ELEMENTARY ORGANIC CHEMISTRY
LECTURE
AROMATIC HYDROCARBONS
Quiz # 4
Rationalization (3 points each)
1. Bromination of (3E)-hex-3-ene produces one compound. Same process
for (3Z)-hex-3-ene produces two products.
2. In hydrohalogenation of conjugated dienes, the 1,4-addition product is
predominant at high temperatures.
3. Acid-catalyzed hydration of three-carbon terminal alkynes produce
ketones and never aldehydes.
Draw what is asked
4. (2 points) Aliphatic C4H8 compound that has the lowest melting point.
5. (3 points) Intermediate of the hydroboration-oxidation reaction of 2methylpent-2-ene.
6. (5 points) Ozonolysis products of an alkyne that produces
when brominated.
Stability of Benzene
Six -electrons spread equally around the ring
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
benzoic acid
acetophenone
Aromatic Hydrocarbons (Benzene derivatives)
methoxybenzene nitrobenzene
anisole
Aromatic Hydrocarbons (benzene derivatives)
chlorobenzene methylbenzene aminobenzene hydroxybenzene
toluene
aniline
phenol
Chemical Properties
Delocalized electrons
Reaction with E+ requires acid catalyst to polarize E+
No halogenation
No reduction in ordinary
conditions
No hydration
No addition of halogen
No oxidation
Reacts by substitution for ring preservation
Reactions of Benzene
a. KMnO4
b. HX
c. H2O, H2SO4
d. H2, Pt
e. Br2
f. H2, Pt in
very high
T and P
Reactions of Arene Side-chain
Reactions of Arene Side-chain
benzoic acid
Note: benzylic carbon must have H for oxidation to
occur
Regardless of side-chain length
Reagent: KMnO4
Product: benzoic acid
Oxidation
product
Free-radical halogenation
Reagent: Cl2 or Br2, h or
Intermediate: Benzyl free radical
Benzyl free radical
ethylbenzene
Reactions of Arene Side-chain
very stable due to
resonance
Substituted Benzenes
NBS source of bromine radical
(PhCO2)2 radical initiator
Intermediate: Benzyl free radical
product
Reagent: N-bromosuccinimide (NBS), (PhCO2)2, CCl4
Free-radical halogenation
Examples
benzylic carbon
Arenes - aromatic hydrocarbon with alkyl sidechain/s
General formula
Benzyl free radical
Reactions of Arene Side-chain
Halogenation
EArS Reactions
A
l
X
3
Electrophilic Aromatic Substitution (EArS)
+
X
2
Reagent: X2, FeX3 or AlX3
Electrophile: X+
X2 + AlX3 AlX4-X+ AlX4- + X+
Product: halobenzene
Oxidation
Reagent: KMnO4
Product: benzoic acid
Regardless of side-chain length
Note: benzylic carbon must have H for oxidation to
occur
tert-butylbenzene
Reactions of Arene Side-chain
Oxidation
Reagent: KMnO4
Product: benzoic acid
Regardless of side-chain length
benzoic acid
Note: benzylic carbon must have H for oxidation to
occur
isopropylbenzene
EArS Reactions
Friedel Crafts Alkylation
EArS Reactions
Only 1, 2 , and 3 RX can be used.
Rearrangement of R+ can occur.
