Hydrocarbons

15.3 Arenes
 i - Nomenclature
• Benzene molecular formula C6H6, skeletal formula ,
structural/displayed formula
methylbenzene (toluene) ethylbenzene propylbenzene

The C6H5- aromatic ring grouping is called a phenyl group when

quoted as a substituent prefix.
 i - Nomenclature

When have two substituents, use ortho (1,2), meta (1,3) and para
(1,4)
CH3 CH3 CH3 CH3
CH3

CH3
CH3
toluene o-xylene m-xylene p-xylene

1,2-diethylbenzene 1,3-dipropylbenzene
 i - Nomenclature
• If the OH group (hydroxy) is directly attached to a benzene ring, the
molecule is classified as a 'phenol'.
If not, the molecule is classified as an
aliphatic alcohol.

2-chlorophenol (o-chlorophenol) 3-methylphenol (m-methylphenol)

If the OH is not attached to a benzene ring you get an aliphatic alcohol

which is isomeric with a phenols or an ether.

phenylmethanol (old name 'benzyl alcohol') is a primary

aliphatic alcohol
 i - Nomenclature

benzene derivatives :
Example : .
2-aminophenol 4-aminophenol 2-nitrophenol

3-hydroxybenzoic acid 2,5-dichloro-4-methylphenol

2-hydroxybenzaldehyde 1-phenylethanone
Substitution Reactions of Benzene and Its
Derivatives
• Benzene is aromatic: a cyclic conjugated compound
with 6  electrons
• Reactions of benzene lead to the retention of the
aromatic core
• Electrophilic aromatic substitution replaces a proton
on benzene with another electrophile

McMurry Organic Chemistry 6th edition

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Chapter 16 (c) 2003
 .
.
 Nitration of benzene
• The combination of nitric acid and sulfuric acid produces
NO2+ (nitronium ion)
• The reaction with benzene produces nitrobenzene

9
MECHANISM FOR NITRATION OF BENZENE
Step 1: .
An acid / base reaction. Protonation of the hydroxy
group of the nitric acid. This provides a better leaving
group.....
Step 2:
Loss of the leaving group, a water molecule provides the
nitronium ion, the reactive electrophile.
Step 3:
The electrophilic nitronium ion reacts with the
nucleophilic C=C of the arene. This is the rate
determining step as it destroys the aromaticity of the
arene.
Step 4:
Water functions as a base to remove the proton from the
sp3 C bearing the nitro- group and reforms the C=C and
the aromatic system.
 Halogenation of Benzene
Overall transformation : Ar-H to Ar-X
Reagent : normally the halogen (e.g. Br2) with a Lewis acid catalyst
The active catalyst is not Fe (0) but the FeX3 formed by reaction of
Fe with X2
Electrophilic species : the halonium ion (i.e. X +) formed by the
removal of a halide ion by the Lewis acid catalyst
Restricted to Cl2 and Br2. I- or F- are usually introduced using
alternative methods
Step 1:
.
The bromine reacts with the Lewis acid to form
a complex that makes the bromine more electrophilic.
Step 2:
The p electrons of the aromatic C=C act as a
nucleophile, attacking the electrophilic Br, and
displacing iron tetrabromide. This step destroys
the aromaticity giving the cyclohexadienyl
cation intermediate.
Step 3:
Removal of the proton from the sp3 C bearing
the bromo- group reforms the C=C and the
aromatic system, generating HBr and regenerating
the active catalyst.
 Aromatic Chlorination and Iodination
• Chlorine and iodine (but not fluorine, which is too
reactive) can produce aromatic substitution with the
addition of other reagents to promote the reaction
• Chlorination requires FeCl3
• Iodine must be oxidized to form a more powerful I+
species (with Cu+ or peroxide)

