Aromatic

Compounds
 Discovery of Benzene
Isolated in 1825 by Michael Faraday
who determined C:H ratio to be 1:1.
Synthesized in 1834 by Eilhard
Mitscherlich who determined
molecular formula to be C6H6.
Other related compounds with low
C:H ratios had a pleasant smell, so
they were classified as aromatic.
 Benzene Structures
Proposed in 1866 by Friedrich Kekul,
shortly after multiple bonds were
suggested.
Failed to explain existence of only
one isomer of 1,2-dichlorobenzene.
H
C H
H C C
C C
H C H
Prismane Structure
H
Kekule Structure
 Benzene Structures
Each sp2 hybridized C in the ring has
an unhybridized p orbital
perpendicular to the ring which
overlaps around
Resonance the ring.
Structure

=>
 Unusual Reactions
Alkene + KMnO4 diol (addition)
Benzene + KMnO4 no reaction.
Alkene + Br2/CCl4 dibromide
(addition)
Benzene + Br2/CCl4 no reaction.
With FeCl3 catalyst, Br2 reacts with
benzene to form bromobenzene + HBr
(substitution!). Double bonds remain.
Unusual Stability
 Annulenes
All cyclic conjugated
hydrocarbons were
proposed to be
aromatic. [6]anulene

However,
cyclobutadiene is so
[4]anulene
reactive that it
dimerizes before it
can be isolated.
And [8]anulene
cyclooctatetraene
adds Br2 readily.
 What Does It Take to Be
Aromatic?
Alternating double and single bonds
A magic number of pi electrons
Resonance structures must be able
to move the pi electrons in a circular
manar.
Non bonding electrons can also
participate in the resonance
structures.
 Hckels Rule
Hckels Rule is used to generate the
magic number of pi electrons.
If the compound has a continuous
ring of overlapping p orbitals and has
4N + 2 pi electrons, it is aromatic.
If the compound has a continuous
ring of overlapping p orbitals and has
4N electrons, it is antiaromatic.
N is any integer, starting at zero
 Generation of Magic Pi
Electrons

Value of N 4N + 2
0 2
1 6
2 10
3 14
 [N]Annulenes
[4]Annulene is antiaromatic (4N e-s)
[8]Annulene would be antiaromatic,
but its not planar, so its nonaromatic.
[10]Annulene is aromatic except for
the isomers that are not planar.
Larger 4N annulenes are not
antiaromatic because they are flexible
enough to become nonplanar.
 Tropylium Ion
The cycloheptatrienyl cation has 6 p
electrons and an empty p orbital.
Aromatic: more stable than open chain
ion. H OH
H
+ +
H , H2O
 Which of the Following are
Aromatic?

a. b. c. d.

e. f. g. h.
 Disubstituted Benzenes
The prefixes ortho-, meta-, and para- are
commonly used for the 1,2-, 1,3-, and 1,4-
positions, respectively.

=>
 3 or More Substituents
Use the smallest possible numbers, but
the carbon with a functional group is #1.
OH
O2N NO 2 O2N NO 2

NO2 NO2
1,3,5-trinitrobenzene 2,4,6-trinitrophenol
 Common Names of Benzene
Derivatives
OH CH3 NH2 OCH3

phenol toluene aniline anisole

H O O O
C CH2 C C C
CH3 H OH

styrene acetophenone benzaldehyde benzoic acid

 Phenyl and Benzyl
Phenyl indicates the benzene ring
attachment. The benzyl group has
an additional carbon.
Br CH2Br

phenyl bromide benzyl bromide

 Fused Ring

Hydrocarbons
Naphthalene

Anthracene

Phenanthrene
 Larger Polynuclear
Aromatic Hydrocarbons
Formed in combustion (tobacco
smoke).
Many are carcinogenic.
Epoxides form, combine with DNA
base.

=>
pyrene
 Physical Properties
Melting points: More symmetrical than
corresponding alkane, pack better into
crystals, so higher melting points.
Boiling points: Dependent on dipole
moment, so ortho > meta > para, for
disubstituted benzenes.
Density: More dense than
nonaromatics, less dense than water.
Solubility: Generally insoluble in water.
 Electrophilic Aromatic
Substitution
Electrophile, a species that loves electrons,
and substitutes for a hydrogen on the benzene
ring.

