Chapter 12

Arenes and Aromaticity

Carey, F. A.; Giuliano, R. M.; Allison, N. T.; Bane, S. L. In Organic Chemistry,

11th Edition, 2019.
Chem 211 B. R. Kaafarani 1
 Arenes and Aromaticity
¾ Arenes or aromatic compounds are based on benzene
as a fundamental structural unit.
¾ Arenes contain a cyclic array of linked π bonds.
¾ Arenes enjoy special stability and participate in unique
types of reactions due to their aromaticity.
¾ In this chapter, we will study the structures and
reactions of arenes and learn to identify aromaticity,
even when heteroatoms are involved.

Chem 211 B. R. Kaafarani 2

 12.2. The Structure of Benzene
¾ Kekulé (1866) proposed a cyclic structure for C6H6 with
alternating single and double bonds.
¾ Later, Kekulé revised his proposal by suggesting a rapid
equilibrium between two equivalent structures.

¾ However, this proposal suggested isomers of the kind shown

were possible. Yet, none were ever found.

X X

H X H X

H H H H

H H
Chem 211 B. R. Kaafarani 3
 The Structure of Benzene
¾ Structural studies of benzene DO NOT support the
Kekulé formulation. Instead of alternating single and
double bonds, all of the C—C bonds are the same

Benzene has the shape

of a regular hexagon

Chem 211 B. R. Kaafarani 4

 All C—C bond distances = 140 pm

140 pm 140 pm 146 pm

140 pm 140 pm

140 pm 140 pm 134 pm

¾ 140 pm is the average between the C—C single bond

distance and the double bond distance in 1,3-butadiene.

Chem 211 B. R. Kaafarani 5

 Resonance Picture of Bonding in Benzene
¾ Instead of Kekulé's suggestion of a rapid equilibrium
between two structures.
¾ Express the structure of benzene as a resonance
hybrid of the two Lewis structures. Electrons are not
localized in alternating single and double bonds, but are
delocalized over all six ring carbons.

H H
H H H H

H H H H

Chem 211
H B. R. Kaafarani
H 6
 Resonance Formulation of Benzene

¾ Circle-in-a-ring notation stands for resonance

description of benzene (hybrid of two Kekulé structures).

Chem 211 B. R. Kaafarani 7

 12.3. The Stability of Benzene

¾ Benzene is the best and most familiar example of

a substance that possesses "special stability" or
"aromaticity”.

¾ Aromaticity is a level of stability that is

substantially greater for a molecule than would be
expected on the basis of any of the Lewis structures
written for it.

Chem 211 B. R. Kaafarani 8

 Thermochemical Measures of Stability
¾ Heat of hydrogenation: compare experimental value
with "expected" value for hypothetical “cyclohexatriene”.

Pt
+ 3H2

ΔH°= – 208 kJ

Chem 211 B. R. Kaafarani 9

¾ Observed heat of hydrogenation is 152 kJ/mol less than
"expected“.
¾ Benzene is 152 kJ/mol more stable than expected.
¾ 152 kJ/mol is the resonance energy of benzene.

Figure 12.2

Chem 211 B. R. Kaafarani 10

 Cyclic conjugation versus noncyclic conjugation

3H2

Pt

Heat of hydrogenation = 208 kJ/mol

3H2

Pt

Heat of hydrogenation = 337 kJ/mol

Chem 211 B. R. Kaafarani 11

 Resonance Energy of Benzene
¾ Compared to localized 1,3,5-cyclohexatriene
152 kJ/mol

¾ Compared to 1,3,5-hexatriene
129 kJ/mol

¾ Exact value of resonance energy of benzene

depends on what it is compared to, but regardless of
model, benzene is more stable than expected by a
substantial amount.

Chem 211 B. R. Kaafarani 12

 12.4. Bonding in Benzene
Planar ring of 6 sp2 hybridized carbons

¾ Each carbon contributes a p orbital.

¾ Six p orbitals overlap to give cyclic π system; six π
electrons delocalized throughout π system.
¾ High electron density above and below plane of ring.