Limitations:
Sulfonation
Reagents: fuming H2SO4
Electrophile: +SO3H
Product: sulfonic acid
SO3H
EArS Reactions
+ fum
ing
H2SO4
EArS Reactions
Reagents: RX, FeX3 or AlX3
Electrophile: R+
RX + AlX3 R-AlX4 R+ + AlX4 Product: aromatic alkane
Friedel Crafts Alkylation
N
O
2
Nitration
Reagents: HNO3, H2SO4
Electrophile: NO2+
HNO3 + H2SO4 + H2NO3 + -HSO4 +NO2 + H2O
Product: nitrobenzene
H
2
S
O
4
+
H
N
O
3
Electrophile:
Rearrangement to form
the more stable R+
Monosubstituted Benzene
S may act as an activating or
deactivating group
S
activating: makes the aromatic
ring more nucleophilic
deactivating: makes the aromatic
o
ring less nucleophilic
S determines the point of attack
A lX 3
O
C
Monosubstituted Benzene
O
H
Electro-donating group (EDG)
Substituent Effects
E
D
G
N
H
2
O
C
o
O
R
N
H
R
N
R
2
N
H
C
m
R
p
ortho or para position
more stable if E+ is attached at the
m
Intermediate of the reaction is
Ortho or para director
Makes the aromatic ring to be
o
more nucleophilic, thus, more
reactive to E+
Activating group
Electro-donating group (EDG)
Substituent Effects
E
D
G
Monosubstituted Benzene
of an incoming E+
m
Ortho (carbon next to S)
p
Meta (carbon two steps from S)
Para (carbon opposite of S)
EArS Reactions
Friedel Crafts Acylation
H 3C
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
Monosubstituted Benzene
C
R C
C
C
C
l
3
Substituent Effects
E
W
G
O
R
C
H
O
H
o
C
F
3
Monosubstituted Benzenes
Exercises:
Meta Directors
Ortho-Para Directors
Stability
of Benzene
N R
CN
SO
3H
O
R
CR
CH
O
H
Moderately deactivating
N
O
2
N
R
2
C
F
3
C
C
l
3
Strongly deactivating
2
N H
O H
OC
N H R
Moderately activating
OR
NHC
R
Weakly activating
Strongly activating
O
2
O
3
HN
N
R
2
C
N S
m
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
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
Weakly deactivating
- F, - I, - Br, - Cl
Monosubstituted Benzenes
Exercises:
Monosubstituted Benzenes
H
N
CCl3
m-nitrobenzenesulfonic acid
1-tert-butyl-4-chlorobenzene
from styrene, synthesize C6H5CH2CH2OH
Propose a synthesis of the following compounds
Exercises:
Rank the following compounds from fastest to slowest
as they react in an EAS reaction with HNO3 and
H2SO4. O
A
O
Monosubstituted Benzenes
Monosubstituted Benzenes
Exercises:
Exercises:
C
O
O
H
Propose a synthesis of the following compound from
benzene.
f
r
o
m
B
r
Disubstituted Benzene
Substituent Effects:
Reinforcement
O
C
H
3
groups are located so that effects
are additive
Examples:
EDG para- to an EWG
S
O
H
3
Pointed carbons are
ortho- wrt EDG and
meta- wrt EWG
groups are located so that effects
are additive
Substituent Effects:
Reinforcement
Disubstituted Benzene
S
S
Opposing effects:
strong activating > deactivating or
weakly activating
Substituent Effects:
Reinforcement
Disubstituted Benzene
C
N
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:
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
Substituent Effects:
Opposing effects:
N
H
2
strong activating > deactivating or
weakly activating
C
H
3
NH2 > OH > OR > NHCOR > Ph, R > X > meta directors
Disubstituted Benzene
Substituent Effects:
Opposing effects:
O
H
strong activating > deactivating
or weakly activating
O
C
H
C
H
2
3
NH2 > OH > OR > NHCOR > Ph, R > X > meta directors
Disubstituted Benzene
Exercises:
Case 1
C
l
strong activating > deactivating or
weakly activating
small differences leads to mixture
of products
Often, theres little substitution
for groups meta to each other.
Substituent Effects:
Opposing effects:
Disubstituted Benzene
B
r
Case 2
NH2 > OH > OR > NHCOR > Ph, R > X > meta directors
Disubstituted Benzene
Exercises:
Nucleophilic Aromatic Substitution (NArS)
to Nu
is unreactive
C
l aryl halide
-
Disubstituted Benzene
EWG that are ortho- or
para- to X greatly
activates aryl halides
towards displacement
by a Nu-
Disubstituted Benzene
Exercises:
synthesize
Exercises:
Propose a synthesis of the following compounds.
2-bromo-4-nitroaniline from aniline
4-bromo-2-nitroaniline from aniline
Nucleophilic Aromatic Substitution (NArS)
The more EWG that are ortho or para to the leaving
group, the faster the NArS
N aO H (aq )
N a O H (a q )
NR
NR
EWG meta to X
does not activate
the ring
Nucleophilic Aromatic Substitution (NArS)
Cl
Cl
NO2
Nucleophilic Aromatic Substitution (NArS)
Nu- Group Replacing X
-OH
-OH
-OR
-OR
H2O
-OH
ROH
-OR
NH3
-NH2
RNH2
-NHR
Nucleophilic Aromatic Substitution (NArS)
There is very little differences in reactivity among
various halides.
Br
C H 3C H 2O H
H O 3S
O C H 2C H
3
Nucleophilic Aromatic Substitution (NArS)
O 2N
NO2
Synthesize this compound
from benzene.
Br
Br
NO2
NO2
C H 3C H 2N H 2
Nucleophilic Aromatic Substitution (NArS)
O 2N
H O 3S
C H 3C H 2O N a
Quiz # 5
