrid between the previous
two structures, they differ only in the position of
the bond.
The structures that can be drawn for benzene are
called contributing structure, it is not an
equilibrium.
Stability of Benzene
Although benzene is unsaturated compds , it is much
more stable than typical alkenes and fail to undergo the
alkenes reaction i.e no decolourization to Br2 and KMNo4 .
Benzene stability can be measured by heat of
hydrogenation: Heat of hydrogenation is the heat evolve
when one mole of unsatureated compds
hydrogenated.
Cyclohexene heat of hydrogenation -28.6 Kcal/mol and
cyclohexadiene a coniugated diene is -55.6 kcal which is a
little bit less than double (57.2) which shows that the
conjugated diene is more stable than the isolated diene.
+ H2
+ 2H2
Benzene if considered as cycloheatriene
expected to evolve heat of hydrognation 85.8 Kcal
/ mole whereas the observed one is 49.8 which
36 Kcal less than the theoratially expected,i.e
benzene is stable by 36 Kcal than cyclohexatriene.
This stability is due to delocalization of the es
and it is called delocalization energy.
catalyst H = -28.6 Kcal/mole
+ H2
Expected 57.2 Kcal/ mole
catalyst H =
+ H2 Found 55.6 Kcal/mole
C6H6 + H2 catalyst H= Expected 28.6 X 3 = 85.8

found 49.8
Benzene difference 36
Benzene
1,3-cycloheadiene Difference
36 Kcal
cyclohexene
55.6 Kcal 85.8 Kcal (Expected actual 49.8 Kcal
28.6 Kcal
Cyclohexane
Aromaticity and the Huckel Rule
Benzene is cyclic and conjugated.
Benzene is unusually stable (heat of
hydrogenation).
Benzene is planar regular hexagon with angles of
120 all carbon atoms are sp2 hybridized C-C
lengths 139
Benzene undergoes substitution reactions that
retain cyclic conjugated system rather than
addition reaction that destroy the conjugation.
This list provide good description to benzene and
other aromatic cpds but isnt enough, something
else called Huckel 4n +2 rule is needed to
complete description of the aromaticity.
Huckel German scientist state theory that:
A molecule is aromatic only if it has a planar,
monocyclic system of conjugation and contain a
total of (4n +2) electrons .
where (n = 0,1,2,3,) in other word only molecules
with 2,6,10,14,18, .. electrons can be aromatic.
Examples:
Cyclobutadiene
Contain 4 es localized in two double bonds, its not
Aromatic, very reactive can dimerizes by Diels
Alder reaction at -78 C.
Benzene has six electrons (4n+2= 6 when n = 1) and
is aromatic.
Cyclooctatetraene has 8 electrons and is not
aromatic. The electrons are localized in to 4 double
bonds, because its tubed shape not planar, therefore
neighbouring p orbitals dont have necessary parallel
alignment for overlap.
Cyclooctatetraene
Cyclopentadienyl anion and cycloheptatrienyl cation

are aromatic.
H
H
Cyclopentadienyl anion cycloheptatrienyl cation
Nomenclature of aromatic hydrocarbon
Principles govern naming of Aromatic HC are:
1. Many of benzene derivatives are named by pre-
fixing the name of the substituent to the word
benzene e.g
NO2 I
Br
bromobenzene
Nitro benzene iodobenzene
2. Other derivatives have special names which shows no
similarity to the name of the substituents e.g
NH2 CH3 OH
Aniline Toluene Phenol

3. If more than one substituents are attached to benzene ring we
must specify their name as well as their relative positions:
a) In disubstituted benzene ring we use ortho (o) meta (m) or

para (p) to indicate the relative positions of the 2 substituents
e.g Cl Cl
Cl
Cl
Cl
Cl
o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene
NO2 NO2
NO2
Cl
Cl
Cl
o-chloronitrobenzene m-chloronitrobenzene p-dichloronitrobenzene
b) If more than 2 gps are attached to the benzene ring, numbers

are used to indicate their relative positions:
Br
6 1 2
5 4
3 NO2
No2
1-bromo-3,4-dinitrobenzene
4. If one of the grs is the one that gives a special name
to the molecule, then the compd is named as a
derivative of that special compd e.g
OH NH2 CH3
NO2 O2N 1
NO2
6 2
5 4 3
Cl
NO2
o-nitrophenol m-chloroaniline 2,4,6-trinitrotoluene
(see McMurry organic chemistry textbook for more examples)

