Chapter 12

Arenes and Aromaticity

 Arenes and Aromaticity
• Arenes or aromatic compounds are based on benzene as a
fundamental structural unit
• Arenes contain a cyclic array of linked π bonds

• Arenes enjoy special stability and participate in unique types of

reactions due to their aromaticity
• In this chapter, we will study the structures and reactions of
arenes and learn to identify aromaticity, even when heteroatoms
are involved
Section 12.1

BENZENE
 Benzene
• The simplest aromatic compound is benzene (C6H6)
• Benzene was isolated from illuminating gas in 1825 and
prepared from benzoic acid shortly thereafter

• The presence of benzoic acid and benzene in fragrant

plant extracts led to the name aromatic
• Nowadays, most benzene is isolated from petroleum
Section 12.2

THE STRUCTURE OF
BENZENE
 C6H6: A Strange Hydrocarbon
• Despite its formula of C6H6, benzene does not react like other
alkenes or alkynes
– Substitution instead of addition with electrophilic reagents
– Very strong electrophiles are required

• Kekulé first proposed that the double bonds in benzene are

arranged in a cyclic, conjugated array

• The double bonds in benzene are stabilized

by a special kind of cyclic conjugation (aromaticity)
 Resonance in Benzene
• Kekulé’s structure suggests that 1,2- and 1,6-disubstituted
benzenes ought to be different compounds…

• No examples of this kind of isomerism are known. They could be

equilibrating rapidly…
 Resonance in Benzene
• Kekulé’s structure suggests that 1,2- and 1,6-disubstituted
benzenes ought to be different compounds…

• …but the “isomers” cannot be isolated at low temperatures. The

two structures are resonance forms

The C–C bond order is 1.5 and all bonds are of equal length.
Section 12.3

THE STABILITY OF BENZENE

 Heats of Hydrogenation
The heat of hydrogenation of
benzene is remarkably low.
Benzene is very stable, even
relative to a hypothetical
cyclohexatriene.

The 152 kJ/mol difference between ∆H for cyclohexatriene

and ∆H for benzene is called resonance energy.
Section 12.4

BONDING IN BENZENE
 Valence-bond Perspective
• Each carbon in benzene is sp2 hybridized and trigonal
planar. Benzene is completely planar
• Unhybridized 2p orbitals overlap with one another to
form π bonds
• This picture cannot explain the remarkable stability of
benzene to a satisfactory degree
 Molecular Orbitals of Benzene
• Overlap of the six 2p atomic orbitals leads to six π-type
molecular orbitals

• Three of the π MOs are bonding (lower in energy than

the 2p AOs) and three are antibonding (higher in energy
than the 2p AOs)

• There are six π electrons, leaving three MOs occupied

and three unoccupied
Molecular Orbitals of Benzene

• All π bonding orbitals are fully occupied

• All π electrons occupy bonding orbitals
• The π system reaches the maximum stability: aromaticity
Section 12.5

SUBSTITUTED DERIVATIVES OF
BENZENE AND THEIR
NOMENCLATURE
 Substituted Benzenes
• Atoms other than H may be attached to the “core” benzene ring
• Monosubstituted benzenes are often named as derivatives of
benzene

• Xylene is an important common name for dimethylbenzenes

Common Derivatives of Benzene
 Disubstituted Benzenes
• Names of disubstituted benzenes must indicate the relative
positions of the substituents. This can be done with “1,n”
nomenclature or common names:
– ortho (o): 1,2-disubstituted benzenes
– meta (m): 1,3-disubstituted benzenes
– para (p): 1,4-disubstituted benzenes
 Polysubstituted Benzenes
• Numbers (locants) must be used when three or more
substituents are present on the benzene ring

• The name of the benzene derivative sets the 1-position

• If no common derivative exists, number to give the
smallest number at the first point of difference
 Benzene as Substituent
• The entire benzene ring itself (C6H5–) is named phenyl
(Ph–)

• The PhCH2– group is called the benzyl group

Section 12.6

POLYCYCLIC AROMATIC
HYDROCARBONS
 Polycyclic Aromatic Hydrocarbons
• Benzene rings may be fused together in larger polycyclic
structures
• These polycyclic aromatic hydrocarbons have very
large resonance energies
• They are also famous for being carcinogenic!
 Resonance in PAHs
• The most important resonance form in a PAH contains
the most rings with the full “Kekulé set” of three double
bonds

