Aromatic Chemistry

AROMATIC CHEMISTRY
History
The study of organic chemistry is divided into:
• based on carbon
Aliphatic chains
• Based on benzene
Aromatic ring
ARENES
 Aromatic chemistry:
 “aromatic’ referred
to pleasant smells originally
 It comes from the fact that many of these
compounds have a distinctive smell
 Important in the synthesis of many important synthetic
compounds such as drugs dyes, explosives and some
plastics
 Found in:
 painkillers
 antiseptics
 polymers
aspirin
Structure
 Friedrich August Kekule’ : 1st person to propose a
structure for benzene
 He suggested:
 Carbons arranged in a hexagon
 With alternating single and double bonds between them
 With one hydrogen attached to each carbon
Problems with the Kekule’ structure
 3 double bonds- highly unsaturated
 Therefore expected to undergo addition reactions
 BUT it undergoes SUBSTITUTION reactions
Kekulé and the Structure of Benzene
Kekule benzene: two forms are in rapid equilibrium
Irregular hexagon
• In fact, it is 0.139 nm (X-ray diffraction) and is a perfectly
REGULAR HEXAGON (intermediate between C-C and C=C)
• C–C–C bond angles are 120°
• Structure is planar
 Stability
 Real benzene more stable than what Kekule’ proposed
 Enthalpy of hydrogenation and atomization provide further
evidence
Thermochemical evidence
 Enthalpy of hydrogenation
 So when Kekule’ benzene undergoes hydrogenation;

 3 moles of hydrogen are required
 However the real benzene enthalpy is 208 kJ/mol

 Which suggest that the addition of hydrogen to benzene does not involve
‘normal’ double bonds and
 it is actually much more stable than expected
THERMODYNAMIC EVIDENCE FOR STABILITY
When unsaturated hydrocarbons are reduced to the corresponding

saturated compound, energy is released. The amount of heat liberated
per mole (enthalpy of hydrogenation) can be measured.
When unsaturated hydrocarbons are reduced to the corresponding saturated
compound, energy is released. The amount of heat liberated per mole (enthalpy of
hydrogenation) can be measured.
When cyclohexene (one C=C bond) is reduced to

cyclohexane, 120kJ of energy is released per
mole.
C6H10(l) + H2(g) ——> C6H12(l)
2 3
- 120 kJ mol-1

mole.
C6H10(l) + H2(g) ——> C6H12(l) Theoretical

- 360 kJ mol-1
(3 x -120)
Theoretically, if benzene contained three separate
C=C bonds it would release 360kJ per mole when
reduced to cyclohexane
C6H6(l) + 3H2(g) ——> C6H12(l) 2 3
- 120 kJ mol-1

mole.
C6H10(l) + H2(g) ——> C6H12(l) Theoretical

- 360 kJ mol-1
(3 x -120)
C6H6(l) + 3H2(g) ——> C6H12(l) 2 3
Experimental
Actual benzene releases only 208kJ per mole - 120 kJ mol-1 - 208 kJ mol-1
when reduced, putting it lower down the energy
scale

mole.
MORE STABLE
C6H10(l) + H2(g) ——> C6H12(l) Theoretical THAN EXPECTED
- 360 kJ mol-1 by 152 kJ mol-1
(3 x -120)
C6H6(l) + 3H2(g) ——> C6H12(l) 2 3
Experimental
scale
It is 152kJ per mole more stable than expected.

This value is known as the RESONANCE ENERGY.

mole.
MORE STABLE
C6H10(l) + H2(g) ——> C6H12(l) Theoretical THAN EXPECTED
- 360 kJ mol-1 by 152 kJ mol-1
(3 x -120)
C6H6(l) + 3H2(g) ——> C6H12(l) 2 3
Experimental
scale
It is 152kJ per mole more stable than expected.

This value is known as the RESONANCE ENERGY.
STRUCTURE OF ALKENES - REVISION
In ALKANES, the four sp3 orbitals

repel each other into a
tetrahedral arrangement.
In ALKENES, the three

sp2 orbitals repel each
other into a planar
arrangement and the
2p orbital lies at right
angles to them
Covalent bonds are formed An sp2 orbital from each carbon

by overlap of orbitals. overlaps to form a single C-C bond.
The resulting bond is

called a SIGMA (δ) bond.
The two 2p orbitals also overlap. This forms a second bond; it

is known as a PI (π) bond.
For maximum overlap and hence the strongest bond, the 2p

orbitals are in line.
This gives rise to the planar arrangement around C=C bonds.