Chem 211 B. R. Kaafarani 13

 The π Molecular Orbitals of Benzene

Antibonding
orbitals

Energy

Bonding
orbitals

6 p AOs combine to give 6 π MOs

3 MOs are bonding; 3 are antibonding
Chem 211 B. R. Kaafarani 14
 Benzene MOs

Antibonding
orbitals

Energy

Bonding
orbitals

All bonding MOs are filled

No electrons in antibonding orbitals
Chem 211 B. R. Kaafarani 15
 Molecular Orbitals of Benzene

Chem 211 B. R. Kaafarani 16

 12.5
Substituted Derivatives of Benzene
and Their Nomenclature

Chem 211 B. R. Kaafarani 17

 General Points
1) Benzene is considered as the parent and comes last
in the name.

Br C(CH3)3 NO2

Bromobenzene tert-Butylbenzene Nitrobenzene

Chem 211 B. R. Kaafarani 18
 General Points
1) Benzene is considered as the parent and
comes last in the name.

2) List substituents in alphabetical order.

3) Number ring in direction that gives lowest

locant at first point of difference.

Chem 211 B. R. Kaafarani 19

 Example

Cl

Br

2-Bromo-1-chloro-4-fluorobenzene

Chem 211 B. R. Kaafarani 20

 Ortho, Meta, and Para

Alternative locants for disubstituted

derivatives of benzene

1,2 = ortho 1,3 = meta 1,4 = para

(abbreviated o-) (abbreviated m-) (abbreviated p-)

o-Xylene m-Xylene p-Xylene

Chem 211 B. R. Kaafarani 21
 Examples

NO2 Cl
CH2CH3

Cl

o-Ethylnitrobenzene m-Dichlorobenzene
(1-Ethyl-2-nitrobenzene) (1,3-Dichlorobenzene)

Chem 211 B. R. Kaafarani 22

 Common Derivatives of Benzene

Chem 211 B. R. Kaafarani 23

 Benzene Derivative names can be
used as parent
OCH3 OCH3

NO2

Anisole p-Nitroanisole
or
4-Nitroanisole
Chem 211 B. R. Kaafarani 24
 Polysubstituted Benzenes
¾ Numbers (locants) must be used when three or
more substituents are present on the benzene ring.

Chem 211 B. R. Kaafarani 25

 Easily confused names

phenyl phenol benzyl

OH CH2—

a group a compound a group

Chem 211 B. R. Kaafarani 26

 12.6. Polycyclic Aromatic Hydrocarbons
Naphthalene
Resonance energy = 255 kJ/mol

Chem 211 B. R. Kaafarani 27

 Polycyclic Aromatic Hydrocarbons
¾ Benzene rings may be fused together in larger
polycyclic structures.
¾ These polycyclic aromatic hydrocarbons have
very large resonance energies.
¾ They are also famous for being carcinogenic!

Chem 211 B. R. Kaafarani 28

 PAH Examples
¾ Benzo[a]pyrene, for example, is present in tobacco
smoke, contaminates food cooked on barbecue grills,
and collects in the soot of chimneys.

¾ Benzo[a]pyrene is a carcinogen (a cancer-causing

substance). It is converted in the liver to diol epoxide
that can induce mutations leading to the uncontrolled
growth of certain cells.
Chem 211 B. R. Kaafarani 29
 12.7. Physical Properties of Arenes

¾ Resemble other hydrocarbons:

- Nonpolar.
- Insoluble in water.
- Less dense than water.

Chem 211 B. R. Kaafarani 30

 π Stacking and PAHs
¾ Crystals of benzene contain
molecules stacked in a
“herringbone” pattern.
¾ The π clouds of adjacent
benzenes overlap in π
stacking interactions.

¾ The importance of π stacking is

especially apparent in the
boiling points of PAHs.

Chem 211 B. R. Kaafarani 31

 12.8. The Benzyl Group
Phenyl as Stabilizing Group
¾ The phenyl ring can act as an electron-donating or –
withdrawing group to stabilize charges on the adjacent
carbon.

Chem 211 B. R. Kaafarani 32

 The Benzyl Group
Phenyl as Stabilizing Group
¾ The adjacent phenyl ring also stabilizes benzylic
radicals by spreading out the spin density of the
unpaired electron.