13
 Sulfonation of Benzene
Overall transformation : Ar-H to Ar-SO3H, a sulfonic acid.
Reagent : for benzene, H2SO4 / heat or SO3 / H2SO4 / heat
(= fuming sulfuric acid)
Electrophilic species : SO3 which can be formed by the loss of water
from the sulfuric acid
Unlike the other electrophilic aromatic substitution reactions,
sulfonation is reversible.
Removal of water from the system favours the formation of the
sulfonation product.
Heating a sulfonic acid with aqueous sulfuric acid can result be the
reverse reaction, desulfonation.
Sulfonation with fuming sulfuric acid strongly favours formation of
the product the sulfonic acid.
Step 1:
.
The p electrons of the aromatic C=C act as
a nucleophile, attacking the electrophilic S,
pushing charge out onto an electronegative
O atom. This destroys the aromaticity giving
the cyclohexadienyl cation intermediate.
Step 2:
Loss of the proton from the sp3 C bearing
the sulfonyl- group reforms the C=C and the
aromatic system.
Step 3:
Protonation of the conjugate base of the
sulfonic acid by sulfuric acid produces the
sulfonic acid.
Alkali Fusion of Aromatic Sulfonic Acids
• Sulfonic acids are useful as intermediates
• Heating with NaOH at 300 ºC followed by neutralization
with acid replaces the SO3H group with an OH
• Example is the synthesis of p-cresol

McMurry Organic Chemistry 6th edition

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Chapter 16 (c) 2003
 Friedel-Crafts Alkylation of Benzene
• Overall transformation : Ar-H to Ar-R
• Named after Friedel and Crafts who discovered the reaction in
1877.
• Reagent : normally the alkyl halide (e.g. R-Br or R-Cl) with aluminum
trichloride, AlCl3, a Lewis acid catalyst
• The AlCl3 enhances the electrophilicity of the alkyl halide by
complexing with the halide
• Electrophilic species : the carbocation (i.e. R +) formed by the
"removal" of the halide by the Lewis acid catalyst
• The reactive electrophile, the carbocation is prone to
rearrangement to a more stable carbocation which will then
undergo the alkylation reaction.
Friedel-Crafts reactions are limited to arenes as or more reactive
than mono-halobenzenes Other . Lewis acids such as BF , FeCl or
3 3
ZnCl2 can also be used .Other sources of carbocations can also
be used:
• from loss of water from alcohols treated with acid
• from the protonation of alkenes by acid
MECHANISM FOR THE FRIEDEL-CRAFTS
ALKYLATION OF BENZENE .

Step 1:
The alkyl halide reacts with the Lewis acid to
form a more electrophilic C, a carbocation
Step 2:
The p electrons of the aromatic C=C act as a
nucleophile, attacking the electrophilic C+.
This step destroys the aromaticity giving the
cyclohexadienyl cation intermediate.
Step 3:
Removal of the proton from the sp3 C bearing
the alkyl- group reforms the C=C and the
aromatic system, generating HCl and
regenerating the active catalyst.
Limitations of the Friedel-Crafts Alkylation

• Only alkyl halides can be used (F, Cl, I, Br)

• Aryl halides and vinylic halides do not react (their
carbocations are too hard to form)
• Will not work with rings containing an amino group
substituent or a strongly electron-withdrawing group

McMurry Organic Chemistry 6th edition

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Chapter 16 (c) 2003
 Friedel-Crafts Acylation of Benzene

• Overall transformation : Ar-H to Ar-COR (a ketone)

• Reagent : normally the acyl halide (e.g. usually RCOCl)
with aluminum trichloride, AlCl3, a Lewis acid catalyst
The AlCl3 enhances the electrophilicity of the acyl
halide by complexing with the halide Electrophilic
species : the acyl cation or acylium ion (i.e. RCO + )
formed by the "removal" of the halide by the Lewis
acid catalyst
 .
• The acylium ion is stabilized by resonance as shown below.
This extra stability prevents the problems associated with
the rearrangement of simple carbocations:

• The reduction of acylation products can be used to give the

equivalent of alkylation but avoids the problems of
rearrangement (more details)
• Friedel-Crafts reactions are limited to arenes more reactive
than mono-halobenzenes
• Other sources of acylium can also be used such as acid
anhydrides with AlCl3
 MECHANISM FOR THE FRIEDEL-CRAFTS ACYLATION
OF BENZENE
Step 1:
The acyl halide reacts with the Lewis acid
to form a more electrophilic C, an acylium
ion
Step 2:
The p electrons of the aromatic C=C act as
a nucleophile, attacking the electrophilic
C+. This step destroys the aromaticity
giving the cyclohexadienyl cation
intermediate.
Step 3:
Removal of the proton from the sp3 C
bearing the acyl- group reforms the C=C
and the aromatic system, generating HCl
and regenerating the active catalyst.
 .
Thus, there are two types of Friedel-Crafts reactions, alkylation
and acylation:

Example :
Stability of benzene towards oxidation
• Double bonds of benzene are more stable than aliphatic
alkenes due to the :
– delocalisation of 6 π electrons among the 6 carbons in the
ring.
– The formation of resonance structures.
• So that, benzene does not undergo oxidation.
• Benzene also does not undergo reduction process since it does
not react with oxidizing agents such as acidified KMnO4 and
acidified KCr2O7. However, the exception occur when benzene
can be reduced to cyclohexane in presence of H2 gas with
Nickel as catalyst at 180 oC.
• The test to differentiate alkene and benzene :
– Put chemical in cold KMnO4. If the chemical decolourise the
dark puple colour, then the chemical does not contain ring
structure.
 Self-assessment

.
 .
.
 15.3 Arenes
Chemicals Reaction of Benzene
From previous section (benzene) here is the summary:

2
 Substituent Effects in Aromatic Rings
• Substituents can cause a compound to be (much) more or
(much) less reactive than benzene

• Substituents affect the orientation of the reaction – the

positional relationship is controlled

• ortho- and para-directing activators, ortho- and para-

directing deactivators, and meta-directing deactivators.
3
 Origins of Substituent Effects
• An interplay of inductive effects and resonance effects

• Inductive effect - withdrawal or donation of electrons through

a s bond = Polar Covalent Bonds

• Resonance effect - withdrawal or donation of electrons

through a  bond due to the overlap of a p orbital on the
substituent with a p orbital on the aromatic ring

4
 Inductive Effects
• Controlled by electronegativity and the polarity of bonds
in functional groups
• Halogens, C=O, CN, and NO2 withdraw electrons through
s bond connected to ring
• Alkyl groups donate electrons

5
 Resonance Effects – Electron Withdrawal
• C=O, CN, NO2 substituents withdraw electrons from the
aromatic ring by resonance
•  electrons flow from the rings to the substituents
• Look for a double (or triple) bond connected to the ring
by a single bond

6
 Resonance Effects – Electron Donation
• Halogen, OH, alkoxyl (OR), and amino substituents donate
electrons
•  electrons flow from the substituents to the ring
• Effect is greatest at ortho and para positions
• Look for a lone pair on an atom attached to the ring

7
 Substituent Effects
E
+ E+
Nucleophile Electrophile

 Substituent that donate electrons make ring more nucleophilic

 Electron donating groups (EDG) activate the ring toward EAS
 Substituent that withdraw electrons make less nucleophilic
 Electron withdrawing groups (EWG) deactivate the ring toward EAS

8
 Substituent Effects
• Substituents influence by induction

EDG activate the ring toward EAS EWG deactivate the ring toward EAS

Halogens, C=O, CN, and NO2

withdraw electrons through s
bond connected to ring
Alkyl groups donate electrons
9
 Substituent Effects
• Substituents influence by resonance
Halogen, OH, alkoxyl (OR), and amino substituents donate electrons

EDG activate the ring toward EAS

10
 Substituent Effects
• Substituent influence by resonance
C=O, CN, NO2 substituents withdraw electrons from the aromatic ring by resonance

11
ewg deactivate the ring toward EAS
 Ortho- & Para-Directing Activators: Alkyl
Groups
• Alkyl groups activate: direct further substitution to positions ortho and para
to themselves

12
 Ortho- and Para-Directing Activators: OH
and NH2
• Alkoxyl, and amino groups have a strong, electron-donating resonance
effect

Most pronounced
at the ortho and
para positions
13
 Ortho- & Para-Directing Deactivators:
Halogens
• Electron-withdrawing inductive effect outweighs weaker electron-donating
resonance effect