or any other reference book
Electrophilic Aromatic Substitution
The characteristic rxns of benzene is substitution rxn in
which the resonance stabilizing the ring is preserved.
Benzene has got a cloud of electron above and below the
ring which is loosely held compared with the sigma electrons.
Accordingly benzene acts as a source of electron i.e as base.
The compound with which benzene can react must be
electron deficient we call them electrophile i.e acids.
The typical rxn of alkenes is electrophilic addition, whereas
benzene is electrophilic substitution.
The electrophilic aromatic substitution rxns are characteristic
not only of benzene but also the other aromatic hydrocarbon.
H H
H H H E
+ E + H
H H H H
H H
Examples of elecrtophilc aromatic substitution rxns:
OH
OH NO2
CHO
H + H2O
+ NaOH + CHCl3
Nitration
Reimer - Tiemann rxn
O H2SO4
C + HNO3 SO3H
CH3 H
O
SO3 + H2O
AlCl3 + H2SO4
CH3 C Cl +
Friedel Craft acylation Acetyl chloride +
Sulphonation
X2
Fe
+ CH3Cl
X
methylchloride
AlCl3
+ HX
CH3
+ HCl
Halogenation
( X2 = Cl2, Br2)
Friedel Craft alkylation Dr Elrashied A E Garelnabi
Effect of substituent groups
Toluene like benzene can undergo electrophilic
aromatic substitution e.g sulphonation. Although there
are three possible monosubstitution products, this
reaction gives only 2-products.
CH3 CH3
CH3
orth (o)
o SO3H
H2so4
+
m SO3
meta (m)
SO3H
para (p) o-Toluenesulphonic acid (32%) p-Toluenesulphonic acid (62%)
When shaken with fuming H2SO4 at room temp,

benzene reacts completely within 20-30 min whereas
toluene is found to react within only a minute or 2.
(nitration, halogenation & Friedel crafts gives similar
results). Dr Elrashied A E Garelnabi
Nitobenzene on the other hand, has been found to
undergo substitn more slowly than benzene and to
yield chiefly the m-isomer.
NO2 NO2
HNO3
H2SO4
NO2
Like methyl or nitro, any group attached to

benzene ring affects the reactivity and determines
the orientation of the substitution.
A group that makes the ring more reactive than
benzene is called an activating grp.
A grp that makes the ring less reactive than
benzene is called a deactivating grp.
A grp that causes attack to occur chiefly at position
ortho and para to it is called an ortho- para director.
Agrp that causes attack to occur chiefly at position
meta to it is called meta director.
Classification of substituents groups
Nearly all grps attached to the benzene ring can be

divided into 2 classes:
a) Activating which are also ortho-para directors.
b) Deactivating which are also meta directors.
Halogens are deactivating but are ortho-para directors
this why they fall in a separate class.
Deactivating meta director
Activating orth-para directors:
CH3
Strongly activating
Strongly deactivating N CH3
-NH2 , -NHR , -NR3
-OH CH3
Moderately activating -NO2

-OCH3 , (-OC2H5 ect) -CN
-NHCOCH3 O O
(R)
C CH3 ; C H
Weakly activating
O O
-CH3 (C2H5 ect)
C OH ( C OR)
SO3H
phenyl Weakly deactivating
Deactivating: ortho-para directors:
-F , - Cl , - Br , - I
The effect of the substituent on the orientation and rate of
reaction of benzene can now be easily predicted e.g
O O O
HN C CH3 HN C CH3 HN C CH3
NO2
HNO3
H2SO4
Acetanilide NO2
Ortho-para substitution rxn which is faster than benzene

NO2 NO2
Fe
+ Br2
Br
meta substitution rxn which is slower than benzene

Orientation in disubstituted benzene
The presence of 2 substituents on benzene ring makes

the prediction need to be according to the following
principles:
1. Re-inforces : if the two substituents direct the
substitution to the same direction or orientation
NO2 NO2
Fe
+ Br2
Br
CH3 CH3
2. If the 2 substituents are opposing each other then the
following generalization can be made:
Strong activating groups win over weakly activating
and deactivating gps.
OH OH
NO2
H2SO4
+ HNO3 Only product
CH3 CH3
CH3 CH3
O NH O NH
Br
Fe
+ Br2
Chief product
CH3 CH3
3. Substitution rarely occurs between the 2 gps in a
meta disubstituted benzene
CH3
Sterric hindrance
Cl
Orientation and synthesis
Prepare o-, m-, p- bromonitrobenzene start from benzene?
NO2 NO2
HNO3 Br2 / Fe m- bromonitrobenzene

H2So4
Br
Br Br Br
NO2
Br2 / Fe HNO3
+
H2So4 o-bromonitrobenzene
NO2
p-bromonitrobenzene
According to which isomer required the order of the steps
of the reaction is specified.
If the synthesis involves conversion of one group into
another, then the proper time for the conversion must be
consider base on the isomer need to be synthesized e.g
oxidation of alkyl group (methyl) to carboxyl
CH3 COOH
Kmno4
or K2Cr2O7 / H2SO4
CH3 COOH
Kmno4
or K2Cr2O7 / H2SO4
COOH
HNO3
H2So4 m-nitrobenzoic acid
NO2
CH3 CH3 CH3
NO2
HNO3
+
H2So4
NO2
Kmno4 or K2Cr2O7 / H2SO4
COOH COOH
NO2
+
p-nitrobenzoic acid
NO2 o-nitrobenzoic acid
It is possible to separate the pure p-nitrobenzoic acid from the

o-nitrobenzoic acid isomer by fractional crystallization. The
p-isomer is more symmetrical it is less soluble therefore
crystallized out first.
Home work:
Show how you can synthesize p-bromobenzoic
acid from benzene?
Mechanism of Nitration
A mixture of conc HNO3 & H2SO4 is used for
nitration. NO2
HNO3
H2SO4
The mechanism of this reaction using the HNO3 &