¾ Benzylic ions and radicals are important intermediates

in many reactions of phenyl-substituted compounds:
™ SN1
™ Acid-base reactions
™ Free-radical benzylic halogenation
Chem 211 B. R. Kaafarani 33
 12.9
Nucleophilic Substitution in
Benzylic Halides

Chem 211 B. R. Kaafarani 34

 SN1 of Benzylic Halides
¾ Benzylic halides are even more reactive than tertiary
alkyl halides in SN1.

¾ Resonance stabilization (electron delocalization) of

the benzylic cation intermediate is responsible.

Chem 211 B. R. Kaafarani 35

 What about SN1?
Relative solvolysis rates in aqueous acetone

CH3 CH3

C Cl CH3 C Cl

CH3 CH3

600 1
¾ Tertiary benzylic carbocation is formed
more rapidly than tertiary carbocation;
therefore, more stable.
Chem 211 B. R. Kaafarani 36
 What about SN1?
Relative rates of formation:

CH3 CH3

C+ CH3 C+
CH3 CH3

more stable less stable

Chem 211 B. R. Kaafarani 37

 Resonance in Benzyl Cation

H + H H H H H H H
C C C C
H H H H H H H H
+ +
+
H H H H H H H H
H H H H

¾ Positive charge is delocalized between benzylic carbon

and the ring carbons that are ortho and para to it.

Chem 211 B. R. Kaafarani 38

 Solvolysis
CH3

C Cl

CH3

CH3CH2OH

CH3

C OCH2CH3

CH3 (87%)
Chem 211 B. R. Kaafarani 39
 SN2 of Benzylic Halides
¾ Benzylic halides are more reactive than primary
alkyl halides and even allylic halides in SN2 reactions.

¾ The highly dispersed, low-energy LUMO of

benzyl chloride is responsible for this effect.

Chem 211 B. R. Kaafarani 40

 Products of SN2
¾ Benzylic halides are more reactive than primary
alkyl halides and even allylic halides in SN2 reactions.

¾ Note the lack of β-hydrogens in the starting material.

¾ Secondary and tertiary benzylic halides may still
undergo elimination to form vinylbenzenes. Trends
are the same as we’ve seen previously for alkyl
halides.
Chem 211 B. R. Kaafarani 41
12.10. Benzylic Free-Radical Halogenation
The Benzene Ring as a Substituent

C
C C• C•

Allylic radical Benzylic radical

Benzylic carbon is analogous to allylic carbon.

Chem 211 B. R. Kaafarani 42

 Resonance in Benzyl Radical

H . H H
C
H H
C
H H
C
H
C
H H H
. H H H H
. H

H H H H H
. H H H
H H H H

¾ Unpaired electron is delocalized between benzylic

carbon and the ring carbons that are ortho and para to it.

Chem 211 B. R. Kaafarani 43

 Spin Density in Benzyl Radical

¾ Unpaired electron is delocalized between benzylic

carbon and the ring carbons that are ortho and para to it.
Chem 211 B. R. Kaafarani 44
 Free-Radical Chlorination of Toluene
¾ Industrial process.
¾ Highly regioselective for benzylic position.

Cl2
CH3 CH2Cl
light
or
heat
Toluene Benzyl chloride

Chem 211 B. R. Kaafarani 45

 Free-Radical Chlorination of Toluene
¾ Similarly, dichlorination and trichlorination are
selective for the benzylic carbon. Further
chlorination gives:

CHCl2 CCl3

(Dichloromethyl)benzene (Trichloromethyl)benzene

Chem 211 B. R. Kaafarani 46

 Benzylic Bromination
¾ Is used in the laboratory to introduce a halogen
at the benzylic position.

CH3 CH2Br

CCl4, 80°C
+ Br2 + HBr
light

NO2 NO2
p-Nitrotoluene p-Nitrobenzyl
bromide (71%)
Chem 211 B. R. Kaafarani 47
 N-Bromosuccinimide (NBS)
¾ NBS is a convenient reagent for benzylic bromination.
Br

CH2CH3 CHCH3
O O
CCl4
NBr + NH +
benzoyl
O peroxide, O
heat
(87%)

Chem 211 B. R. Kaafarani 48

 12.11. Benzylic Anions
¾ Benzylic hydrogens are acidic relative to alkyl
hydrogens.
¾ The benzylic anion is stabilized by electron
delocalization.
¾ Additional phenyl rings leads to further lowering of
the pKa and greater stability of the conjugate base.

