Quercetin

Aromatic Compounds

1
 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. He named it benzin.
• Other related compounds with low C:H ratios
had a pleasant smell, so they were classified
as aromatic.
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
3
 Resonance Structures of Benzene

• Benzene is actually a resonance hybrid between the two

Kekulé structures.
• The C—C bond lengths in benzene are shorter than typical
single-bond lengths, yet longer than typical double-bond
lengths (bond order 1.5).
• Benzene's resonance can be represented by drawing a circle
inside the six-membered ring as a combined representation.
4
 Structure of Benzene

• Each sp2 hybridized C in the ring has an

unhybridized p orbital perpendicular to the ring
which overlaps around the ring.
• The six pi electrons are delocalized over the six
carbons.
5
Unusual Addition of Bromine to Benzene

• When bromine adds to benzene, a catalyst such as FeBr3 is

needed.
• The reaction that occurs is the substitution of a hydrogen
by bromine.
• Addition of Br2 to the double bond is not observed.
6
 Resonance Energy
• Benzene does not have the predicted heat of
hydrogenation of -360 kJ/mol.
( 3 X heat of hydrogenation of cyclohexene -
120kJ/mol)
• The observed heat of hydrogenation is
-208 kJ/mol, a difference of 151 kJ.
• This difference between the predicted and
the observed value is called the resonance
energy. 7
Molar Heats of Hydrogenation

8
 Annulenes

• Annulenes are hydrocarbons with alternating single

and double bonds.
• Benzene is a six-membered annulene, so it can be
named [6]-annulene. Cylobutadiene is [4]-annulene,
cyclooctatetraene is [8]-annulene.
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 Annulenes
• All cyclic conjugated
hydrocarbons were
proposed to be aromatic.
• However, cyclobutadiene is
so reactive that it dimerizes
before it can be isolated.
• Cyclooctatetraene adds Br2
readily to the double bonds.

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 Aromatic Requirements
• Structure must be cyclic with conjugated
pi bonds
• Each atom in the ring must have an unhybridized p
orbital (sp2 or sp).
• The p orbitals must overlap continuously around the
ring. Structure must be planar (or close to planar for
effective overlap to occur)
• Delocalization of the pi electrons over the ring must
lower the electronic energy.
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 Anti- and Nonaromatic
• Antiaromatic compounds are cyclic,
conjugated, with overlapping p orbitals
around the ring, but electron delocalization
increases its electronic energy.
• Nonaromatic compounds do not have a
continuous ring of overlapping p orbitals
and may be nonplanar.

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 Hückel’s Rule
• Once the aromatic criteria (monocyclic,
planar, conjugated pi bond) is met,
Huckel’s rule applies.
• If the number of pi electrons is (4N + 2) the
compound is aromatic (where N is an
integer)
• If the number of pi electrons is (4N) the
compound is antiaromatic.
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 Orbital Overlap of Cyclooctatetraene

• Cyclooctatetraene assumes a nonplanar tub

conformation that avoids most of the overlap
between the adjacent pi bonds. Huckel's rule
simply does not apply.
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 Annulenes
• [4]Annulene is antiaromatic.
• [6] Annulene is benzene
• [8]Annulene would be antiaromatic, but it’s not
planar, so it’s nonaromatic.
• [10]Annulene is aromatic except for the isomers
that are nonplanar.
• Larger 4N annulenes are not antiaromatic because
they are flexible enough to become nonplanar.