H2SO4 mixture involve the following sequence of
rxns:
1) Generation of the electrophile
O H O O
O N + H2SO4 O N H2O + N
H O H O O
Nitronium ion
(electrophile)
2) Attack of the electrophile to benzene ring
seeking for electrons.
H H H
O
O2N
Slow O2N
N O2N
H
O2N
Equivalent to Carbocation
3)Stabilization of the carbocation to itself by losing

proton to a base HSO4- to form nitrobenzene and
H2SO4
NO2
H
O2N
Fast + H2SO4
HSO4
The last step is a fast step in which a charged molecule
was been converted to neutral molecule.
Benzene ring retained its resonance stability.
Nitration rxn does not occur in nature but it is
important in the lab
Mechanism of sulphonation:
SO3H
SO3
+ H2SO4
1) Generation of the electrophile (SO3 or HSO3+)

H2SO4 + H2SO4 SO3 + H3O + HSO4 O
S O
Dr Elrashied A E Garelnabi Electrophile (neutral molecule)

2) Slow step attack of the electrophile to the
H H H
SO3 SO3 SO3
O
S O
O
H
SO3
Equv to
3) Retaining of the resonance stabilizing the

aromaticity by losing a proton to base (fast step)
H SO3
SO3
fast + H2SO4
+ HSO4
SO3 SO3H
Fast
4) + H 3O + H 2O
Sulphonation usually performed with conc. H2SO4 acid
fumed with SO3, also it can be performed with conc. H2SO4
only but it is slow reaction. This confirm that the SO3
formed in step one is the actual attacking reagent.
The electrophile SO3 it doesnt contain an actual positive
charge. But the electron deficient suphar atom, due to the
withdrawal effect of its electron by the three oxygen atoms
generate its electrophilicity.
O
S O
Sulphonic acid v. strong acid, therefore it is highly ionizable

SO3H SO3
+ H
Sulphonation is reversible reaction
desulphonation can take place in hot dil H2SO4.
SO3H
dil H2SO4
+ H2SO4
Like nitration sulphonation does not occur in

nature but it is very important in labs specially
in the synthesis of sulphar Drugs.
O
H 2N S
O Sulphonamides (antibiotic)
H2N
Mechanism of Halogenation
Benzene does not react with chlorine and bromine
directly a Lewis acid catalyst is need.
Frequently used Lewis acids for halogenation FeCl3,
FeBr3 and AlCl3.
When Fe is used it first converted to FeCl3 or FeBr3
which is the actual catalyst. Br
Fe i.e (FeBr3)
+ Br2 + HBr
75%
Cl
Fe i.e (FeCl3)
+ Cl2 + HCl
Dr Elrashied A E Garelnabi 90%

The mechansim of halogenation if we took chlorination as
example :
1) The Lewis acid polarize the halogen to generate the
electrophile
Cl Cl
Cl Cl + Fe Cl Cl Cl Fe Cl
Cl Cl
Polarized Cl2 molecule
2) Attack of the electrophile to the electrons:
H
H Cl
Cl
+ FeCl4
+ Cl Cl Fe Cl
Cl
H
Cl H
Cl H
Equivalent Cl
4) Removal of a proton to a base to generate the
resonance stabilized aromaticity
H
Cl
Cl
+ FeCl4 + HCl + FeCl3
The order of reactivity of halogens is F2, Cl2, Br2, I2
H3 C
Diazepam anxiety drug N
O
synthesized by this method
N
Cl
Mechanism of Friedel Craft Alkylation
In 1877 the Frensh chemist Charles Friedel and his
American collaborator James Craft discovered a new
R
method for making alkylbenzene.
The general equation for Friedel-Craft alkylation is

R
H
AlCl3 + HX
+ R X
Alkylhalide
CH3
Example: H H3C
CH
AlCl3 CH3
+ CH Cl + HCl
H3C
Isopropylchloride
Mechanism:
H3C H3C
Cl + AlCl3 CH + AlCl4
1) CH
H3C
H3C
Isopropylcarbocation
(Actual electrophilic particle)