Chem 211 B. R. Kaafarani 49

 12.12. Oxidation of Alkylbenzenes
Benzylic Oxidation
¾ Benzylic oxidation occurs when alkylbenzenes are
treated with O2 via a radical mechanism.

¾ In the first steps of propagation, O2 abstracts H

and the resulting benzylic radical adds to O2.

Chem 211 B. R. Kaafarani 50

 Benzylic Oxidation
Site of Oxidation is Benzylic Carbon

CH3

or Na2Cr2O7 O
H2SO4
CH2R COH
H2O
or heat

¾ At least one benzylic

CHR2
hydrogen needs to be present.
Chem 211 B. R. Kaafarani 51
 Example
O

CH3 COH
Na2Cr2O7
H2SO4
H2O
heat
NO2 NO2
p-Nitrotoluene p-Nitrobenzoic
acid (82-86%)

Chem 211 B. R. Kaafarani 52

 Examples

Chem 211 B. R. Kaafarani 53

 12.13. Preparation of Alkenylbenzenes
Dehydrogenation (industrial)

Dehydration

Dehydrohalogenation

Chem 211 B. R. Kaafarani 54

 Reactivity of Vinylbenzenes
¾ The “alkenic” double bond is much more reactive than
the aromatic ring.
¾ With rare exceptions, reactions of alkenes we’ve already
discussed apply to arene-substituted alkenes as well.

Chem 211 B. R. Kaafarani 55

 Markovnikov Selectivity
¾ In electrophilic additions involving carbocations, the
benzylic cation intermediate is formed exclusively.

¾ Protonation occurs at the carbon farther from the

aromatic ring.

Chem 211 B. R. Kaafarani 56

 Acid-Catalyzed Dehydration
of Benzylic Alcohols

Cl Cl
KHSO4
CHCH3 CH CH2
heat
(80-82%)
OH
Cl

CHCH3
+

Chem 211 B. R. Kaafarani 57

 Dehydrohalogenation

H3C CH2CHCH3

Br

NaOCH2CH3 ethanol, 50°C

H3C CH CHCH3

(99%)

Chem 211 B. R. Kaafarani 58

 Free-Radical Addition of HBr

HBr
CH CH2 CH2CH2Br
peroxides

CH CH2Br
•
via benzylic radical

Chem 211 B. R. Kaafarani 59

 12.14. Polymerization of Styrene
¾ Vinylbenzene is also known as styrene.
¾ Addition of a cation, anion, or radical to styrene
produces a benzylic cation, anion, or radical—which
is reactive itself.
¾ Repeated additions of benzylic radicals results in
polymerization of styrene.

Chem 211 B. R. Kaafarani 60

 Radical Polymerization
¾ Initiation, step 1: homolytic cleavage of initiator

¾ Initiation, step 2: addition of alkoxy radical to styrene.

Chem 211 B. R. Kaafarani 61

 Radical Polymerization
¾ Propagation: addition of benzylic radical to styrene

¾ Repeat to produce a polystyrene chain.

Chem 211 B. R. Kaafarani 62

 12.15. The Birch Reduction
H H H
H H H H
Na, NH3
CH3OH
H H H H

H H H
(80%)
¾ Product is non-conjugated diene.
¾ Reaction stops here. There is no further reduction.
¾ Reaction is not hydrogenation. H2 is NOT involved in any way.

Chem 211 B. R. Kaafarani 63

 Mechanism of the Birch Reduction

Step 1: Electron transfer from sodium.

H H
H H H H
•
+ • Na + Na+
H H H •• H
–
H H

Chem 211 B. R. Kaafarani 64

 Mechanism of the Birch Reduction

Step 2: Proton transfer from methanol.

H H
H • H H H
•

–
H H H •• H
H H H
H
– ••
•• OCH3 •• OCH3
Chem 211
••
B. R. Kaafarani
•• 65
 Mechanism of the Birch Reduction

Step 3: Electron transfer from sodium.

H H
H H H – H
• ••
+ • Na + Na+
H H H H
H H H H

Chem 211 B. R. Kaafarani 66

 Mechanism of the Birch Reduction

Step 4: Proton transfer from methanol.