• Note that phenanthrene is slightly more stable than

anthracene, consistent with this rule
Section 12.7

PHYSICAL PROPERTIES OF
ARENES
 Physical Properties of Arenes
• Benzene resembles other hydrocarbons of comparable
molecular weight in its physical properties

• However, a new class of intermolecular forces has been

identified for arenes!
 π Stacking and PAHs
• Crystals of benzene contain molecules stacked in a
“herringbone” pattern
• The π clouds of adjacent benzenes
overlap in π stacking interactions

• The importance of π stacking is especially apparent

in the melting points of PAHs
Section 12.8

THE BENZYL GROUP

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

• Resonance structures illustrate the delocalization of charge

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

• Benzylic ions and radicals are important intermediates in many

reactions of phenyl-substituted compounds
– SN1
– Acid-base reactions
– Free-radical benzylic halogenation
Section 12.9

NUCLEOPHILIC SUBSTITUTION IN
BENZYLIC HALIDES
 SN1 of Benzylic Halides
• Benzylic halides are even more reactive than tertiary alkyl
halides in SN1

• Resonance stabilization (electron delocalization) of the benzylic

cation intermediate is responsible
 Retained Aromaticity
• We have seen that allylic halides react to form multiple products
in SN1 reactions
• Benzylic halides do not give isomeric products in SN1!
Aromaticity is retained in the only observed product

• There is a severe energetic penalty associated with the

destruction of aromaticity
• In general, very few reactions of arenes give products that are
not aromatic
 SN2 of Benzylic Halides
• Benzylic halides are more reactive than primary alkyl halides and
even allylic halides in SN2 reactions

• The highly dispersed, low-energy LUMO of benzyl chloride is

responsible for this effect
 Products of SN2
• Primary benzylic halides are great for nucleophilic substitution—
elimination is not possible!

• Note the lack of β-hydrogens in the starting material

• Secondary and tertiary benzylic halides may still undergo
elimination to form vinylbenzenes. Trends are the same as we’ve
seen previously for alkyl halides
Section 12.10

BENZYLIC FREE-RADICAL
HALOGENATION
 Benzylic Radicals
• The homolytic BDE of a benzylic C–H bond is remarkably low—
benzylic radicals are stable!

Abstraction of H at the benzylic

position is relatively easy.
 Benzylic Halogenation
• Radical halogenation is regioselective for the benzylic position,
even in substrates with tertiary carbons
• NBS is used with a radical initiator for benzylic bromination

• Note that the product benzylic bromide can be used in

substitution or elimination reactions!
Section 12.11

BENZYLIC ANIONS
 Acidity of Benzylic C–H
• Benzylic hydrogens are acidic relative to alkyl hydrogens
• The benzylic anion is stabilized by electron
delocalization
• Additional phenyl rings leads to further lowering of the
pKa and greater stability of the conjugate base
Section 12.12

OXIDATION OF
ALKYLBENZENES
 Benzylic Oxidation
• Benzylic oxidation occurs when alkylbenzenes are
treated with O2 via a radical mechanism

• In the first steps of propagation, O2 abstracts H and the

resulting benzylic radical adds to O2
Benzylic Oxidation in the Laboratory
• Inorganic oxidizing agents are usually used for benzylic oxidation
in the laboratory
• At least one benzylic hydrogen is required for reactivity
• Alkyl substituents with at least one benzylic C–H are “chewed up”
to carboxylic acid groups
Section 12.13

ALKENYLBENZENES
 Preparation of Alkenylbenzenes
• Alkenylbenzenes are prepared from arenes using methods we’ve
seen before
– Dehydrogentation (industrial)

– Dehydration

– Dehydrohalogenation
Note the regioselectivity below!
 Reactivity of Vinylbenzenes
• The “alkenic” double bond is much more reactive than the
aromatic ring
• With rare exceptions, reactions of alkenes we’ve already
discussed apply to arene-substituted alkenes as well
 Reactivity of Vinylbenzenes
• The “alkenic” double bond is much more reactive than the
aromatic ring
• With rare exceptions, reactions of alkenes we’ve already
discussed apply to arene-substituted alkenes as well
 Markovnikov Selectivity
• In electrophilic additions involving carbocations, the benzylic
cation intermediate is formed exclusively