2) CH3 CH3
H H
H CH CH
CH3 CH3 CH3
+ HC Equv
CH3
3) Removal of a proton to a base to retain back the

aromaticity of the ring
CH3 CH3
H
CH CH
CH3 CH3
+ AlCl4 + HCl + AlCl3
The Friedel-Craft Acylation
O
The R C group called acyl group and the reaction

where an acyl group is introduced in a compd is called
acylation.
Two common acyl group is acetyl and benzoyl group
O O
H3C C C
H O C
AlCl3 CH3
+ H 3C C Cl
The Friedel - Craft alkylation and acylation can be

catalylized by metal halides as well as mineral acid. The
order of potency of these catalyst in decreasing order is
AlCl3 > FeCl3 > SnCl4 >ZnCl2 > HF > H2SO4 > H3PO4
Reactivity and orientation
Mechanism of activation and deactivation:
The general mechanism of aromatic substn is:
1) Generation of the electrophile . E + B E+ + B
2) Attack of the electrophile to the electron of the
aromatic ring. H H H
E
E E
H
slow Equv
+
+ E
H
E
1) Lost of the proton to a base

H
E E
Fast
+ B + HB
The rate of step 2 determine the overall rate of the
reaction. Any factor that will reduce the energy of
activation Eact for this step will increase the rate of the
reaction.
H
E
Ea
Energy
Reaction progress
Factors that stabilize the carbocation are the same
factors that reduce Ea required for the formation of
this intermediate carbocation.
Carbocations are stabilized by grps that reduce the
acquired positive charge.
Let us compare the stability of carbocations
intermediates resulting in electrophilc aromatic
substn in benzene, toluene and nitobenzene
H
E
H
E
CH3
Methyl gp is es releasing by I+ then
neutralize +ve charge, which stabilizes the
intermediate Carbocation, Then makes the
rxn faster than in case of benzene
H
E
NO2
Nitro gp es withdrawing (I+ and M+) then
intensify the +ve charge, which
destabilizes the intermediate carbocation,
this makes the rxn slower than benzene
Substituents that
release electrons, Substituents that
stabilize the withdraw electrons,
carbocation and destabilize the
activate the reaction carbocation and
-NH2, -NHR, -NR2 deactivate the reaction
CH3
-OH N
CH3
-OCH3 CH3
-NHCOCH3
-CH3 (R) -NO2, -CN,
-C6H5 phenyl -COR
-CHO
Substituents release -COOH
electrons, stabilize the -COOR
carbocation and are -SO3H
o,p-director Electron withdrawing
gp are deactivator and
m-director
Activation:
Two way of activation inductive effect i.e releasing
of electron by inductive effect (+I) this occur from
alkyl and phenyl gps.
Other activation is by releasing electrons through
mesomeric (+M) or resonance this occur mainly
from gps contain atoms with unshared electrons :
NH2 , NHR , NHCOCH, 3 NR2, OH
i.e with the general structure

Z
Unshared of electrons
on an atom directly attached
to the ring
Groups which contain atoms with unshared electrons
strongly activate the ring by donating electrons
through resonance (+M) lone pair of electron flow
from the substituent into the ring e.g oxygen and
nitrogen can share with one pair and accommodate the
+ve charge.
O O
NR2 NR2
Although O and N are electronegative atoms that can

withdraw es by inductive but their resonance effect
predominate.
Deactivation:
Electron withdrawing by inductive effect (-I), this
is due to the electronegativety of the halogens.
X
X = Cl, Br, I
The carbonyl, cyano and nitro gps inductively

electron withdrawing because of the functional
gp polarity
O O

C N C N
O
The carbonyl, cyano and nitro gps withdraw es

through resonance, pi electrons flow from the
ring to the substituents leaving +ve charge in the
ring. Dr Elrashied A E Garelnabi

O O
C N
C N

O
O
O
C N
N
O
Substituents with e-withdrawing resonance effect have

general structure Y= Z where Z is more electronegative

than Y. Z
H.W
Write resonance structures for chlorobenzene to show electron-donating
resonance effect?
Mechanism of the Orientation
Activating group activate all the positions in the
ring but it activate ortho and para more than meta
this why are ortho-para director
CH3 CH3 CH3 CH3
NO2
HNO3
+ +
H2SO4 25 C
NO2
NO2
34% 3% 63%
Deactivating gps deactivate all the ring but their
deactivation is less on the meta position this why
they are meta director.
To confirm these facts let us compare the stability
of carbocations result from the different attacks
CH3 CH3 CH3
H H H
NO2 NO2 NO2
ortho
34%
CH3
most stable
CH3 CH3 CH3
meta
H H H
3%
NO2 NO2 NO2
CH3 CH3
CH3
para
34%
NO2 NO2
NO2
H H
H
Dr Elrashied A E Garelnabi more stable