Resonance
effect is only at
the ortho and
para positions,
stabilizing
carbocation
intermediate
14
 Meta-Directing Deactivators
• Inductive and resonance effects reinforce each other
• Ortho and para intermediates destabilized by deactivation of carbocation
intermediate

Resonance
cannot produce
stabilization

15
 Reactivity
• .
 Orientation

17
 1) Halogenation of alkylbenzene
• There are two conditions :
• If ultraviolet or sunlight present : Free radical
substitution of the alkyl side chain
• If Lewis acid is present : Electrophilic aromatic
substitution of the benzene ring
 1.1 Free-radical Chlorination of Toluene

Cl2
CH3 CH2Cl
light
or
heat

Toluene Benzyl chloride

industrial process
highly regioselective for benzylic position
 Free-radical Chlorination of Toluene

Similarly, dichlorination and trichlorination are

selective for the benzylic carbon. Further
chlorination gives:

CHCl2 CCl3

(Dichloromethyl) benzene (Dichloromethyl) benzene

 Benzylic Bromination

is used in the laboratory to introduce a

halogen at the benzylic position
CH3 CH2Br

CCl4, 80°C
+ Br2 + HBr
light

NO2 NO2

p-Nitrotoluene p-Nitrobenzyl
bromide (71%)
 N-Bromosuccinimide (NBS)

is a convenient reagent for benzylic bromination

Br

O CH2CH3 O CHCH3

CCl4
NBr + NH +
benzoyl
peroxide,
O heat O

(87%)
 .
• .
 1.2 EAS on benzene ring
• Substitution in the ring happens in the presence of
aluminium chloride (or aluminium bromide if you are using
bromine) or iron.
• This is exactly the same as the reaction with benzene,
except that you have to worry about where the halogen
atom attaches to the ring relative to the position of the
methyl group.
• Methyl groups are 2,4-directing, which means that
incoming groups will tend to go into the 2 or 4 positions on
the ring - assuming the methyl group is in the 1 position. In
other words, the new group will attach to the ring next
door to the methyl group or opposite it.
 .
• With chlorine, substitution into the ring gives
a mixture of 2-chloromethylbenzene and 4-
chloromethylbenzene.
 2)Oxidation of Alkylbenzene
• Methylbenzene is heated under reflux with a solution of
potassium manganate(VII) made alkaline with sodium carbonate.
The purple colour of the potassium manganate(VII) is eventually
replaced by a dark brown precipitate of manganese(IV) oxide.
• The mixture is finally acidified with dilute sulphuric acid.
• Overall, the methylbenzene is oxidised to benzoic acid.

26
 .
CH3

or
Na2Cr2O7
O
H2SO4
CH2R COH
H2O

or heat

CHR2
 Example

CH3 COH
Na2Cr2O7
H2SO4

H2O
heat

NO2 NO2

p-Nitrotoluene p-Nitrobenzoic
acid (82-86%)
Example
O

CH(CH3)2 COH
Na2Cr2O7
H2SO4

H2O
heat

CH3 COH

(45%)
 3) Friedel-Crafts acylation of
alkylbenzene
• The reaction is just the same with benzene except that you
have to worry about where the acyl group attaches to the
ring relative to the methyl group.

• Normally, the methyl group in methylbenzene directs new

groups into the 2- and 4- positions (assuming the methyl
group is in the 1- position
 4) Friedel-Crafts alkylation of
alkylbenzene
• Again, the reaction is just the same with benzene
except that you have to worry about where the
alkyl group attaches to the ring relative to the
methyl group.
 4) Nitration of alkylbenzene
• Methylbenzene reacts rather faster than benzene - in nitration, the
reaction is about 25 times faster. That means that you would use a
lower temperature to prevent more than one nitro group being
substituted - in this case, 30°C rather than 50°C. Apart from that,
the reaction is just the same - using the same nitrating mixture of
concentrated sulphuric and nitric acids.
• Products formed: 2-nitromethylbenzene and 4-nitromethylbenzene.