Benzene and Friedel-
Craft reactions
01
Benzene
Reactions
Learning Objectives
01 02
Reactions of Friedel-Craft
benzene reactions
03 04
Naming of aromatic Electrophilic
compounds substitution
Reactions as Hydrocarbon:Hydrogenation
Reactions as Hydrocarbon: Hydrogenation
Reactions as Hydrocarbon:Hydrogenation
Conditions
Catalyst: Nickel
Temperature: 300 C
Pressure : 30 atm
Reactions as Hydrocarbon: Combustion
Burns with smoky flame
Reactions as an Arene
Arenes are very stable compounds due to the delocalisation of π electrons in the ring
This is because the negative charge is spread out over the molecule instead of being confined to a small
area
Arenes undergo a series of reactions including:
Substitution :
● Arenes undergo substitution reactions with chlorine (Cl2) and
bromine (Br2) in the presence of anhydrous AlCl3 or AlBr3
catalyst respectively to form halogenoarenes (aryl halides)
● The chlorine or bromine act as an electrophile and replaces a
hydrogen atom on the benzene ring
● The catalyst is required for the reaction to take place, due to the
stability of the benzene structure
During chemical reactions such as substitution reactions, this delocalised ring is maintained
Addition reactions however, disrupt the aromatic stabilisation
NITRATION :
● Another example of a
substitution reaction is the
nitration of arenes
● In these reactions, a nitro (-NO2)
group replaces a hydrogen atom
on the arene
● The benzene is reacted with a
mixture of concentrated nitric
acid (HNO3) and concentrated
sulfuric acid (H2SO4) at a
temperature between 25 and
60C
02
Friedel Craft
Reactions
Types: Acylation and alkylation
Friedel-Crafts Reaction: Acylation
Acylation is the substitution of one of the hydrogen atoms of benzene by an acyl
group. The reagent is an acyl chloride and the product is a ketone
(phenylethanone) and hydrogen chloride. The equation of this reaction with
ethanoyl chloride is:
Acylation mechanism
This process is electrophilic substitution
○ An acyl group is an alkyl group containing a carbonyl, C=O group
● The benzene ring is reacted with an acyl chloride in the presence of an AlCl3 catalyst
Friedel Crafts Reaction: Alkylation
Alkylation means the substitution of one of the hydrogen atoms with benzene by
an alkyl group.The reagent is a halogenoalkane and the products are;
● AlkylBenzene
● Hydrogen chloride (HCL)
A catalyst is needed -often aluminium chloride although iron(iii)chloride and
iron(iii)Bromide could also work.
Anhydrous conditions are needed because water could react with the catalyst
and sometimes also with the organic product.
Alkylation mechanism
Friedel-Crafts alkylation
● In this type of Friedel-Crafts reaction, an alkyl chain is substituted into the benzene ring
● The benzene ring is reacted with a chloroalkane in the presence of an AlCl3 catalyst
● An example of an alkylation reaction is the reaction of benzene with chloropropane (CH3CH2CH2Cl) to form propylbenzene.
Step 1
The Lewis acid catalyst (AlCl3) undergoes reaction with the alkyl halide,
resulting in the formation of an electrophilic carbocation.
Step 2
The carbocation proceeds to attack the aromatic ring, forming a cyclohexadienyl
cation as an intermediate. The aromaticity of the arene is temporarily lost due to
the breakage of the carbon-carbon double bond.
Step 3
The deprotonation of the intermediate leads to the reformation of the carbon-
carbon double bond, restoring aromaticity to the compound. This proton goes
on to form hydrochloric acid, regenerating the AlCl3 catalyst
SULFONATION
Sulfonation is a reversible reaction that refers to the replacement of a hydrogen atom by a-
SO3H group
● The reaction is carried out by warming benzene with fuming sulfuric acid at 40
degrees celcius for 20 to 30 mins
● The reaction is reversed by adding hot aqueous acid to benzenesulfonic acid to
produce benzene
+H2
O
BROMINATION OF BENZENE
● A SUBSTITUTION REACTION
● BENZENE AND BROMINE ARE HEATED UNDER REFLUX
● CATALYST- A HALOGEN CARRIER (eg. aluminium chloride, aluminium
bromide or iron (III) bromide
● PRODUCTS ARE BROMOBENZENE AND HYDROGEN BROMIDE
BROMINATION MECHANISM
STEP 3: AROMATIC PRODUCT
STEP 1: ELECTROPHILE FORMATION FORMATION
STEP 2: ELECTROPHILIC ATTACK STEP 4: CATALYST REGENERATION
Nitration of benzene
The reaction is carried out by warming benzene with a mixture of concentrated nitric and sulfuric acids.
The nitric acid can be considered as the source of the NO2 group and the sulfuric acid as a catalyst. The
products are nitrobenzene and water.
The temperature should not exceed 50 degrees C because as temperature increases there is a greater
chance of getting more than one nitro group, -NO2, substituted onto the ring.
Thanks
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