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AROMATIC HYDROCARBONS
LECTURE
Benzene
Formula: C6H6
All carbons and hydrogens
are equivalent
All C-C bond lengths are
equivalent.
All C-H bonds are
equivalent.
Each C is sp2 hybridized
Stability of Benzene
Six -electrons spread equally around the ring
methoxybenzene nitrobenzene
anisole
benzoic acid
acetophenone
Reactions of Benzene
a. KMnO4
b. HX
c. H2O, H2SO4
d. H2, Pt
e. Br2
f. H2, Pt in
very high
T and P
No oxidation
No addition of halogen
No hydration
No reduction in ordinary
conditions
No halogenation
Chemical Properties
Delocalized electrons
Reaction with E+ requires acid catalyst to polarize E+
Substituted Benzenes
Arenes - aromatic hydrocarbon with alkyl sidechain/s
benzylic carbon
General formula
Examples
product
product
ethylbenzene
benzoic acid
isopropylbenzene
benzoic acid
tert-butylbenzene
EArS Reactions
Halogenation
Reagent: X2, FeX3 or AlX3
Electrophile: X+
X2 + AlX3 AlX4-X+ AlX4- + X+
Product: halobenzene
A
l
X
3
+
X
2
EArS Reactions
Nitration
Reagents: HNO3, H2SO4
Electrophile: NO2+
HNO3 + H2SO4 + H2NO3 + -HSO4 +NO2 + H2O
Product: nitrobenzene
N
O
2
H
2
S
O
4
+
H
N
O
3
EArS Reactions
Sulfonation
Reagents: fuming H2SO4
Electrophile: +SO3H
Product: sulfonic acid
SO3H
+ fum
ing
H2SO4
EArS Reactions
Friedel Crafts Alkylation
Reagents: RX, FeX3 or AlX3
Electrophile: R+
RX + AlX3 R-AlX4 R+ + AlX4 Product: aromatic alkane
EArS Reactions
Friedel Crafts Alkylation
Limitations:
Only 1, 2 , and 3 RX can be used.
Rearrangement of R+ can occur.
Electrophile:
Rearrangement to form
the more stable R+
EArS Reactions
Friedel Crafts Acylation
Reagents: RC(=O)X, FeX3 or AlX3
Electrophile: R+C(=O)
RC(=O)X + AlX3 RC(=O)-AlX4 R+C(=O) + AlX4 Product: aromatic ketone
O
X
C
A lX 3
+
H 3C
Monosubstituted Benzene
S may act as an activating or
S
deactivating group
activating: makes the aromatic
ring more nucleophilic
deactivating: makes the aromatic
o
ring less nucleophilic
Monosubstituted Benzene
Substituent Effects
E
D
G
Electro-donating group (EDG)
Activating group
Makes the aromatic ring to be
o
more nucleophilic, thus, more
reactive to E+
m
Intermediate of the reaction is
more stable if E+ is attached at the
p
ortho or para position
Monosubstituted Benzene
Substituent Effects
E
D
G
Electro-donating group (EDG)
O
H
N
H
2
o
O
R
N
H
R
N
R
2
O
C
m
N
H
C
p
R
Monosubstituted Benzene
Substituent Effects
E
W
G
Electro-withdrawing group (EDG)
Deactivating group
Makes the aromatic ring to be less
o
nucleophilic, thus, less reactive to
E+
Meta director
m
Intermediate of the reaction is
more stable if E+ is attached at the
p
meta position
exemption: halides (X) are EWG
but ortho or para director
Monosubstituted Benzene
Substituent Effects
E
W
G
O
H
C
H
C
R C
O
R
o
O
O
2
O
3
HN
C
N S
C
C
l
3
N
R
2
C
F
3
m
p
Ortho-Para Directors
Stability of Benzene
Meta Directors
Strongly activating
Strongly deactivating
N H
N R
N
O
2
N
R
2
C
F
3
C
C
l
3
O H
N H R
Moderately activating
OR
NHC
Moderately deactivating
OC
O
R
Weakly activating
Weakly deactivating
- F, - I, - Br, - Cl
SO
3H
CN
O
H
O
R
CH
CR
Monosubstituted Benzenes
Exercises:
Monosubstituted Benzenes
Exercises:
Monosubstituted Benzenes
Exercises:
Rank the following compounds from fastest to slowest
as they react in an EAS reaction with HNO3 and
H2SO4. O
H
N
O
CCl3
O
Monosubstituted Benzenes
Exercises:
Propose a synthesis of the following compound from
benzene.
C
O
O
H
f
r
o
m
B
r
Monosubstituted Benzenes
Exercises:
Propose a synthesis of the following compounds
m-nitrobenzenesulfonic acid
1-tert-butyl-4-chlorobenzene
from styrene, synthesize C6H5CH2CH2OH
Disubstituted Benzene
S
Substituent Effects:
Reinforcement
S
Opposing effects:
strong activating > deactivating or
weakly activating
Disubstituted Benzene
Substituent Effects:
O
C
H
3
Reinforcement
groups are located so that effects
are additive
Examples:
EDG para- to an EWG
S
O
H
3
Disubstituted Benzene
Substituent Effects:
Reinforcement
N
O
groups are located so that effects
2
are additive
Examples:
EDG para- to an EWG
EWG meta- to each other
S
O
H
3
Pointed carbon is
meta- wrt to both EWG
Disubstituted Benzene
C
N
Substituent Effects:
Reinforcement
groups are located so that effects
N
H
C
O
C
H
are additive
3
Examples:
EDG para- to an EWG
EWGs meta- to each other
EDG ortho- to an EWG
Pointed carbons:
left (ortho- wrt to EDG, meta- wrt EWG)
Right (para- wrt to EDG, meta- wrt EWG)
Disubstituted Benzene
Substituent Effects:
O
H
Opposing effects:
strong activating > deactivating
or weakly activating
O
C
H
C
H
2
3
NH2 > OH > OR > NHCOR > Ph, R > X > meta directors
Disubstituted Benzene
Substituent Effects:
N
H
2 Opposing effects:
strong activating > deactivating or
weakly activating
C
H
3
NH2 > OH > OR > NHCOR > Ph, R > X > meta directors
Disubstituted Benzene
C
l
Case 1
B
r
Substituent Effects:
Opposing effects:
strong activating > deactivating or
weakly activating
small differences leads to mixture
of products
Often, theres little substitution
for groups meta to each other.
Case 2
NH2 > OH > OR > NHCOR > Ph, R > X > meta directors
Disubstituted Benzene
Exercises:
Disubstituted Benzene
Exercises:
Disubstituted Benzene
Exercises:
synthesize
Disubstituted Benzene
Exercises:
Propose a synthesis of the following compounds.
2-bromo-4-nitroaniline from aniline
4-bromo-2-nitroaniline from aniline
aryl
halide
is
unreactive
C
l
to Nu EWG that are ortho- or
para- to X greatly
activates aryl halides
towards displacement
by a Nu-
N aO H (aq )
EWG meta to X
does not activate
the ring
NR
Cl
N a O H (a q )
NO2
NR
NO2
C H 3C H 2N H 2
NO2
Br
H O 3S
C H 3C H 2O N a
C H 3C H 2O H
NO2
O C H 2C H
H O 3S
Quiz # 5