In the nitration of toluene whether o, m or p
there are three resonance hybrids structures
(carbocation intermediate), all of them are
resonance stabilized but the ortho and para
isomers were more stabilized than meta
intermediates.
The special stable hybrid in which the +ve charge

located at the carbon carrying the electron release
gp which occurs only in case of o and p was behind
the extra stability.
Nitrobenzene on the other hand shows the
following E.A.S NO NO2 NO2 2
H H H
E E E
ortho
E+
Special unstable
NO2 NO2
NO2 NO2
E+
H H
meta H
E E
E
NO2 NO2 NO2
E+
para
H H H
E E E
Dr Elrashied A E Garelnabi Special unstable

In each case the resulting carbocation is a
resonance hybrids contribution.
o, p attacks shows a hybrid in which the +ve

charge located at the carbon carrying the electron
withdrawing gp (nitro gp), this hybrid is specially
unstable.
meta attack doesnt show such special unstable

hybrid, this why the nitro gp push the reaction to
the lower energy isomer (Ea) at the meta position.
Electron releasing via resonance: OH and NH2
OH and NH2 activate the benzene ring towards

E.A.S by strong electron releasing through
resonance effect.
Their direction to the reaction towards o and p

can be seen from the stability of the intermediate
carbocation resulting its as follows:
NH2 NH2 NH2 NH2
H H H H
E E E E
ortho
E+
Special stable
NH2 NH2
NH2 NH2
E+ H
H
H
meta E
E
E
NH2 NH2 NH2 NH2
E+
para
H H H H
E E E E
Special stable
H.W
1) Work out the electrophilic substitution on phenol ?
OH
2) Acetanilide is less reactive than aniline toward electrophilic

substitution. Explain?
H
N O
CH3
Effect of Halogens on Electrophilic aromatic Substn
Halogens are unusual, they are deactivating and
at the same time ortho, para director.
Their strong electronwithdrawing by inductive
effect (-I) behind their effect on the reactivity.
H
E
Cl
Concerning the orientation electron release by

resonance effect play the role.
Cl
Cl Cl H
Cl
H H E
H
E E E
ortho
Relatively stable
E+ special unstable
Cl Cl
Cl
Cl
E+ H
H
H
meta E
E
E
Cl
Cl Cl Cl
E+
para
H
H H H E
E E E
special unstable relatively stable
Arenes
Aliphatic - aromatic hydrocarbon
Alkylbenzene obtained from coal tar and petroleum,
and they consumed in huge quantities in chemical
industries.
Arenes are aliphatic and aromatic hydrocarbon i.e
contain both units and their chemical properties are
combination between the two. For example ethyl
benzene consist of benzene and ethyl side chain.
H2
C
CH3 Aliphatic portion
of alkylbenzene
(side chain)
Two sets of chemical properties expected to be
shown by alkylbenzene, the ring undergo
E.A.S and ethyl gp undergo free radical subst
characteristic of ethane.
The properties of each portion will be affected

by the presence of the second one.
Treatment of ethylbenzene with conc HNO3 and
H2SO4 introduces a NO2 gp into the ring more
readily than in benzene and in the ortho and para
positions.
Treatment of ethylbenzene with Br2 in the
presence of UV light introduces a bromo gp into
the side chain exclusively at the carbon attached
to the ring and the rxn occur more readily than in
ethane
NO2
H2 H2 H2
C C C
CH3 HNO3 CH3 CH3
+
H2SO4
O2N
Br
H2 CH
C Br2 CH3
CH3
UV
Each portion of the molecule affects the reactivity
of the other portion and determines the
orientation of the attack.
Nomenclature of Arenes
The simplest arene is toluene (methylbenzene )

whereas the simplest dialkylbenzene are given
the special name Xylenes C2H5
CH3 CH3
CH
CH3 H 3C CH3
Toluene O, m, p-xylene
CH3
C2H5
CH
C 2 H5 H 3C CH3
p-ethyltoluene
Named as derivative of p-ethylisopropylbenzene
toluene
Alkylbenzen contain a complicated side chain is
named as a derivative of alkane
CH3
H
H 3C HC C CH2 CH3
2-methyl-3-phenylpentane
The simplest alkenylbenzene has special name

styrene
CH CH2
Styrene
Preparation of alkylbenzene
1. By the Friedel Craft alkylation: this is useful
method for preparation of alkyl benzenes
R
AlCl3
+ R X + HX (X = F, Cl, Br, I )
However there is limitation to the use of Friedel