••
– •• •• OCH3
•• OCH
•• 3
H H H H
H H H – H
••

H H H H
H H H H

Chem 211 B. R. Kaafarani 67

 Birch Reduction of an Alkylbenzene
H H H
H H Na, NH3 H H

CH3OH
H C(CH3)3 H C(CH3)3

H H H
(86%)

¾ If an alkyl group is present on the ring, it ends up as

a substituent on the double bond.

Chem 211 B. R. Kaafarani 68

 12.17. Cyclobutadiene and Cyclooctatetraene
¾ Cyclobutadiene and cyclooctatetraene are both cyclic
and fully conjugated like benzene. We might expect
them to enjoy the same stability as benzene.

¾ However, cyclobutadiene is extremely unstable; it

readily dimerizes.

¾ Cyclooctatetraene can be synthesized and

stored, but it is not as stable as we would expect.
Chem 211 B. R. Kaafarani 69
 Cyclooctatetraene
¾ Cyclooctatetraene (COT) is
nonplanar and it contains distinct
single and double bonds.
¾ In other words, it’s not really fully
conjugated

¾ Heat of hydrogenation of COT is more

than four times as large as cyclooctene’s!

Cyclooctatetraene is surprisingly unstable.

Chem 211 B. R. Kaafarani 70

 Antiaromaticity
¾ Compounds that are cyclic and conjugated but
unstable nonetheless are called antiaromatic.
¾ Their nonbonding or antibonding π MOs are
occupied (4n).
¾ To get around this issue, they deform and act like
unconjugated alkenes.

Chem 211 B. R. Kaafarani 71

 Requirements for Aromaticity
¾ Cyclic conjugation is necessary, but not sufficient.

not not
aromatic
aromatic aromatic
Antiaromatic Antiaromatic
when square when planar

Chem 211 B. R. Kaafarani 72

 12.18 Hückel’s Rule for Aromaticity
¾ Among planar, monocyclic, completely conjugated
polyenes, only those with 4n+2 π electrons possess
special stability (are aromatic):

n 4n+2
0 2
1 6 Benzene!
2 10
3 14
4 18
Chem 211 B. R. Kaafarani 73
 Hückel’s Rule
¾ Hückel restricted his analysis to planar,
completely conjugated, monocyclic polyenes.

¾ He found that the π molecular orbitals of

these compounds had a distinctive pattern.

¾ One π orbital was lowest in energy, another

was highest in energy, and the others
were arranged in pairs between the highest
and the lowest.

Chem 211 B. R. Kaafarani 74

 Hückel’s Rule
¾ Frost's circle is a mnemonic that allows us to
draw a diagram showing the relative energies of
the π orbitals of a cyclic conjugated system.
1) Draw a circle.
2) Inscribe a regular polygon inside the circle
so that one of its corners is at the bottom.
3) Every point where a corner of the polygon
touches the circle corresponds to a π electron
energy level.
4) The middle of the circle separates bonding
and antibonding orbitals.
Chem 211 B. R. Kaafarani 75
 Frost's Circle

Antibonding

Bonding

π MOs of Benzene

Chem 211 B. R. Kaafarani 76

 π-MO’s of Benzene

Antibonding

Benzene

Bonding
6 p orbitals give 6 π orbitals.
3 orbitals are bonding; 3 are antibonding.
Chem 211 B. R. Kaafarani 77
 π-MO’s of Benzene

Antibonding

Benzene
Bonding

6 π electrons fill all of the bonding orbitals.

all π antibonding orbitals are empty.
Chem 211 B. R. Kaafarani 78
 Note the filled
nonbonding
MOs in the
antiaromatic
molecules!

Chem 211 B. R. Kaafarani 79

 Completely Conjugated Polyenes

6 π electrons;
6 π electrons;
not completely
completely conjugated
conjugated

H H
not
aromatic
aromatic

Chem 211 B. R. Kaafarani 80

 12.19. Annulenes
¾ Annulenes are planar, monocyclic, completely
conjugated polyenes. That is, they are the kind of
hydrocarbons treated by Hückel's rule.
¾ Annulenes are monocyclic conjugated hydrocarbons
with more than six carbons.
¾ The prefix [x] identifies the number of carbons in the
ring.
¾ Small annulenes are nonaromatic
due mostly to steric factors and/or
angle strain.

