Rationalizing Substituent Effects for Electrophilic

Aromatic Substitution Reactions

RDS
EWG
EWG
RDS
A + E
RDS
E

free energy
H
H

the intermediate
TS≠ resembles
B + E

E
A B C
EDG starting A B C
EDG substrates products
progress of reaction
C + E
Since the benzene ring is the
nucleophile the reaction is
__________,
E accelerated by EDGs
 Comparing Intermediates
For Rings with an EWG vs. EDG
EWG O H O H
O H
deactivating
A + E

E H E H

EDG activating CH3 CH3 CH3 CH3

CH3 CH3 N N
N

C + E

E H E H all atoms have a

complete octet
Substituents and Regiochemistry in
Electrophilic Aromatic Substitution
X
X X X
H E
+ E or or

E
E
X is EWG
or EDG ortho meta para

•  All activating substituents (EDG) and weakly

ortho / para directors
deactivating halogens are __________
•  All substituents more deactivating than the
halogens are meta
____ directors (i.e., the EWGs)
 Substituent - Reactivity Correlation Chart

Ortho / para
directing

From P. Y. Bruice
Organic Chemistry (5th Ed.)