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 Annulenes

Cyclooctatetraene

[18] Annulene 16
 Cyclopentadienyl Ions

• The cation has an empty p orbital, 4 electrons,

so it is antiaromatic.
• The anion has a nonbonding pair of electrons
in a p orbital, 6 electrons, it is aromatic.
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 Deprotonation of Cyclopentadiene

• By deprotonating the sp3 carbon of cyclopentadiene,

the electrons in the p orbitals can be delocalized over
all five carbon atoms and the compound would be
aromatic.
• Cyclopentadiene is acidic because deprotonation will
convert it to an aromatic ion.
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 Orbital View of the Deprotonation of
Cyclopentadiene

• Deprotonation will allow the overlap of all the p

orbitals in the molecule.
• Cyclopentadiene is not necessarily as stable as
benzene and it reacts readily with electrophiles.
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 Resonance Forms of
Cyclopentadienyl Ions

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 Tropylium Ion

aromatic

• The cycloheptatrienyl cation has 6 pi electrons and an

empty p orbital.
• The cycloheptatrienyl cation is easily formed by
treating the corresponding alcohol with dilute (0.01N)
aqueous sulfuric acid.
• The cycloheptatrienyl cation is commonly known as the
tropylium ion.
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 Cyclooctatetraene Dianion

• Cyclooctatetraene reacts with potassium metal

to form an aromatic dianion.
• The dianion has 10 pi electrons and is
aromatic.
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 Which of the following is an
aromatic compound?

Non-aromatic Aromatic
There is an sp3 carbon in All carbons are sp2
the ring, delocalization hybridized and it obeys
will not be complete. Huckel’s rule.

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 Pyridine Pi System

• Pyridine has six delocalized electrons in its pi

system.
• The two non-bonding electrons on nitrogen are in
an sp2 orbital, and they do not interact with the pi
electrons of the ring.
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 Pyridine

• Pyridine is basic, with a pair non-bonding

electrons available to abstract a proton.
• The protonated pyridine (the pyridinium ion) is
still aromatic.
25
 Pyrrole Pi System

• The pyrrole nitrogen atom is sp2 hybridized with a

lone pair of electrons in the p orbital. This p orbital
overlaps with the p orbitals of the carbon atoms to
form a continuous ring.
• Pyrrole is aromatic because it has 6 pi electrons
(N = 1).
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 Pyrrole

• Also aromatic, but lone pair of electrons is

delocalized, so much weaker base.
27
 Basic or Nonbasic?
Pyrimidine has two basic
N N
nitrogens.

N N H
Imidazole has one basic
nitrogen and one nonbasic.
Not basic
N
N
Only one of purine’s nitrogens
N N is not basic.
H
Not basic
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Other Heterocyclics

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Is the molecule below aromatic, anti-
aromatic or non-aromatic?

H
N
N N

Aromatic

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 Naphthalene

• Fused rings share 2 atoms and the bond

between them.
• Naphthalene is the simplest fused aromatic
hydrocarbon.
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Fused Ring Hydrocarbons
anthracene phenanthrene

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 Polynuclear Aromatic
Hydrocarbons
H Br

Br
H
H Br
H Br

As the number of aromatic rings increases, the

resonance energy per ring decreases, so larger
polynuclear aromatic hydrocarbons will add Br 2.

33
 Larger Polynuclear
Aromatic Hydrocarbons
• Formed in combustion (tobacco smoke).
• Many are carcinogenic.
• Epoxides form, combine with DNA base.
12 1
11 2
10
3
9

8 4
7 6 5

pyrene Benzo[pyrene
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 Fused Heterocyclic Compounds
Common in nature

Antimalarial
Synthesized for drugs

Cancer AIDS 35
Common Names of Benzene
Derivatives

36
 Disubstituted Benzenes

Numbers can also be used to identify the

relationship between the groups; ortho- is 1,2-
disubstituted, meta- is 1,3, and para- is 1,4.
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 Three or More Substituents
Use the smallest possible numbers, but
the carbon with a functional group is #1.

38
 Common Names for
Disubstituted Benzenes

O OH
CH3 CH3 C
CH3 OH

CH3 H3C CH3 H3C

m-xylene mesitylene o-toluic acid p-cresol

39
 Phenyl and Benzyl

Br CH2Br

phenyl bromide benzyl bromide

Phenyl indicates the benzene ring attachment. The

benzyl group has an additional carbon.

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Importance of Aromatic Compounds

Aspirin DDT

AZT Valium
AIDS drug (A tanquilizer)
41
 Physical Properties of Aromatic
Compounds
• 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.

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