ORBITAL OVERLAP IN ETHENE - REVIEW
two sp2 orbitals overlap to form a sigma two 2p orbitals overlap to form a pi
bond between the two carbon atoms bond between the two carbon atoms
s orbitals in hydrogen overlap with the the resulting shape is planar

sp2 orbitals in carbon to form C-H bonds with bond angles of 120º
STRUCTURE OF BENZENE - DELOCALISATION
Theory suggested that

instead of three localised (in one position) double bonds,
the six p (p) electrons making up those bonds were delocalised (not in any one
particular position) around the ring by overlapping the p orbitals.
There would be no double bonds and all bond lengths would be equal.
It also gave a planar structure.
6 single bonds

6 single bonds one way to overlap

adjacent p orbitals

6 single bonds one way to overlap another

adjacent p orbitals possibility

6 single bonds one way to overlap another delocalised pi

adjacent p orbitals possibility orbital system
6 single bonds one way to overlap another delocalised pi

adjacent p orbitals possibility orbital system
 This final structure was particularly

stable
 resisted attempts to break it down
through normal electrophilic addition.
 Undergoes substitution reaction.
The Stability of Benzene
Aromaticity: cyclic conjugated organic compounds such as

benzene, exhibit special stability due to resonance delocalization
of  -electrons.
6 -electron delocalized
over 6 carbon atoms
30
30
STRUCTURE OF BENZENE
Substituted Derivatives of Benzene and their Nomenclature
Generally, mono-substituted benzenes are named in a similar manner as

hydrocarbons with -benzene as the parent name
32
32
Nomenclature of Benzene Derivatives
• To name a benzene ring with one substituent, name the substituent and add the word
benzene.
Br CH2CH3
NO2
bromobenzene ethylbenzene (1-methylethyl)benzene nitrobenzene

(isopropylbenzene)
• Many monosubstituted benzenes have common names which you must also learn.
33
Large number of non-systematic names that can serve as the
parent name (Table 11.1)
O H O OH
CH3 OH OCH3 NH2
benzene toluene phenol anisole aniline styrene benzaldehyde benzoic acid

• There are three different ways that two groups can be attached to a benzene
ring, so a prefix—ortho, meta, or para—can be used to designate the
relative position of the two substituents.
ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or or or
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
35
• If the two groups on the benzene ring are different, alphabetize the names
of the substituents preceding the word benzene.
• If one substituent is part of a common root, name the molecule as a
derivative of that monosubstituted benzene.
36
WHY ELECTROPHILIC ATTACK?
Theory
The high electron density of the ring makes it open to attack by
electrophiles (+ species)
HOWEVER...
Because the mechanism involves an initial disruption to the ring,
electrophiles will have to be more powerful than those which react
with alkenes.
A fully delocalised ring is stable so will resist attack.

WHY SUBSTITUTION?
Theory Addition to the ring would upset the delocalised electron system
STABLE DELOCALISED ELECTRONS ARE NOT DELOCALISED

SYSTEM AROUND THE WHOLE RING - LESS
STABLE
Substitution of hydrogen atoms on the ring does not affect the
delocalisation
Overall there is ELECTROPHILIC SUBSTITUTION
ELECTROPHILIC SUBSTITUTION
Theory The high electron density of the ring makes it open to attack by electrophiles
Addition to the ring would upset the delocalised electron system
Substitution of hydrogen atoms on the ring does not affect the delocalisation
Because the mechanism involves an initial disruption to the ring,
electrophiles must be more powerful than those which react with alkenes
Overall there is ELECTROPHILIC SUBSTITUTION
ELECTROPHILIC SUBSTITUTION
Mechanism
• a pair of electrons leaves the delocalised system to form a bond to the

electrophile
• this disrupts the stable delocalised system and forms an unstable

intermediate
• to restore stability, the pair of electrons in the C-H bond moves back into the
ring
• overall there is substitution of hydrogen ... ELECTROPHILIC SUBSTITUTION

ELECTROPHILIC SUBSTITUTION REACTIONS - NITRATION
Reagents conc. nitric acid and conc. sulphuric acid (catalyst)
Conditions reflux at 55°C
Equation C6H6 + HNO3 ———> C6H5NO2 + H2O

nitrobenzene

nitrobenzene
Mechanism

nitrobenzene
Mechanism
Electrophile NO2+ , nitronium ion or nitryl cation; it is generated in an acid-base reaction...

2H2SO4 + HNO3 2HSO4¯ + H3O+ + NO2+
acid base

nitrobenzene
Mechanism
Electrophile NO2+ , nitronium ion or nitryl cation; it is generated in an acid-base reaction...