Chapter 17 21
 Mechanism
Step 1: Attack on the electrophile forms the sigma complex.

Step 2: Loss of a proton gives the substitution product.

Chapter 17 22
 Bromination of Benzene
Requires a stronger electrophile than Br2.
Use a strong Lewis acid catalyst, FeBr3.
+ -
Br Br FeBr3 Br Br FeBr3
H
H H
H
H H + - _
Br
Br Br FeBr3 + + FeBr4
H H
H H
H
H

Br
+ HBr

Chapter 17 23
Comparison with Alkenes
Cyclohexene adds Br2, H = -121 kJ
Addition to benzene is endothermic,
not normally seen.
Substitution of Br for H retains
aromaticity, H = -45 kJ.
Formation of sigma complex is rate-
limiting.

Chapter 17 24
Energy Diagram for
Bromination

Chapter 17 25
 Nitration of Benzene
Use sulfuric acid with nitric acid to
form the nitronium ion electrophile.
O O H O
_
H O S O H H O N H O N + HSO4
+
O O O
H O O
NO2+ then forms a sigma complex
H O N H2O + N+ with
+ benzene, loses H+ to form
O O
nitrobenzene.

Chapter 17 26
 Nitration of Toluene
Toluene reacts 25 times faster than benzene.
The methyl group is an activating group.
The product mix contains mostly ortho and
para substituted molecules.

Chapter 17 27
Sigma Complex

Intermediate
is more
stable if
nitration
occurs at
the ortho
or para
position.
=>

Chapter 17 28
Energy Diagram

Chapter 17 29
 Activating, O-, P-Directing
Substituents
Alkyl groups stabilize the sigma complex by
induction, donating electron density
through the sigma bond.
Substituents with a lone pair of electrons
stabilize the sigma complex by resonance.

+
OCH3 OCH3
+
NO 2 NO 2
H H

Chapter 17 30
Substitution on
Anisole

Chapter 17 31
 The Amino Group
Aniline, like anisole, reacts with bromine
water (without a catalyst) to yield the
tribromide. Sodium bicarbonate is added
to neutralize the HBr thats also formed.

Chapter 17 32
Summary of Activators

Chapter 17 33
Deactivating Meta-Directing
Substituents
Electrophilic substitution reactions for
nitrobenzene are 100,000 times
slower than for benzene.
The product mix contains mostly the
meta isomer, only small amounts of
the ortho and para isomers.
Meta-directors deactivate all positions
on the ring, but the meta position is
less deactivated.

Chapter 17 34
Ortho Substitutionon
Nitrobenzene

Chapter 17 35
Para Substitution on
Nitrobenzene

Chapter 17 36
Meta Substitution on
Nitrobenzene

Chapter 17 37
Energy Diagram

Chapter 17 38
Structure of Meta-Directing
Deactivators
The atom attached to the aromatic ring
will have a partial positive charge.
Electron density is withdrawn
inductively along the sigma bond, so
the ring is less electron-rich than
benzene.

Chapter 17 39
Summary of
Deactivators

Chapter 17 40
More Deactivators

Chapter 17 41
 Halobenzenes
Halogens are deactivating toward
electrophilic substitution, but are ortho,
para-directing!
Since halogens are very electronegative,
they withdraw electron density from the
ring inductively along the sigma bond.
But halogens have lone pairs of
electrons that can stabilize the sigma
complex by resonance.

Chapter 17 42
 Sigma Complex for
Bromobenzene

Ortho and para attacks produce a bromonium ion

and other resonance structures.

No bromonium ion
possible with meta attack.

Chapter 17 43
Energy Diagram

Chapter 17 44
Summary of Directing
Effects

Chapter 17 45
 Multiple Substituents
The most strongly activating substituent
will determine the position of the next
substitution. May have mixtures.

