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SCH 2202 Part 3 Organic Chemistry II 2nd March 2024

The document covers the structure and properties of benzene, including its molecular orbital structure and criteria for aromaticity. It discusses the toxicity of benzene and the five main electrophilic substitution reactions that occur with benzene, detailing mechanisms and effects of substituents on reactivity. Additionally, it addresses the reactions of substituted benzenes and the influence of activating and deactivating groups on electrophilic aromatic substitution.

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27 views55 pages

SCH 2202 Part 3 Organic Chemistry II 2nd March 2024

The document covers the structure and properties of benzene, including its molecular orbital structure and criteria for aromaticity. It discusses the toxicity of benzene and the five main electrophilic substitution reactions that occur with benzene, detailing mechanisms and effects of substituents on reactivity. Additionally, it addresses the reactions of substituted benzenes and the influence of activating and deactivating groups on electrophilic aromatic substitution.

Uploaded by

perismbici526
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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SCH 2202 ORGANIC CHEMISTRY II

JANUARY-APRIL 2024
JKUAT- DEPT OF CHEMISTRY
BENZENE AND AROMATICITY
STRUCTURE OF BENZENE
Molecular orbital structure of benzene
Criteria for Aromaticity
Cont.d…
Cont.d…
Contd..
Note that:
Examples of Aromatic Rings
Aromatic Heterocyclic Compounds
Nomenclature of Benzene derivatives

Systematic names(mono and disubstituted)


Two different substituents
Common names
Note that:-
Three substituents
THE TOXICITY OF BENZENE
 Although benzene has been widely used in
chemical synthesis and has been frequently used
as a solvent, it is toxic.
 Its major toxic effect is on the central nervous
system and on bone marrow.
 Chronic exposure to benzene causes leukemia
and aplastic anemia.
 Toluene has replaced benzene as a solvent
because, although it is a central nervous system
depressant like benzene, it does not cause
leukemia or aplastic anemia.
ELECTROPHILIC SUBSTITUTION REACTIONS -
How Benzene Reacts
 When an electrophile attaches itself to a benzene
ring, a carbocation intermediate is formed
Stability of aromatic product
Reaction coordinate
Five most common electrophilic aromatic substitution
reactions:
 1. Halogenation: A bromine (Br), a chlorine (Cl), or an
iodine (I) substitutes for a hydrogen.
 2. Nitration: A nitro group substitutes for a hydrogen.
 3. Sulfonation: A sulfonic acid group substitutes for a
hydrogen.
 4. Friedel–Crafts acylation: An acyl group substitutes for
a hydrogen.
 5. Friedel–Crafts alkylation: an alkyl (R) group
substitutes for a hydrogen.
All of these electrophilic aromatic
substitution reactions take place by the
same two-step mechanism.
Halogenation of Benzene
Mechanisms of bromination and chlorination
Nitration of Benzene

• To generate the necessary electrophile, sulfuric acid


protonates nitric acid.
• Loss of water from protonated nitric acid forms a nitronium
ion, the electrophile required for nitration.
• Any base present in the reaction mixture ( eg HSO4¯) can
remove the proton in the second step of the aromatic
substitution reaction
mechanism
Sulfonation of Benzene
Friedel–Crafts Acylation of Benzene
Mechanism:-
(Acylium ion is the electrophile)
Because the product of a Friedel–Crafts acylation
reaction contains a carbonyl group that can complex
with AlCl3 Friedel–Crafts acylation reactions must be
carried out with more than one equivalent of AlCl3.
When the reaction is over water is added to the
reaction mixture to liberate the product from the
complex.
Friedel–Crafts Alkylation of Benzene
Rearrangement of carbocations:-
1. Primary to secondary carbocation
Contd…
2. primary carbocation rearranges to a
tertiary carbocation
In addition to reacting with carbocations generated from
alkyl halides, benzene can react with carbocations generated
from the reaction of an alkene or an alcohol with an acid.
Alkylation of Benzene by Acylation–Reduction-
Good yield of an alkylbenzene containing a straight-
chain alkyl group via a Friedel–Crafts alkylation
reaction is not possible due to carbocation
rearrangement reactions.

This can be achieved by carrying out a Friedel–Crafts


acylation reaction, followed by reduction of the carbonyl
group to a methylene group.
Only a ketone carbonyl group that is adjacent to
a benzene ring can be reduced to a methylene
group by catalytic hydrogenation
Other reduction methods
Questions
REACTIONS OF SUBSTITUTED BENZENES
 Substituted benzenes ALSO undergo the five electrophilic
aromatic substitution reactions
 Electron-donating substituents increase the reactivity of the
benzene ring toward electrophilic aromatic substitution

 Electron-withdrawing substituents decrease the reactivity of


the benzene ring toward electrophilic aromatic substitution
Activating groups:- Consider the nitration of toluene

What is the effect of the methyl group on the rate of


nitration? Toluene reacts much faster than benzene. The
CH3 group is electron-donating, making the ring a better
nucleophile
What is the effect of the methyl group on the
regioselectivity of the reaction?
There are three possible products: the nitro group could
be installed at ortho, meta or para positions
Activating groups

 The ortho and para products predominate. Very


little meta product is formed
Compare the relative stability of the carbocation
(sigma-complex) intermediate
The carbocations obtained from ortho and para attack
has positive charge delocalized adjacent to the electron
donating CH3 group, giving a more stable intermediate
More ortho is formed because there are two
ortho positions and only one para position
Activating groups:- Methoxy(–OCH3) group
• The methoxy group in anisole activates the ring
400 times more than benzene
• The methoxy group donates electron density via
resonance
The –OCH3 group is activating and an ortho-para
director

Here, para is the major, due to the ortho position(s)


being more sterically hindered
Resonance stabilizes carbocations of ortho and para
attack
Deactivating groups –e.g; The nitro (–NO2) group
 It is both inductively electron withdrawing

and withdraws electron density from


the ring via resonance:-
Meta director
 Nitrobenzene deactivates benzene and
 undergoes nitration much slower than benzene
Carbocation intermediates
Summary

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