• Protonation occurs at the carbon farther from the aromatic ring

Section 12.14

POLYMERIZATION OF STYRENE
(READING SECTION)
 Polymerization of Styrene
• Vinylbenzene is also known as styrene
• Addition of a cation, anion, or radical to styrene produces a
benzylic cation, anion, or radical—which is reactive itself
• Repeated additions of benzylic radicals results in
polymerization of styrene
 Radical Polymerization
• Initiation, step 1: homolytic cleavage of initiator

• Initiation, step 2: addition of alkoxy radical to styrene

 Radical Polymerization
• Propagation: addition of benzylic radical to styrene

• Repeat to produce a polystyrene chain

Section 12.15

THE BIRCH REDUCTION

 Reduction of Arenes
• We have seen previously that Na, NH3(l)—“solvated electron”
conditions—can reduce alkynes to alkenes
• When combined with an alcohol, the same conditions reduce
aromatic compounds to isolated dienes and destroy aromaticity!
• This reaction is called the Birch reduction

• Note the regioselectivity of the reaction: the more substituted

alkene forms preferentially (Zaitsev’s rule redux!)
 Mechanism of the Birch Reduction
• Analogous to reductions of alkynes:
– Electron transfer
– Proton transfer (from ROH)
– Electron transfer
– Proton transfer (from ROH)
• Proton transfer is thermodynamically controlled (hence
the Zaitsev regioselectivity)
 Mechanism of the Birch Reduction
• Analogous to reductions of alkynes:
– Electron transfer
– Proton transfer (from ROH)
– Electron transfer
– Proton transfer (from ROH)
• Proton transfer is thermodynamically controlled (hence
the Zaitsev regioselectivity)
 Mechanism of the Birch Reduction
• Analogous to reductions of alkynes:
– Electron transfer
– Proton transfer (from ROH)
– Electron transfer
– Proton transfer (from ROH)
• Proton transfer is thermodynamically controlled (hence
the Zaitsev regioselectivity)
 Mechanism of the Birch Reduction
• Analogous to reductions of alkynes:
– Electron transfer
– Proton transfer (from ROH)
– Electron transfer
– Proton transfer (from ROH)
• Proton transfer is thermodynamically controlled (hence
the Zaitsev regioselectivity)
Section 12.16

BENZYLIC SIDE CHAINS AND

RETROSYNTHETIC ANALYSIS
 Benzylic Functionalization
• Functionalization of benzylic carbons is enabled by the stability of
benzylic radicals, cations, and anions
• Consider the synthesis of (Z)-1-phenyl-2-butyne
 Benzylic Functionalization
• Functionalization of benzylic carbons is enabled by the stability of
benzylic radicals, cations, and anions
• Consider the synthesis of (Z)-1-phenyl-2-butyne

The (Z)-alkene can be prepared by sodium-liquid

ammonia reduction of the corresponding alkyne.
 Benzylic Functionalization
• Functionalization of benzylic carbons is enabled by the stability of
benzylic radicals, cations, and anions
• Consider the synthesis of (Z)-1-phenyl-2-butyne

the key bond

The alkyne can be prepared via SN2 of a benzylic halide, which

can be produced from toluene via radical halogenation.
 Benzylic Functionalization
• Functionalization of benzylic carbons is enabled by the stability of
benzylic radicals, cations, and anions
• Consider the synthesis of (Z)-1-phenyl-2-butyne
• In the forward direction,

Replacement of benzylic H with X opens the door to a variety of reactions.

Section 12.17

CYCLOBUTADIENE AND
CYCLOOCTATETRAENE
 Other Cyclic, Conjugated Compounds
• Cyclobutadiene and cyclooctatetraene are both cyclic and fully
conjugated like benzene. We might expect them to enjoy the
same stability as benzene

• However, cyclobutadiene is extremely unstable; it readily

dimerizes

• Cyclooctatetraene can be synthesized and stored, but it is not as

stable as we would expect
 Cyclooctatetraene
• Cyclooctatetraene (COT) is nonplanar and it contains distinct
single and double bonds
• In other words, it’s not really fully conjugated

• The heat of hydrogenation of COT is more

than four times as large as cyclooctene’s!