craft alkylation rxn these include:
a)The alkyl gp that end attached to ring is not
always the same as the alkyl gp of the parent
alkylhalide. This is because as actual
electrophile is a carbocation, it may rearrange to
give a more stable carbocation which attack the
ring. Dr Elrashied A E Garelnabi
H3C CH3
CH
AlCl3
+ CH3CH2CH2Cl + HCl
CH3CH2CH2
1 carbocation
rearrange
CH3CHCH3
2 Carbocation
Sometimes the product resulting from rearrangement of the
carbocation the sole product
CH3
H3C CH3
C
CH3
AlCl3
+ H3C C CH2Cl + HCl
H
Isobutylchloride
H.W
Indicate why this is a sole product?
b) Friedel Crafts alkylation is limited to alkyl halides,
aryl halides and vinyl halides cannot be used as they
are not reactive
Cl
AlCl3
no reaction
+
Aryl chloride
AlCl3
+ H2C CH Cl no reaction
Vinyl chloride
c) Friedel Craft alkylation cannot be
performed on aromatic rings substituted with
strongly deactivating gps.
AlCl3
+ R X no reaction
CH3
Y= N CH3 , NO2 , CN , COR, SO3H
CH3
CHO , COOH
d) On benzene ring contain NH2, -NHR, -NR2 which are
activating gps, but in the presence of the catalyst Lewis
acids (Friedel- Craft alkylation catalyst) a complex is
formed and this complexation places a +ve charge on the
N and converts the amino gp from an activator to powerful
deactivator.
NH2 Cl3Al NH2
+ AlCl3
Activated aromatic ring Deactivated aromatic ring
e) A fundamental difficulty of Friedel Craft
alkylation is that the product is more reactive
than the starting material.
This is due to the fact that the substituted alkyl gp

activates the ring so once an alkyl gp is introduced
it facilitates the entrance of a 2nd gp. The result is a
polyalkylation.
CH3 CH3
H 3C CH3 H 3C CH3
C C
H 3C CH3 AlCl3
+
+ C Cl
CH3
CH3
C
H 3C CH3
Minor product
Major product
2)Friedel-Craft acylation
Acyl gp introduced in the aromatic ring when an

acid chloride or acid anhydride react with the ring
in the presence of Lewis acid catalyst. The product
is arylketone
O C
AlCl3 R
+ R C Cl
O
O
CH3
AlCl3
+ H3C C Cl
Acetylchloride Acetophenone
O
O
H 3C C CH3
AlCl3
+ O
+ CH3COOH
H 3C C
Mechanism
O O
1) R C Cl + AlCl3 R C R C O + AlCl4
Acylium ion, resonance stabilized

(actual attacking particle)
O O
O H H
H
H R R Equv
R
2) + R C O O
H
3) Removal of the proton to base to generate the resonance

O
stabilized aromatic ring H O
R
R
+ AlCl3 + HCl
+ AlCl4
Unlike the carbocation intermediate produced in
Friedel Craft alkylation, the acylium ion does not
rearrange and hence the acyl gp attached to the ring is
corresponding to the acid chloride used.
The acyl gp introduced in the ring deactivate the ring
therefore unlike Friedel Craft alkylation no
polyacylation will tock place.
The acylbenzene may be reduced to the corresponding
alkylbenzene by Clemmensen (Amalgamated Zn &
Conc. HCl).
O
H2
C C
CH3 CH3
Zn / Hg
conc. HCl
Wolf Kishner reduction of the C=O to CH2 by using
(Hydrazine & Base)
O
H2
C C
CH3 CH3
NH2-NH2
Base
Like Friedel Craft alkylation, the Friedel Craft
acylation cannot be performed on rings carrying
strong es withdrawing gps.
NO2 O
AlCl3 no Rxns
+ H3C C Cl
H. W : How would you make m-nitroacetophenone

from benzene and any other reagents?
O
NO2
H3C
Reaction of alkyl benzene
Hydrogenation:
Alkyl benzenes are converted into alkyl cyclohexanes
when hydrogenated over a rhodium-on-charcoal
catalyst.
CH3 CH3
H2 Rh /C
CH3 CH3
p-xylene 1,4-dimethylcyclohexane
The usual platinum, palladium catalyst used in the
hydrogenation of alkenes do not affect aromatic rings.
O
H O
C C C CH3 H2
H C C C CH3
H2 , Pd H2
Note the ring and carbonyl gp not affected.

Benzene catalytical hydrogenation with Pt or Pd can
only occurs at very high pressure (hundred
atmospheric pressure)
Oxidation:
Both aromatic hydrocarbons and aliphatic
hydrocarbons are resistant to oxidation.
Benzene although its unsaturated but it resist
oxidation by strong oxidizing agent such as
KMNO4 and Na2Cr2O7 which on the other hand
cleave alkene C=C
Presence of aromatic ring, however affect the side
chain of arenes, they can be oxidized by KMNO4
or Na2Cr2O7 in H2SO4 more readily.
H2
C COOH
CH3
KMNO4
or Na2Cr2O7/H
For side chain to undergo oxidation it must have a
hydrogen i.e CH which required for the formation of
benzylic radical.
CH3
C CH3 KMNO4
CH3 No Rxn
or Na2Cr2O7/H
Oxidation of the side chain used in industry in

preparation of terephthalic acid from oxidation of p-
xylene used in production of polyster fibre.
CH3 COOH
O2
Co (III)
CH3 COOH
Nitration (EAS):
Like benzene, alkyl benzene nitrated by a mixture of
conc HNO3 and H2SO4. because the alkyl gp
activating gp the rxn is faster than in case of benzene
and occurs at ortho and para positions
CH3 CH3 CH3
NO2
HNO3 4%
+
+ meta
H2SO4 isomer
NO2
H2SO4 HNO3
CH3
CH3
NO2
NO2
+
NO2
NO2
H2SO4 HNO3
CH3
No2 NO2 2,4,6-trinitotoluene

