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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.

ELEMENTARY ORGANIC CHEMISTRY

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

Aromatic Hydrocarbons (benzene derivatives)

chlorobenzene methylbenzene aminobenzene hydroxybenzene


toluene
aniline
phenol

Aromatic Hydrocarbons (Benzene derivatives)

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+

Reacts by substitution for ring preservation

Substituted Benzenes
Arenes - aromatic hydrocarbon with alkyl sidechain/s
benzylic carbon

General formula

Examples

Reactions of Arene Side-chain


Free-radical halogenation
Reagent: Cl2 or Br2, h or
Intermediate: Benzyl free radical

Benzyl free radical


very stable due to
resonance

product

Reactions of Arene Side-chain


Free-radical halogenation
Reagent: N-bromosuccinimide (NBS), (PhCO2)2, CCl4
NBS source of bromine radical
(PhCO2)2 radical initiator

Intermediate: Benzyl free radical

Benzyl free radical

product

Reactions of Arene Side-chain


Oxidation
Reagent: KMnO4
Product: benzoic acid
Regardless of side-chain length

Note: benzylic carbon must have H for oxidation to


occur

ethylbenzene

benzoic acid

Reactions of Arene Side-chain


Oxidation
Reagent: KMnO4
Product: benzoic acid
Regardless of side-chain length

Note: benzylic carbon must have H for oxidation to


occur

isopropylbenzene

benzoic acid

Reactions of Arene Side-chain


Oxidation
Reagent: KMnO4
Product: benzoic acid
Regardless of side-chain length

Note: benzylic carbon must have H for oxidation to


occur

tert-butylbenzene

Electrophilic Aromatic Substitution (EArS)

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

S determines the point of attack


of an incoming E+
m
Ortho (carbon next to S)
p
Meta (carbon two steps from S)
Para (carbon opposite of S)

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+

Ortho or para director

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

groups are located so that effects


are additive

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

Pointed carbons are


ortho- wrt EDG and
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
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

Nucleophilic Aromatic Substitution (NArS)

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-

Nucleophilic Aromatic Substitution (NArS)


Cl

N aO H (aq )

EWG meta to X
does not activate
the ring

NR

Cl

N a O H (a q )

NO2

NR

Nucleophilic Aromatic Substitution (NArS)


The more EWG that are ortho or para to the leaving
group, the faster the NArS

Nucleophilic Aromatic Substitution (NArS)


There is very little differences in reactivity among
various halides.

Nucleophilic Aromatic Substitution (NArS)


Nu- Group Replacing X
-OH
-OH
-OR
-OR
H2O
-OH
ROH
-OR
NH3
-NH2
RNH2
-NHR

Nucleophilic Aromatic Substitution (NArS)


Br
O 2N

NO2

C H 3C H 2N H 2

NO2

Br
H O 3S

C H 3C H 2O N a

Nucleophilic Aromatic Substitution (NArS)


Br
O 2N

C H 3C H 2O H

NO2

O C H 2C H

Synthesize this compound


from benzene.

H O 3S

Quiz # 5