OCH3 OCH3 OCH3

SO3H
SO3
+
H2SO4
O2N O2N O2N
SO3H

Chapter 17 46
Friedel-Crafts Alkylation
Synthesis of alkyl benzenes from
alkyl halides and a Lewis acid,
usually AlCl3.
Reactions of alkyl halide with Lewis
acid produces a carbocation which
is the electrophile.
Other sources of carbocations:
alkenes + HF, or alcohols + BF3.

Chapter 17 47
 Examples ofCarbocation
Formation
Cl CH3 + _
CH3 CH CH3 + AlCl3 C Cl AlCl3
H3C H
_
HF F
+
H2C CH CH3 H3C CH CH3
+ BF3
H O
OH _
BF3 +
H3C CH CH3 H3C CH CH3 H3C CH CH3 + HOBF3

Chapter 17 48
 Formation of Alkyl
Benzene
CH3 H
+C H CH(CH3)2
+
CH3 H
F
-
F B OH CH3 HF
H
F CH + F
+ CH(CH3)2
CH3 B OH
F
H

Chapter 17 49
 Friedel-
CraftsAcylation
Acyl chloride is used in place of alkyl
chloride.
The acylium ion intermediate is
resonance stabilized and does not
rearrange like a carbocation.
The product is a phenyl ketone that is
less reactive than benzene.

Chapter 17 50
Mechanism of Acylation

O
O O HCl
C R _
C+ Cl AlCl3 C R +
H AlCl3
R +
H

Chapter 17 51
Catalytic Hydrogenation
Elevated heat and pressure are required.
Possible catalysts: Pt, Pd, Ni, Ru, Rh.
Reduction cannot be stopped at an
intermediate stage.

CH3 CH3

3 H2, 1000 psi

Ru, 100C
CH3 CH3

Chapter 17 52
 Side-Chain Oxidation
Alkylbenzenes are oxidized to benzoic
acid by hot KMnO4 or Na2Cr2O7/H2SO4.
_
CH(CH3)2 COO
-
KMnO4, OH
_
H2O, heat COO
CH CH2

Chapter 17 53
 Side-Chain
Halogenation
Benzylic position is the most reactive.
Chlorination is not as selective as
bromination, results in mixtures.
Br2 reacts only at the benzylic position.

Br
CH2CH2CH3 CHCH2CH3
Br2, h

Chapter 17 54
AROMATIC
REVIEW
 Give the shape of benzene.
a. Tetrahedral
b. Bent
c. Trigonal pyramidal
d. Planar
 Answer
a. Tetrahedral
b. Bent
c. Trigonal pyramidal
d. Planar

All six carbons and six hydrogens are in

the same plane.
 Give the hybridization of each
carbon in benzene.
a. sp
b. sp2
c. sp3
d. sp4
 Answer
a. sp
b. sp2
c. sp3
d. sp4

Each carbon in benzene is sp2

hybridized.
 Give the bond angle of the
atoms in benzene.
a. 45 d. 109.5
b. 60 e. 120
c. 90
 Answer
a. 45 d. 109.5
b. 60 e. 120
c. 90

The carbons are 120o apart in benzene.

 Classify .

a. Aromatic
b. Antiaromatic
c. Nonaromatic
d. Acyclic
 Answer
a. Aromatic
b. Antiaromatic
c. Nonaromatic
d. Acyclic

The compound gives a whole number for

N in Hckels rule (4N + 2 = 6, N = 1).
 Classify .

a. Aromatic
b. Antiaromatic
c. Nonaromatic
d. Acyclic
 Answer
a. Aromatic
b. Antiaromatic
c. Nonaromatic
d. Acyclic

The compound is cyclic and has

continuous delocalized electrons, but
does not give a whole number for
Hckels rule (4N + 2 = 8, N = 3/2).
 Classify .

a. Aromatic
b. Antiaromatic
c. Nonaromatic
d. Acyclic
 Answer
a. Aromatic
b. Antiaromatic
c. Nonaromatic
d. Acyclic

This cyclic compound does not have a

continuous, overlapping ring of p
orbitals and is nonaromatic.
 Name

a. Anthracene
b. Naphthalene
c. Phenanthrene
d. Benzene
 Answer
a. Anthracene
b. Naphthalene
c. Phenanthrene
d. Benzene