Chem 211 B. R. Kaafarani 81

 [18] Annulenes

H H
H
H H
H

¾ 18 π electrons satisfies Hückel's rule.

¾ Resonance energy = 418 kJ/mol.

¾ Bond distances range between 137-143 pm.

Chem 211 B. R. Kaafarani 82

 12.20. Aromatic Ions
Cycloheptatrienyl Cation
¾ 6 π electrons delocalized over 7 carbons.
¾ Positive charge dispersed over 7 carbons.
¾ Very stable carbocation also called tropylium cation.

H H H H

H H H H
+
+
H H H H
H H
Chem 211 B. R. Kaafarani 83
 Cycloheptatrienyl Cation

Chem 211 B. R. Kaafarani 84

 Cycloheptatrienyl Cation
6 π electrons delocalized
over 5 carbons.
H H
Negative charge dispersed
over 5 carbons stabilized anion.
H ••
– H

Cyclopentadienyl anion is a very important

ligand in organometallic chemistry.
Chem 211 B. R. Kaafarani 85
 Acidity of Cyclopentadiene
H H H H

H+ +
H H H ••
– H

H H H
pKa = 16
Ka = 10-16 ¾ Cyclopentadiene is unusually acidic
for a hydrocarbon.
¾ Increased acidity is due to stability of
cyclopentadienide anion.
Chem 211 B. R. Kaafarani 86
 Electron Delocalization in Cyclopentadienide Anion

H H H H H H

H H H H H H
H H H

H H H H

H H H H
H H
Chem 211 B. R. Kaafarani 87
 Compare Acidity of Cyclopentadiene
& Cycloheptatriene

H H H H

H H
H H

H H H H
H H

pKa = 16 pKa = 36
Ka = 10-16 Ka = 10-36

Chem 211 B. R. Kaafarani 88

 Compare Acidity of Cyclopentadiene
& Cycloheptatriene

H H H H

H H
H ••
– H
••
H – H
H
H
Aromatic anion Anion not aromatic
6 π electrons 8 π electrons

Chem 211 B. R. Kaafarani 89

 Cyclopropenyl Cation

H H H H
+
+ also written as

H H

n=0
4n +2 = 2 π electrons

Chem 211 B. R. Kaafarani 90

 Cyclooctatetraene Dianion

H H H H

H – H
•• H H
also 2–
••–
written as
H H H H

H H H H
n=2
4n +2 = 10 π electrons

Chem 211 B. R. Kaafarani 91

 12.21. Heterocyclic Aromatic Compounds

Examples

•• •• ••
N N O S
•• •• ••
H

Pyridine Pyrrole Furan Thiophene

Chem 211 B. R. Kaafarani 92

 Polycyclic Heteroaromatics
¾ Heteroaromatics may be fused to benzene rings or
other heteroaromatic rings.

¾ The nucleobases are polycyclic heteroaromatics!

Chem 211 B. R. Kaafarani 93

 Multiple Heteroatoms
¾ Heteroaromatics may be fused to benzene rings or
other heteroaromatic rings.

¾ Again, it is important to consider whether lone

pairs are part of the π system or in hybrid orbitals.

Chem 211 B. R. Kaafarani 94

 Pyridine
¾ 6 π electrons in ring.
¾ Lone pair on nitrogen is in an sp2 hybridized
orbital; not part of π− system of ring.

Chem 211 B. R. Kaafarani 95

 Pyrrole
¾ Lone pair on nitrogen must be part of ring π−
system if ring is to have 6 π-electrons.
¾ Lone pair must be in a p orbital in order to overlap
with ring π-system.

Chem 211 B. R. Kaafarani 96

 Pyridine and Pyrrole
¾ ESP maps show where the lone pairs are in each
compound—note the orange-red colors!

Chem 211 B. R. Kaafarani 97

 Furan
¾ Two lone pairs on oxygen one pair is in a p orbital
and is part of ring π-system; other is in an sp2
hybridized orbital and is not part of ring π-system.

Chem 211 B. R. Kaafarani 98