Cyclooctatetraene is surprisingly unstable.

 Antiaromaticity
• Compounds that are cyclic and conjugated but unstable
nonetheless are called antiaromatic
• Their nonbonding or antibonding π MOs are occupied
• To get around this issue, they deform and act like unconjugated
alkenes
Section 12.18

HÜCKEL’S RULE
 Hückel’s Rule
• Hückel noticed that only monocyclic conjugated
molecules with 4n + 2 π electrons (where n is an
integer)—2, 6, 10, 14, etc.—are especially stable
• Having 4n + 2 π electrons is a prerequisite for
aromaticity
• The rule is a consequence of the π molecular orbitals of
cyclic conjugated molecules
 The Frost Circle
• To draw the MOs of a cyclic conjugated compound
easily, we draw the molecule as a regular polygon and
inscribe it in a circle vertex down
Note the filled
• This is called a Frost circle nonbonding MOs in the
antiaromatic molecules!
Section 12.19

ANNULENES
 Annulenes
• Annulenes are monocyclic conjugated hydrocarbons with more
than six carbons
• The prefix [x] identifies the number of carbons in the ring
• Small annulenes are nonaromatic due mostly to steric factors
and/or angle strain
– For example, all-cis [10]annulene has painful angle strain

– Other isomers have hydrogens that sterically interfere with one another

These molecules deform into nonplanar

structures that are nonaromatic.
 [18]Annulene
• [18]Annulene is able to achieve planarity and should be
aromatic according to Hückel’s rule
• It does have considerable resonance energy, but
undergoes addition reactions that destroy its
“aromaticity”
Section 12.20

AROMATIC IONS
 Cycloheptatrienyl Cation
• Shoving a cationic carbon into the six-membered ring of
benzene should yield an aromatic molecule according to
Hückel’s rule!
• Cycloheptatrienyl cation is in fact aromatic
 Cyclopentadienyl Anion
• Two π bonds and a lone pair on an anionic carbon are
also anionic according to Hückel’s rule
• The structure here is called cyclopentadienyl anion

Cyclopentadienyl anion is a very important

ligand in organometallic chemistry.
Section 12.21

HETEROCYCLIC AROMATIC
COMPOUNDS
 Heteroaromatic Compounds
• Aromatic compounds may contain heteroatoms with lone
pairs as well! Usually N, O, or S
• The simplest monocyclic heteroaromatics are pyrrole,
pyridine, furan, and thiophene

• It is important to consider whether the lone pair(s) on the

heteroatom are π electrons or in hybrid orbitals
 Polycyclic Heteroaromatics
• Heteroaromatics may be fused to benzene rings or other
heteroaromatic rings

• The nucleobases are polycyclic heteroaromatics!

 Multiple Heteroatoms
• Heteroaromatic compounds often contain two
heteroatoms separated by one carbon

• Again, it is important to consider whether lone pairs are

part of the π system or in hybrid orbitals
Section 12.22

HETEROCYCLIC AROMATIC
COMPOUNDS AND HÜCKEL’S
RULE
 Pyridine and Pyrrole
• How do we decide whether the lone pair on nitrogen is
part of the π system or not? Consider the role of the
unhybridized p orbital!
• In pyridine, the p orbital is involved in π bonding. The
lone pair is in an sp2 hybrid orbital
 Pyridine and Pyrrole
• How do we decide whether the lone pair on nitrogen is
part of the π system or not? Consider the role of the
unhybridized p orbital!
• In pyrrole, the p orbital is not involved in π bonding. The
lone pair resides in this orbital!
 Pyridine and Pyrrole
• How do we decide whether the lone pair on nitrogen is
part of the π system or not? Consider the role of the
unhybridized p orbital!
• ESP maps show where the lone pairs are in each
compound—note the orange-red colors!
 Oxygen and Sulfur
• Oxygen and sulfur bear two lone pairs in neutral
heteroaromatics
• One lone pair is in an sp2 hybrid orbital and the other is
involved in the aromatic π system