Naphthalene contains two benzene

rings fused together.
 Name

a. Anthracene
b. Naphthalene
c. Phenanthrene
d. Benzene
 Answer
a. Anthracene
b. Naphthalene
c. Phenanthrene
d. Benzene

Anthracene contains three benzene rings

fused together.
 Identify how carbon,
diamond, and graphite are
related.
a. They are enantiomers of carbon.
b. They are diastereomers of carbon.
c. They are allotropes of carbon.
d. They have the same properties.
 Answer
a. They are enantiomers of carbon.
b. They are diastereomers of carbon.
c. They are allotropes of carbon.
d. They have the same properties.
 Cl NH2
Name
Br

a. 4-Bromo-3- d. 1-Bromo-2-
chloroaniline chloro-4-aniline
b. 4-Bromo-3- e. 1-Bromo-2-
chlorophenol chloro-4-phenol
c. 4-Bromo-3-
chloroanisole
 Answer
a. 4-Bromo-3- d. 1-Bromo-2-
chloroaniline chloro-4-aniline
b. 4-Bromo-3- e. 1-Bromo-2-
chlorophenol chloro-4-phenol
c. 4-Bromo-3-
chloroanisole

Aniline is the parent compound. The NH2 is

at position one.
 CH3

Name
OH

a. p-Methylphenol
b. m-Methylphenol
c. o-Methylphenol
d. 4-Methylphenol
e. 3-Methylphenol
 Answer
a. p-Methylphenol
b. m-Methylphenol
c. o-Methylphenol
d. 4-Methylphenol
e. 3-Methylphenol

The groups are on adjacent carbons,

which is ortho.
NameO C NO2

a. 3-Amino-5- d. 5-Nitro-3-
benzaldehyde benzaldehyde
b. 5-Amino-3- e. 3-Nitro-
benzaldehyde benzaldehyde
c. 3-Amino-
benzaldehyde
 Answer
a. 3-Amino-5- d. 5-Nitro-3-
benzaldehyde benzaldehyde
b. 5-Amino-3- e. 3-Nitro-
benzaldehyde benzaldehyde
c. 3-Amino-
benzaldehyde

Benzaldehyde is the parent compound.

NameO C NO2

a. o-Amino- d. o-Nitro-
benzaldehyde benzaldehyde
b. m-Amino- e. m-Nitro-
benzaldehyde benzaldehyde
c. p-Amino-
benzaldehyde
 Answer
a. o-Amino- d. o-Nitro-
benzaldehyde benzaldehyde
b. m-Amino- e. m-Nitro-
benzaldehyde benzaldehyde
c. p-Amino-
benzaldehyde

Benzaldehyde is the parent compound.

 Name C6H5CH2CH2CCCH3.

a. 1-Phenyl-3-pentyne
b. 5-Phenyl-2-pentyne
c. 4-Phenyl-2-pentyne
d. 1-Phenyl-2-butyne
e. 1-Phenyl-3-butyne
 Answer
a. 1-Phenyl-3-pentyne
b. 5-Phenyl-2-pentyne
c. 4-Phenyl-2-pentyne
d. 1-Phenyl-2-butyne
e. 1-Phenyl-3-butyne
 Identify the slow step in
electrophilic aromatic
substitution.
a. Formation of a stronger
nucleophile.
b. Formation of the benzenonium
ion.
c. Deprotonation to regain
aromaticity.
d. Formation of a carbanion.
 Answer
a. Formation of a stronger nucleophile.
b. Formation of the benzenonium ion.
c. Deprotonation to regain aromaticity.
d. Formation of a carbanion.

