Chapter 15

the electrons in PhH

are more tightly held
than in oleIin.
loose enough to
react with electrophile
electron source
(act as a base)
electrophilic substitution
rxn rather than electrophilic
addition rxn to maintain
aromaticity
SO
3
H
CH
3
CH
3
SO
3
H
CH
3
CH
3
SO
3
H
SO
3
H

H
2
SO
4
, SO
3
RT, 20~30min
H
2
SO
4
, SO
3
RT, 1~2min
reactivity : activating group & deactivating group
orientation : ortho, para director & meta director
CH
3
: activating group & ortho, para director
Table 15.1 (orientation)
reactivity :
NO
2 H
2
SO
4
60
o
HNO
3

CH
3
NO
2
CH
3
NO
2

HNO
3
1 : 1
(excess)
1 : 25
Table 15.3
NO
2 H
2
SO
4
90
o
HNO
3
NO
2
NO
2
32 62 6
the time required Ior rxns
the severity oI conditions
competitive rxns
CH
3
COOH COOH
NCOCH
3
CN
CH
3
SO
3
H
NO
2
NO
2
H
reinIorced
CH
3
Cl
Cl
Br
CH
3
Cl
(little) (little)
strongly activating
groups win over
deactivating or weakly
activating groups.
CHO CH
3
CH
3
NCOCH
3
H
CH
3
OH
( )
H
2
SO
4
HNO
3
NO
2
Br
2
, Ee
NO
2
Br
Br
2
, Ee
Br Br
NO
2
Br
NO
2
KMnO
4
CH
3
CH
3
NO
2
NO
2
COOH
NO
2
NO
2

HNO
3
, H
2
SO
4
HNO
3
, H
2
SO
4
HNO
3
, H
2
SO
4

COOH
NO
2
K
2
Cr
2
O
7
K
2
Cr
2
O
7

Nitration
HONO
2
H
2
SO
4
H
3
O HSO
4
NO
2
O N O

NO
2

NO
2
H
NO
2
H
NO
2
H
slow
benzenonium ion
NO
2
H


HSO
4

Iast
NO
2
H
2
SO
4

SulIonation
H
2
SO
4
H
3
O HSO
4
SO
3
S O


O
O
SO
3

slow
S
H

O
O
O

SO
3
H
3
O

SO
3
H
SO
3
H
2
SO
4

H
2
O
HSO
4

Iast

NO
2
H

S
H

O
O
O

Eriedel-CraIts alkylation

RX

AlCl
3
( Lewis acid, BE
3
, SnCl
4
, HE, H

)
R
R X

AlCl
3
AlCl
4
R

slow
H
R
H
R

AlCl
4

Iast
R
AlCl
3
HCl
Halogenation

Cl
2
or Br
2
EeCl
3
X

Cl
2
EeCl
3

Cl
3
Ee Cl Cl
Cl
3
Ee Cl Cl
slow
Cl
H
EeCl
4

Cl
H
EeCl
4

Cl
EeCl
3
HCl
highly reactive aromatic compds react with halogen
without Lewis acid.
C
6
H
6
H
2
SO
4
C
6
H
5
SO
3
H H
2
O

large excess oI conc or Iuming sulIuric acid
(removal oI
dilute acid
distill hydrocarbon
H
2
O by SO
3
)

C
6
H
5
SO
3 H

SO
3
H

SO
3
General mechanism oI electrophilic aromatic substitution
(1) ArH Y Ar
H
Y
slow (r.d.s)
(2) Ar
H
Y
Z Ar Y HZ Iast
not
ArH Y
Ar
Y
H

ArY H

Ior nitration, bromination, Eriedel-CraIts alkylation no signiIicant
isotope eIIect
Eig 15.2
step(1) is r.d.s.
step(2) is Iast
not one step
reaction
CH bond breaking
is not r.d.s.
Ior sulIonation, k
H
/k
D
2 comparable oI Iorward and reverse
Eig 15.3
~
~
Ea
Ar
SO
3
H
rxn oI

S
H

O
O
O

reactivity oI
PhH, PhCH
3
, PhNO
2
Y H Y H Y H
CH
3
NO
2
stabilize
positive charge
destabilize
positive charge
lower
higher
Iaster rxn slower rxn
Ea Ea
electron-releasing group : activate
the ring
electron-withdrawing group : deactivate
the ring
( Table on p537)
( 25 times Iaster
than PhH)
CH
3
CH
2
Cl CHCl
2
CCl
3
more reactive
activating groups : activate all positions
deactivating groups : deactivate all positions
ortho & para orientation
activate ortho & para much more.
deactivate ortho & para much more.
meta orientation
Ior toluene~
para attack meta attack
ortho attack
CH
3
H Y
CH
3
H Y
CH
3
H Y
CH
3
Y
H
CH
3
Y
H
CH
3
Y
H
H
3
C
Y
H
H
3
C
Y
H
H
3
C
Y
H
especially
stable
especially
stable

aniline~
para meta
ortho
NH
2
H Y
NH
2
H Y
NH
2
H Y
NH
2
Y
H
NH
2
Y
H
NH
2
Y
H
H
2
N
Y
H
especially
stable
(complete octet)
Ior nitrobenzene~
para attack meta attack
ortho attack
NO
2
H Y
NO
2
H Y
NO
2
H Y
NO
2
Y
H
NO
2
Y
H
NO
2
Y
H
O
2
N
Y
H
O
2
N
Y
H
O
2
N
Y
H
especially
unstable
especially
unstable
PhNRR', PhOR : N and O show electron-withdrawing inductive eIIects
but electron-donating resonance eIIect strong activator
much more reactive than benzene
especially
stable
(complete octet)
NH
2
H Y

naphthalene~
Cl
Y
H
Cl
Y
H
Cl
Y
H
phenol~
para para (ortho) ortho
OH
H Y
HO
Y
H
especially
unstable
others~
NHMe
H Y
NMe
H Y
HN
H Y
OMe
H Y
Me CCH
3
O
PhX : X deactivate
para, ortho orientation
electron - withdrawing
electron - donating
by inductive eIIect
by resonance eIIect
chlorobenzene~
para (ortho)
Cl
H Y
Cl
H Y
Cl
H Y
Cl
H Y
more stable
(complete octet)
meta
Cl
Y
H
H O
2
N H O
2
N H O
2
N
NO
2
H
NO
2
H
NO
2
H