2H2SO4 + HNO3 2HSO4¯ + H3O+ + NO2+
acid base
Use The nitration of benzene is the first step in an historically important

chain of reactions. These lead to the formation of dyes, and explosives.
ELECTROPHILIC SUBSTITUTION REACTIONS - HALOGENATION
Reagents chlorine and a halogen carrier (catalyst)
Conditions reflux in the presence of a halogen carrier (Fe, FeCl 3, AlCl3)

chlorine is non polar so is not a good electrophile
the halogen carrier is required to polarise the halogen
Equation C6H6 + Cl2 ———> C6H5Cl + HCl
Mechanism
Electrophile Cl+ it is generated as follows...
Cl2 + FeCl3 FeCl4¯ + Cl+

a
Lewis Acid
Play video nitration of benzene
FRIEDEL-CRAFTS REACTIONS OF BENZENE - ALKYLATION
Overview Alkylation involves substituting an alkyl (methyl, ethyl) group
Reagents a halogenoalkane (RX)
Conditions anhydrous aluminium chloride AlCl3 and heat under reflux
Electrophile a carbocation ion R+ (e.g. CH3+)
Equation C6H6 + C2H5Cl ———> C6H5C2H5 + HCl

Overview Alkylation involves substituting an alkyl (methyl, ethyl) group
Reagents a halogenoalkane (RX)
Conditions anhydrous aluminium chloride AlCl 3 and heat under reflux
Electrophile a carbocation ion R+ (e.g. CH3+)
Equation C6H6 + C2H5Cl ———> C6H5C2H5 + HCl
Mechanism
General A catalyst is used to increase the positive nature of the electrophile
and make it better at attacking benzene rings.

Catalyst anhydrous aluminium chloride acts as the catalyst

the Al in AlCl3 has only 6 electrons in its outer shell; a LEWIS ACID
it increases the polarisation of the C-Cl bond in the haloalkane
this makes the charge on C more positive and the following occurs
RCl + AlCl3 AlCl4¯ + R+

FRIEDEL-CRAFTS REACTIONS - INDUSTRIAL ALKYLATION
IndustrialAlkenes are used instead of haloalkanes but an acid must be present

Phenylethane, C6H5C2H5 is made by this method
Reagents ethene, anhydrous AlCl3 , conc. HCl
Electrophile C2H5+ (an ethyl carbonium ion)
Equation C6H6 + C2H4 ———> C6H5C2H5 (ethyl benzene)
Mechanism the HCl reacts with the alkene to generate a carbonium ion
electrophilic substitution then takes place as the C 2H5+ attacks the ring
Use ethyl benzene is dehydrogenated to produce phenylethene (styrene);

this is used to make poly(phenylethene) - also known as polystyrene
FRIEDEL-CRAFTS REACTIONS OF BENZENE - ACYLATION
Overview Acylation involves substituting an acyl (methanoyl, ethanoyl) group
Reagents an acyl chloride and anhydrous aluminium chloride AlCl3
Conditions anhydrous aluminium chloride AlCl 3 and heat under reflux 50°C
Electrophile RC+= O ( e.g. CH3C+O )
Equation C6H6 + CH3COCl ———> C6H5COCH3 + HCl
Mechanism
Product A carbonyl compound (aldehyde or ketone)

SULPHONATION
Overview Involves substituting a HSO3 group into benzene ring.
Reagents fuming sulfuric acid + SO3
Conditions 400C
Electrophile HSO3+
H2SO4
Equation C6H6 + SO3 ———> C6H5SO3H + H+
Mechanism HSO3+ SO3H SO3H

FURTHER SUBSTITUTION OF ARENES
Theory It is possible to substitute more than one functional group.

But, the functional group already on the ring affects...
• how easy it can be done • where the next substituent goes
Group ELECTRON DONATING ELECTRON WITHDRAWING
Example(s) OH, CH3, NO2

Electron density of ring Increases Decreases
Ease of substitution Easier Harder
Position of substitution 2,4,and 6 3 and 5
FURTHER SUBSTITUTION OF ARENES
Examples Substitution of nitrobenzene is...

• more difficult than with benzene
• produces a 1,3 disubstituted product
Substitution of methylbenzene is…

• easier than with benzene
• produces a mixture of 1,2 and 1,4
isomeric products
Some groups (OH) make substitution so much

easier that multiple substitution takes place
STRUCTURAL ISOMERISM
RELATIVE POSITIONS ON A BENZENE RING
1,2-DICHLOROBENZENE 1,3-DICHLOROBENZENE 1,4-DICHLOROBENZENE

ortho dichlorobenzene meta dichlorobenzene para dichlorobenzene
Compounds have similar chemical properties but different physical properties

COMBUSTION OF BENZENE
Combustion of benzene produces a yellow smoky flame.
Equation: 2C6H6(l) + 15O2(g) →12CO2(g) + 6H2O(l)