Benzene attacking the electrophile to

form the benzenonium ion is the slow
step.
 Cl2

AlCl3

a. Hexachlorobenzene
b. Hexachlorocyclohexane
c. 5,6-Dichloro-1,3-cyclohexadiene
d. Chlorobenzene
 Answer
a. Hexachlorobenzene
b. Hexachlorocyclohexane
c. 5,6-Dichloro-1,3-cyclohexadiene
d. Chlorobenzene

One chlorine atom substitutes on the

benzene.
 1. HNO3, H2SO4

2. Zn, aq. HCl

a. Nitrobenzene
b. Aniline
c. Chlorobenzene
d. Benzenesulfonic acid
 Answer
a. Nitrobenzene
b. Aniline
c. Chlorobenzene
d. Benzenesulfonic acid

A nitro group is added, which is then

reduced to an amino group.
 SO3

a. Nitrobenzene
b. Aniline
c. Chlorobenzene
d. Benzenesulfonic acid
 Answer
a. Nitrobenzene
b. Aniline
c. Chlorobenzene
d. Benzenesulfonic acid

A sulfonic acid group is added to the

benzene.
 CH2CH3
HNO3

H2SO4

a. 2- and 4-nitroethylbenzene
b. 3-Nitroethylbenzene
c. 2- and 4-ethylbenzenesulfonic
acid
d. 3-Ethylbenzenesulfonic acid
 Answer
a. 2- and 4-nitroethylbenzene
b. 3-Nitroethylbenzene
c. 2- and 4-ethylbenzenesulfonic
acid
d. 3-Ethylbenzenesulfonic acid

The ethyl group is an ortho and para

director.
Classify a bromide.

a. Meta, activating group

b. Meta, deactivating group
c. Ortho and para, deactivating
group
d. Ortho and para, activating group
 Answer
a. Meta, activating group
b. Meta, deactivating group
c. Ortho and para, deactivating group
d. Ortho and para, activating group

The electrons can delocalize into the

bromide, making another benzenonium
ion intermediate.
 Classify a nitro group.

a. Meta, activating group

b. Meta, deactivating group
c. Ortho and para, deactivating
group
d. Ortho and para, activating group
 Answer
a. Meta, activating group
b. Meta, deactivating group
c. Ortho and para, deactivating
group
d. Ortho and para, activating group
 OCH3
AlCl3

CH3CH2CH2Cl

a. 3-Propylanisole
b. 2- and 4-propylanisole
c. 3-Isopropylanisole
d. 2- and 4-isopropylanisole
 Answer
a. 3-Propylanisole
b. 2- and 4-propylanisole
c. 3-Isopropylanisole
d. 2- and 4-isopropylanisole

The methoxy group is an ortho, para

director. The propyl group rearranges.
 Give the intermediate in a
FriedelCrafts acylation.

a. Carbocation
b. Carbanion
c. Radical
d. Acylium ion
 Answer
a. Carbocation
b. Carbanion
c. Radical
d. Acylium ion

An RCO+ is an intermediate in a
FriedelCrafts acylation.
 CO, HCl

AlCl3, CuCl

a. Chlorobenzene
b. Benzoic acid
c. Benzaldehyde
d. Benzene
 Answer

a. Chlorobenzene
b. Benzoic acid
c. Benzaldehyde
d. Benzene

The GattermanKoch formylation forms

benzaldehyde.
 CH2CH2CH3
Br2

light

a. 2-Bromo- d. -Bromo-
propylbenzene propylbenzene
b. 3-Bromo- e. -Bromo-
propylbenzene propylbenzene
c. 4-Bromo-
propylbenzene
 Answer
a. 2-Bromo- d. -Bromo-
propylbenzene propylbenzene
b. 3-Bromo- e. -Bromo-
propylbenzene propylbenzene
c. 4-Bromo-
propylbenzene

Bromine substitutes on the benzylic

carbon.
 OH
(CH3)2CHOH

HF

a. 2-Isopropylphenol
b. 3-Isopropylphenol
c. 4-Isopropylphenol
d. 2-Isopropylphenol and 4-
isopropylphenol
e. 2-Isopropylphenol and 3-
isopropylphenol
 Answer

a. 2-Isopropylphenol
b. 3-Isopropylphenol
c. 4-Isopropylphenol
d. 2-Isopropylphenol and 4-
isopropylphenol
e. 2-Isopropylphenol and 3-
isopropylphenol
Phenols are highly reactive substrates
for electrophilic aromatic substitution.
 End of
Chapter 9

Chapter 17 108