T.N.T
An explosive material. Mixed with
NH4NO3 it form the explosive
NO2
amatol
Sulphonation:
As in nitration, the alkyl gp activates the benzene ring
and tends to direct the entering gp to the o- and para
positions
CH3
CH3 CH3
SO3H
SO3 4%
+ +
meta
H2SO4 isomer
SO3H
O- and p- toluene sulphonic acid
Halogenation: Ring vs side chain:
Alkyl benzenes offer 2 areas for attack by halogens, the
side chain and the ring.
We can control the rxn simply by choosing the right
rxn conditions.
Halogenation of the side chain required conditions
under which halogens atoms are formed in presence
of high temp or ultra violet light.
Halogenation of the benzene ring require conditions
under which the halogen is ionized e.g by the use of
Lewis acid like FeCl3
Cl Halogen atom
CH3
Cl

Cl Cl Fe Cl
Cl
Ionized halogen
CH3 CH2Cl
Cl2
Benzyl chloride
UV ,
CH3 CH3
CH3
Cl
Cl2
+
FeCl3
Cl
Similar results are obtained with other alkyl benzenes and

with chlorine as well as bromine
Bromination of alkyl benzene side chains
N-bromosuccinimide (NBS) and Br2 in presence
of u.v. or energy react with alkyl benzene to
brominate the benzylic position through a radical
chain rxn.
Benzylic carbon
C H Benzylic hydrogen
CH3 Br CH3
H 2C CH
O
Benzoyl peroxide
+ N Br
(Br)
The bromine atom generated in both the NBS or the Br2

and u.v. could abstract a hydrogen to form the free radical
CH3
HC
CH3
H2C
Br2
CH2
H2C
X
The product results from abstraction of a benzylic
hydrogen are easy to abstract
Experiments have shown that benzylic hydrogen,
are extremely easy to abstract. They resemble
allylic hydrogen. The sequence of ease of
abstraction of hydrogen can be shown by the
following :
Allylic & benzylic > 3 > 2 > 1 > CH4 > vinylic
The fact that benzylic hydrogens are easy to
abstract means that benzyl free radical are usualy
easy to form.
Stability of free radical follows the same above
sequence.
Chlorination of alkyl benzenes:
Cl
CH3 Cl CH3 CH2

H 2C CH H2C
Cl2
+
91% 9%
Chlorine atoms, like bromine atoms

preferentially attack benzylic hydrogen, but as
seem from the example given, this because the
chlorine atom is more reactive than bromine
atom therefore less selective.
Resonance stability of allylic free radical
The resonance stability of allylic and benzylic free
radical is as a result of the overlapping of the odd
electron orbit with the p orbit of the electrons.
H H2C C CH2
H
H H
C C C
H H
H2C C CH2
H
Resonance stability of benzylic free radical
Like allylic resonsnce stabilizes the benzylic free
radical as a result of the overlapping of odd electron
orbital with the ring system orbitals.
CH3
CH2 CH2 CH2
Cl
CH2
The spin density surface shows that the unpaired
electron is shared with the ortho and para
Alkenyl benzenes
Preparation:
Alkenyl benzenes that have the double bond
conjugated with the benzene ring are more stable than
those do not .
C C C C
C C
Non conjugated system

Conjugated system
H
C CH3 1-phenylpropene
C
H only product
H2 Alco
C CH CH3
KOH H2
Cl C CH2
C
X H
H
C CH3
C 1-phenylpropene
H
only product
H2 H+
C CH CH3
H2
OH C CH2
C
X H
The unusual stability of the conjugated system is that
the electrons of the side chain would be delocalized
an spread over the ring as a result of the overlapping.
The most important alkenyl benzene is the styrene.
H
C
CH2
It is preparation in industry by dehydrogenation of

ethyl benzene.
H2
C H
H3PO4 C
CH3
Cr2O3/ Al2O CH2
+ H2C CH2 3
600 C
Dr Elrashied A E Garelnabi 90%

