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Substituent Effects on Aromatic Reactions

The document discusses the effects of substituents on the electrophilic aromatic substitution of substituted benzene rings, highlighting how electron-donating groups (EDGs) activate the ring while electron-withdrawing groups (EWGs) deactivate it. It explains that the identity of the first substituent influences the rate and orientation of subsequent substitutions, leading to the formation of isomers. Additionally, it notes that halogens are unique as they act as deactivators yet direct substitutions to ortho and para positions due to resonance effects.

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Robert Simazuo
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24 views18 pages

Substituent Effects on Aromatic Reactions

The document discusses the effects of substituents on the electrophilic aromatic substitution of substituted benzene rings, highlighting how electron-donating groups (EDGs) activate the ring while electron-withdrawing groups (EWGs) deactivate it. It explains that the identity of the first substituent influences the rate and orientation of subsequent substitutions, leading to the formation of isomers. Additionally, it notes that halogens are unique as they act as deactivators yet direct substitutions to ortho and para positions due to resonance effects.

Uploaded by

Robert Simazuo
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© All Rights Reserved
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Substituent Effects of Substituted Benzenes

• Many substituted benzene rings undergo electrophilic aromatic substitution.


• Each substituent either increases or decreases the electron density in the
benzene ring, and this affects the course of electrophilic aromatic substitution.
• Donation of electron density to the ring makes benzene more electron rich and
more likely to react with an electrophile.
• Withdrawal of electron density from the ring makes benzene less electron rich
and less likely to react with an electrophile.
• Electrophilic substitution on an already substituted benzene can produce
isomers, some of which are favored over others.

Substituent Effects on Electrophilic Aromatic Substitution


• Electrophilic aromatic substitution is a general reaction of all aromatic compounds,
including polycyclic aromatic hydrocarbons, heterocycles, and substituted benzene
derivatives.
• A substituent affects two aspects of the electrophilic aromatic substitution reaction:
1. The rate of the reaction: A substituted benzene reacts faster or slower than benzene itself.
2. The orientation: The new group is located either ortho, meta, or para to the existing
substituent.
• The identity of the first substituent determines the position of the second incoming
substituent.
Directing Effects
EDG EWG

electron donating groups electron withdrawing groups


activate ring deactivate ring

atom attached is atom attached is


usually sp3 usually sp2 or sp
ortho/para-Directing
Activating Groups

OCH3 OCH3 OCH3 OCH3

+
d OCH3
- -
d d

-
d
Nitration of Anisole
Nitration Affords
ortho and para Products

OCH3 OCH3 OCH3


NO2
HNO3, H2SO4
+

ortho para
NO2
Activating ortho/para directors
meta-Directing
Deactivating Groups
O O O O
CH CH CH CH

d -
O
CH
+ ortho and para positions
d +
d are deactivated toward
EAS
d+
Electron-Withdrawing Nitro Group Directs
meta
meta Directors
Comparison
CH3 Brominated product
ortho meta para rel. rate
63 3 34 25
rate rel. to
Br2, FeBr3
benzene
CF3
ortho meta para
6 91 3 0.000025
More Limitations with
Friedel Crafts Reactions
Ring must be at least as
activated (reactive) as
Cl Cl

CH3CH2Cl, TiCl4 + ortho

O
NO2 CH2CH3
ClCCH3, AlCl3
No Reaction
Substituent Summary
16
Halogens are the Anomoly
Deactivators and o,p-Directors

Br Br Br
CH2CH3
CH3CH2Cl
+
AlCl3
rel. rate = 0.5
CH2CH3

Inductively withdrawing, hence deactivating


Resonance donation causes o,p directing
Reactions of Rings With
Two or More Substituents

Activating Group Controls Reaction


OCH3 OCH3
Cl
Cl2, FeCl3

NO2 NO2

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