Lecturer 3 21 Oct 2024
ALKYL BENZENE
6.1. Methods of Preparation
6.1.1. Friedel-Crafts Reaction
6.1.3. Using a Grignard Reagent
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6.2. Reactions of alkylbenzenes:
6.2.1. Hydrogenation: Catalytic hydrogenation of toluene yields methyl cyclohexane.
6.2.2. Oxidation: Under the influence of strong oxidizing agents, such as potassium permanganate
or dichromate, the side chain (however long it) is transformed into a carboxylic group, and
benzoic acid is obtained.
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6.2.3. Electrophilic aromatic substitution:
Because of its electron-releasing effect, an alkyl group activates a benzene ring, and directs ortho
and para positions.
6.2.3.1. Nitration: When toluene is treated with the nitrating mixture (conc. HNO3 + conc. H2SO4),
a mixture of o- and p-nitrotoluene is obtained. Further nitration leads to the formation of
trinitrotoluene.
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6.2.3.2. Sulfonation of toluene:
6.2.3.2. ChloroSulfonation of toluene:
6.2.3.3. Friedel-Crafts Reaction
(1) Alkylation: The reaction of toluene with methyl chloride in presence of aluminum chloride yields
a mixture of the xylenes.
(2) Acylation: Acylation of toluene yields the p-substituted derivative.
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6.2.3.4. Halogenation
1) In the presence of a halogen carrier, chloride (or bromide) attacks the ring to give a mixture
of ortho- and para-chlorotoluene.
1) In presence of sunlight and high temperature, the side chain exclusively attacked.
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Aromatic HALOGEN COMPOUNDS
7.1. Preparations of Aryl Halide
7.1.1. Direct halogenation:
(a) Aryl Chlorides and Aryl Bromides are generally prepared by the direct halogenation of aromatic
hydrocarbons in the presence of a Lewis catalyst, such as AlBr3, AlCl3, or FeCl3.
(b) Aryl iodides are obtained in good yield is presence of reagents like HgO, HNO3, which remove
the HI produced in the reaction.
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7.2. Reactions of aryl halides
7.2.1. Electrophilic Substitution in Benzene Ring:
Aryl halides undergo substitution in the benzene ring with electrophilic reagents to form ortho and
para derivatives as the major product. Thus,
(a) Nitration:
However, it may be noted that such electrophilic substitution reactions do not take place very
readily. In the above reaction, the chlorine is not a good donor of electrons by resonance.
(b) Sulphonation:
(b) Friedel-craft Reaction:
(i) Alkylation:
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(ii) Acylation:
c)Halogenation:
7.2.2. Ullmann Reaction: Ullman found that aryl halides when refluxed with copper powder
undergo coupling reaction to form biaryls. Thus,
Aryl chlorides and bromides usually do not give this reaction unless the halogen is activated by
a suitable substiuent (NO2) in trhe ortho or para position.
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7.2.3. Wurtz-Fittig Reaction.
Aryl halides and akly halides undergo coupling reaction in the presence of sodium in ether to
form alkylated aromatic hydrocarbons (arenes). This reaction is often referred to as Wurtz-Fittig
Reaction since it is an extension of Wurtz Reaction discovered by Fittig (1863).
7.2.4. Formation of Grignard reagents:
7.2.5. Nucleophilic aromatic substitution:
The simplest and most obvious nucleophilic substitutions on an aromatic ring, such as the
displacement of bromide from bromobenzene with hydroxide ion, do not occur. Please note—
this mechanism is wrong! No such reactions are known. You might well ask, ‘Why not?’ The reaction
looks all right and, if the ring were saturated, it would be all right.
The low reactivity of aromatic halogen to nucloephiles is attributed to the facts: (1) the halogen has
a charge on it; and (2) aryl halides could be represented as resonance hybrid whereby C-X bond in
them possesses a double bond character and is stronger than C-X bond in alkyl halides.
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The mechanism involves addition of the nucleophile followed by elimination of the leaving group—the
addition–elimination mechanism. It is not necessary to have a carbonyl group—any electron-
withdrawing group will do—the only requirement is that the electrons must be able to get out of
the ring into this anion-stabilizing group. Here is an example with a para-nitro group.
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7.2.5. ADDITION HALOGEN COMPOUNDS
DDT, 2,2-di(p-chlorophenyl)-1,1,1-trichloroethane. The initial DDT
Benzal Chloride, Benzilidene Chloride, C6H5CH2Cl
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Benzotrichlorides, Phenylchloroform, C6H5-CCl3.
It is prepared by passing chlorine into boiling toluene till no further increase in weight takes
place.
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