Reaction of alkenyl benzenes
Alkenyl benzenes undergo two set of reactions: EAS on
the ring and electrophilic addition to the double bond
in the side chain.
Since both the ring and double bond are good sources
of es, there may be competition between the 2 sites for
certain electrophilic reagents. Generally the double
bond show higher reactivity than the resonance
stabilized benzene ring.
Hydrogenation:
Both the benzene ring and the C=C can be
hydrogenated. The condition for the C=C are much
milder.
H H2
C H2 C
CH2 C H2, Ni, 125 CH3
H2, Ni, 20 CH3
2 - 3 atm 110 atm
H2, Rh/C
25
Oxidation:
Milder oxidation of alkenyl benzene give glycol, more
vigorous rxn condition give a carboxylic acid
H OH
C
CH2 CH OH
Cold dil C
H2
Kmno4
Hot Kmno4
COOH
Hot
Kmno4
Addition of Halogen Acids
Addition of HCl or HBr to styrene in the absence of
peroxide gives
X
H
C CH
CH2 CH3
+ HX ( X = Cl , Br)
The addition of HBr in absence of peroxide give a

similar product to that of addition of HCl and
proceeds by a carbocation mechansim.
H Br
C
CH
CH3 Br CH3
H
C
CH2 HBr
H2
C
CH2
X
H H2
C C
CH2Br HBr CH2Br
H
C
CH2 HBr Br
Peroxide
CH
CH2
X
The first step of these rxns takes place in the way that
yields the benzylic carbocation or benzyl free radical
rather than the primary one.
Polymerization of styrene
Polymerization of styrene is the most impt rxn of
styrene, the rxn involve a free radical addn and
produces poly styrene which an important plastic,
especially as an electric insulator
C6H5 COOOCO C6H5 C6H5 CO O Iniation step

H Ln C CH
C H2
CH2
+ C6H5 CO O Propagation
H Ln C CH H2
C H2 Ln C CH C CH
CH2 H2
+
It used in object such as toys, Brush handles and combs
it used in foam may other uses
A polystyrene yogurt container Expanded polystyrene packaging
CD case made from general purpose Disposable polystyrene razor

polystyrene (GPPS)

01 Aromatic Hydrocarbons Benzene

Încărcat de

Informații document

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

01 Aromatic Hydrocarbons Benzene

Încărcat de

Drepturi de autor:

Formate disponibile

Organic compds divided into:

1) Aliphatic compds (Alkane,Alkenes and Alkynes in

The facts upon which the structure of benzene based

4. Only one hydrogen is attached to each carbon

Then the skeleton of benzene is

Each carbon attached itself to one hydrogen and two

Then each carbon is left with a p-orbital having a single

The over lapping of the p-orbitals in the case of the

From this structure it would appear that those pair of

In one structure C1& C2 are joined by a double bond

The actual molecule of benzene is not represented by

C6H6 + H2 catalyst H= Expected 28.6 X 3 = 85.8

Cyclopentadienyl anion and cycloheptatrienyl cation

Aniline Toluene Phenol

a) In disubstituted benzene ring we use ortho (o) meta (m) or

o-chloronitrobenzene m-chloronitrobenzene p-dichloronitrobenzene

b) If more than 2 gps are attached to the benzene ring, numbers

(see McMurry organic chemistry textbook for more examples)

When shaken with fuming H2SO4 at room temp,

Like methyl or nitro, any group attached to

Classification of substituents groups

Nearly all grps attached to the benzene ring can be

Moderately activating -NO2

phenyl Weakly deactivating

Deactivating: ortho-para directors:

HN C CH3 HN C CH3 HN C CH3

Ortho-para substitution rxn which is faster than benzene

meta substitution rxn which is slower than benzene

The presence of 2 substituents on benzene ring makes

Prepare o-, m-, p- bromonitrobenzene start from benzene?

HNO3 Br2 / Fe m- bromonitrobenzene

Kmno4 or K2Cr2O7 / H2SO4

NO2 o-nitrobenzoic acid

It is possible to separate the pure p-nitrobenzoic acid from the

The mechanism of this reaction using the HNO3 &

3)Stabilization of the carbocation to itself by losing

1) Generation of the electrophile (SO3 or HSO3+)

Dr Elrashied A E Garelnabi Electrophile (neutral molecule)

3) Retaining of the resonance stabilizing the

Sulphonic acid v. strong acid, therefore it is highly ionizable

Like nitration sulphonation does not occur in

Dr Elrashied A E Garelnabi 90%

+ FeCl4 + HCl + FeCl3

The order of reactivity of halogens is F2, Cl2, Br2, I2

The general equation for Friedel-Craft alkylation is

(Actual electrophilic particle)

3) Removal of a proton to a base to retain back the

The R C group called acyl group and the reaction

The Friedel - Craft alkylation and acylation can be

1) Lost of the proton to a base

NH2 , NHR , NHCOCH, 3 NR2, OH

i.e with the general structure

Although O and N are electronegative atoms that can

The carbonyl, cyano and nitro gps inductively

The carbonyl, cyano and nitro gps withdraw es

Substituents with e-withdrawing resonance effect have

Dr Elrashied A E Garelnabi more stable

The special stable hybrid in which the +ve charge

Dr Elrashied A E Garelnabi Special unstable

o, p attacks shows a hybrid in which the +ve

meta attack doesnt show such special unstable

OH and NH2 activate the benzene ring towards

Their direction to the reaction towards o and p

NH2 NH2 NH2 NH2