ADDITION REACTIONS OF BENZENE
Hydrogenation
Reagent: Hydrogen gas
Condition: - Ni catalyst
Temperature: of 420K under high pressure
Type of reaction: Electrophilic addition/ reduction
Products: Cyclohexane
Equation:
2. Halogenation
Reagent: Chlorine gas or bromine vapour
Condition: UV light or bright sunlight
Type of reaction: Free radical addition
Products: Hexabromocyclohexane/hexachlorocyclohexane
Equation of benzene with chlorine/bromine:

OXIDATION OF CARBON-CONTAINING SIDE
CHAINS
Reagent: KMnO4 + dil. NaOH followed by dilute H2SO4
Condition: Heat under reflux
Type of reaction: Oxidation
Observation: Colour changes from purple to green
Products: Benzoic acid

Example 1: Oxidation of methylbenzene
Equation:

Example 2: Oxidation of ethylbenzene

Equation:
HALOGENATION OF CARBON-CONTAINING SIDE
CHAINS
Reagent: Chlorine gas or bromine vapour
Condition: UV light
Type of reaction: Free radical substitution
Example: Chlorination of methylbenzene
Equation:

Aromatic Chemistry

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Aromatic Chemistry

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AROMATIC CHEMISTRY

Kekule benzene: two forms are in rapid equilibrium

• In fact, it is 0.139 nm (X-ray diffraction) and is a perfectly

REGULAR HEXAGON (intermediate between C-C and C=C)

• C–C–C bond angles are 120°

 So when Kekule’ benzene undergoes hydrogenation;

 However the real benzene enthalpy is 208 kJ/mol

When unsaturated hydrocarbons are reduced to the corresponding

When cyclohexene (one C=C bond) is reduced to

C6H10(l) + H2(g) ——> C6H12(l)

When cyclohexene (one C=C bond) is reduced to

C6H10(l) + H2(g) ——> C6H12(l) Theoretical

C6H6(l) + 3H2(g) ——> C6H12(l) 2 3

When cyclohexene (one C=C bond) is reduced to

C6H10(l) + H2(g) ——> C6H12(l) Theoretical

C6H6(l) + 3H2(g) ——> C6H12(l) 2 3

When cyclohexene (one C=C bond) is reduced to

C6H6(l) + 3H2(g) ——> C6H12(l) 2 3

It is 152kJ per mole more stable than expected.

When cyclohexene (one C=C bond) is reduced to

C6H6(l) + 3H2(g) ——> C6H12(l) 2 3

It is 152kJ per mole more stable than expected.

In ALKANES, the four sp3 orbitals

In ALKENES, the three

Covalent bonds are formed An sp2 orbital from each carbon

The resulting bond is

The two 2p orbitals also overlap. This forms a second bond; it

For maximum overlap and hence the strongest bond, the 2p

This gives rise to the planar arrangement around C=C bonds.

s orbitals in hydrogen overlap with the the resulting shape is planar

Theory suggested that

Theory suggested that

6 single bonds one way to overlap

Theory suggested that

6 single bonds one way to overlap another

Theory suggested that

6 single bonds one way to overlap another delocalised pi

6 single bonds one way to overlap another delocalised pi

 This final structure was particularly

Aromaticity: cyclic conjugated organic compounds such as

Generally, mono-substituted benzenes are named in a similar manner as

bromobenzene ethylbenzene (1-methylethyl)benzene nitrobenzene

benzene toluene phenol anisole aniline styrene benzaldehyde benzoic acid

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

A fully delocalised ring is stable so will resist attack.

STABLE DELOCALISED ELECTRONS ARE NOT DELOCALISED

• a pair of electrons leaves the delocalised system to form a bond to the

• this disrupts the stable delocalised system and forms an unstable

• overall there is substitution of hydrogen ... ELECTROPHILIC SUBSTITUTION

Reagents conc. nitric acid and conc. sulphuric acid (catalyst)

Conditions reflux at 55°C

Equation C6H6 + HNO3 ———> C6H5NO2 + H2O

Reagents conc. nitric acid and conc. sulphuric acid (catalyst)

Conditions reflux at 55°C

Equation C6H6 + HNO3 ———> C6H5NO2 + H2O

Reagents conc. nitric acid and conc. sulphuric acid (catalyst)

Conditions reflux at 55°C

Equation C6H6 + HNO3 ———> C6H5NO2 + H2O

Electrophile NO2+ , nitronium ion or nitryl cation; it is generated in an acid-base reaction...

Reagents conc. nitric acid and conc. sulphuric acid (catalyst)

Conditions reflux at 55°C

Equation C6H6 + HNO3 ———> C6H5NO2 + H2O

Electrophile NO2+ , nitronium ion or nitryl cation; it is generated in an acid-base reaction...