Organic Chemistry, 5th Edition

L. G. Wade, Jr.

Chapter 16
Aromatic Compounds

Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
2003, Prentice Hall
 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.
Chapter 16
=> 2
 Kekulé Structure
• Proposed in 1866 by Friedrich Kekulé, 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 =>
H
Chapter 16 3
 Resonance Structure
Each sp2 hybridized C in the ring has an
unhybridized p orbital perpendicular to
the ring which overlaps around the ring.

=>
Chapter 16 4
 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.
=>
Chapter 16 5
 Unusual Stability
Hydrogenation of just one double
bond in benzene is endothermic!

=>
Chapter 16 6
 Annulenes
• All cyclic conjugated
hydrocarbons were
proposed to be aromatic.
• However, cyclobutadiene
is so reactive that it
dimerizes before it can
be isolated.
• And cyclooctatetraene
adds Br2 readily.
• Look at MO’s to explain
aromaticity. =>
Chapter 16 7
 MO Rules for Benzene
• Six overlapping p orbitals must form six
molecular orbitals.
• Three will be bonding, three antibonding.
• Lowest energy MO will have all bonding
interactions, no nodes.
• As energy of MO increases, the number of
nodes increases. =>

Chapter 16 8
MO’s for Benzene

=>
Chapter 16 9
 Energy Diagram for
Benzene
• The six electrons fill three bonding pi orbitals.
• All bonding orbitals are filled (“closed shell”),
an extremely stable arrangement.

=>
Chapter 16 10
MO’s for Cyclobutadiene

=>
Chapter 16 11
 Energy Diagram for
Cyclobutadiene

• Following Hund’s
rule, two electrons
are in separate
orbitals.
• This diradical would
be very reactive.

=>

Chapter 16 12
 Polygon Rule
The energy diagram for an annulene has
the same shape as the cyclic compound
with one vertex at the bottom.

=>
Chapter 16 13
 Aromatic Requirements
• Structure must be cyclic with conjugated
pi bonds.
• Each atom in the ring must have an
unhybridized p orbital.
• The p orbitals must overlap continuously
around the ring. (Usually planar structure)
• Compound is more stable than its open-
chain counterpart. =>
Chapter 16 14
 Anti- and Nonaromatic
• Antiaromatic compounds are cyclic,
conjugated, with overlapping p orbitals
around the ring, but the energy of the
compound is greater than its open-chain
counterpart.
• Nonaromatic compounds do not have a
continuous ring of overlapping p orbitals
and may be nonplanar. =>
Chapter 16 15
 Hückel’s Rule
• If the compound has a continuous ring
of overlapping p orbitals and has 4N + 2
electrons, it is aromatic.
• If the compound has a continuous ring
of overlapping p orbitals and has 4N
electrons, it is antiaromatic.

=>
Chapter 16 16
 [N]Annulenes
• [4]Annulene is antiaromatic (4N e-’s)
• [8]Annulene would be antiaromatic, but
it’s not planar, so it’s 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. =>
Chapter 16 17
 MO Derivation of
Hückel’s Rule
• Lowest energy MO has 2 electrons.
• Each filled shell has 4 electrons.

Chapter 16 18 =>
 Cyclopentadienyl Ions
• The cation has an empty p orbital, 4 electrons,
so antiaromatic.
• The anion has a nonbonding pair of electrons
in a p orbital, 6 e-’s, aromatic.

=>
Chapter 16 19
Acidity of Cyclopentadiene
pKa of cyclopentadiene is 16, much more
acidic than other hydrocarbons.

H H H

_
+ OC(CH3)3 + HOC(CH3)3

pKa = 16 pKa = 19

=>
Chapter 16 20
 Tropylium Ion
• The cycloheptatrienyl cation has 6 p
electrons and an empty p orbital.
• Aromatic: more stable than open chain ion
H
H OH
+ +
H , H2O

=>

Chapter 16 21
 Dianion of [8]Annulene
• Cyclooctatetraene easily forms a -2 ion.
• Ten electrons, continuous overlapping p
orbitals, so it is aromatic.

+
+ 2K + 2K

=>
Chapter 16 22
 Pyridine
• Heterocyclic aromatic compound.
• Nonbonding pair of electrons in sp2
orbital, so weak base, pKb = 8.8.

Chapter 16 23 =>
 Pyrrole
Also aromatic, but lone pair of electrons is
delocalized, so much weaker base.

=>
Chapter 16 24
 Basic or Nonbasic?
Pyrimidine has two basic
N N
nitrogens.

N N H
Imidazole has one basic
nitrogen and one nonbasic.

N
N
Purine?
N N =>
H Chapter 16 25
Other Heterocyclics

Chapter 16 26
=>
Fused Ring Hydrocarbons
• Naphthalene

• Anthracene

• Phenanthrene
=>

Chapter 16 27
 Reactivity of
Polynuclear Hydrocarbons
As the number of aromatic rings increases,
the resonance energy per ring decreases,
so larger PAH’s will add Br2.
H Br

Br

Br
H
H H Br
(mixture of cis and trans isomers) =>
Chapter 16 28
 Fused Heterocyclic
Compounds
Common in nature, synthesized for drugs.

=>
Chapter 16 29
 Allotropes of Carbon
• Amorphous: small particles of graphite;
charcoal, soot, coal, carbon black.
• Diamond: a lattice of tetrahedral C’s.
• Graphite: layers of fused aromatic rings.

=>
Chapter 16 30
 Some New Allotropes
• Fullerenes: 5- and 6-membered rings
arranged to form a “soccer ball” structure.
• Nanotubes: half of a C60 sphere fused to a
cylinder of fused aromatic rings.

=>
Chapter 16 31
 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

=>
Chapter 16 32
 Disubstituted Benzenes
The prefixes ortho-, meta-, and para- are
commonly used for the 1,2-, 1,3-, and 1,4-
positions, respectively.
Br NO2

Br HO
o-dibromobenzene or p-nitrophenol or
1,2-dibromobenzene 4-nitrophenol

=>
Chapter 16 33
 3 or More Substituents
Use the smallest possible numbers, but
the carbon with a functional group is #1.
OH
O 2N NO2 O 2N NO2

NO2 NO2
1,3,5-trinitrobenzene 2,4,6-trinitrophenol
=>
Chapter 16 34
 Common Names for
Disubstituted Benzenes

O OH
CH3 CH3 C
CH3 OH

CH3 H3C CH3 H3C

m-xylene mesitylene o-toluic acid p-cresol

=>
Chapter 16 35
 Phenyl and Benzyl
Phenyl indicates the benzene ring
attachment. The benzyl group has
an additional carbon.

Br CH2Br

phenyl bromide benzyl bromide

=>
Chapter 16 36
 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. =>
Chapter 16 37
IR and NMR Spectroscopy
• C=C stretch absorption at 1600 cm-1.
• sp2 C-H stretch just above 3000 cm-1.
• 1H NMR at 7-8 for H’s on aromatic
ring.
• 13C NMR at 120-150, similar to alkene
carbons.

=>
Chapter 16 38
Mass Spectrometry

=>
Chapter 16 39 =>
UV Spectroscopy

=>
Chapter 16 40
End of Chapter 16

Chapter 16 41