Aromatics Hacc

18.
1 Intro to Aromatic Compounds

AROMATIC compounds or ARENES include
benzene and benzene derivatives.
Aromatic compounds are quite common.

Many aromatic compounds were originally isolated from
fragrant oils.
However, many aromatic compounds are odorless.
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Klein, Organic Chemistry 1e
18-1
8 of the 10 best-selling drugs have aromatic

moieties.
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Coal contains aromatic rings fused together and

joined by nonromantic moieties.
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18.2 Nomenclature of Benzene

Derivatives
Benzene is generally the parent name for
monosubstituted derivatives.
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Many benzene derivatives have common names

that become the parent name. (memorize these)
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If the substituent is larger than the ring, the

substituent becomes the parent chain.
Aromatic rings are often represented with a Ph (for

phenyl) or with a (phi) symbol.
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The common name for dimethyl benzene

derivatives is XYLENE.
What do ORTHO, META, and PARA mean?
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Locants are required for rings with more than 2

substituents.
1. Identify the parent chain (generally the aromatic
ring):
Often a common name can be the parent chain.
2. Identify and name the substituents.

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3. Number the parent chain
A substituent that is part of the parent

name must be assigned locant
NUMBER 1.
4. List the numbered substituents

before the parent name in
alphabetical order:
Ignore prefixes (except iso) when

ordering alphabetically.
Complete the name for the molecule
above.
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Section: 18.2 What is the correct name for the following?
NH2
Br
a. o-bromoaniline
b. 2-bromoaniline
c. 1-amino-2-bromobenzene
d. all of the above
18.3 Structure of Benzene
In 1866, August Kekul proposed that benzene is

a ring comprised of alternating double and single
bonds.
Kekul suggested that the exchange of double and

single bonds was an equilibrium process.
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18-11
We now know that the aromatic structures are

resonance contributors rather than in equilibrium.
Sometimes the ring is represented with a circle in

it
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18.4 Stability of Benzene
The stability that results from a ring being

aromatic is striking.
Recall that in general, alkenes readily undergo addition

reactions.
Aromatic rings are stable enough that they do not

undergo such reactions.
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Heats of hydrogenation can be used to quantify

aromatic stability.
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Molecular orbital (MO) theory can help us explain

aromatic stability.
The six atomic p-orbitals of benzene overlap to
make six MOs.
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Summary of Critical Points of MO Theory

MO Theory is good for describing excited states,
ions, exotic species that defy Lewis structures.
Mix n atomic orbitals to form n molecular orbitals
each orbital has max occupation = 2 electrons

Fill from lowest energy MO
An MO has NO EFFECT until it contains an electron
For each bonding MO, there exists an anti-bonding
MO that can exactly cancel the bonding MO
Most likely excitation moves one electron from

HOMO to LUMO
18.4 Stability of Benzene
we can use FROST CIRCLES to predict the

relative MO energies.
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Use the FROST CIRCLES below to explain the

4n+2 rule.
Note that the number of bonding orbitals is always an

odd number; aromatic compounds will always have an
odd number of electron pairs.
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18.5 Aromatic Compounds Other

Than Benzene
Some rings must carry a formal charge to be
aromatic.
Consider a 5-membered ring.
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The pKa value for cyclopentadiene is much lower

than typical C-H bonds. WHY?
vs.
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Consider a 7-membered ring.
If six pi electrons are present, what charge will be

necessary?
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Which of the following are aromatic?

A.
B.
a. A
b. B
c. C
d. A and B
e. B and C
f. A and C
g. none of the above
h. all of the above
C.
Heteroatoms (atoms other than C or H) can also

be part of an aromatic ring.
If the heteroatoms lone pair is necessary, it will be

included in the HCKEL number of pi electrons.
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If the lone pair is necessary to make it aromatic,

the electrons will not be as basic.
pKa=5.2
pKa=0.4
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The difference in electron density can also be

observed by viewing the electrostatic potential
maps.
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18-25
Will the compounds below be aromatic,

antiaromatic, or non aromatic?
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18-27
18.6 Reactions at the Benzylic

Position
A carbon that is attached to a benzene

ring is BENZYLIC.
Recall that aromatic rings and alkyl
groups are not easily oxidized.
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HOWEVER, benzylic positions can readily be fully

oxidized.
The benzylic position needs to have at least one proton

attached to undergo oxidation.
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Permanganate can also be used as an oxidizing

reagent.
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18-30
BENZYLIC positions have similar

reactivity to allylic positions.
Benzylic positions readily undergo free radical

bromination.
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18-31
Once the benzylic position is substituted with a

bromine atom, a range of functional group
transformations are possible.
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18-32
Once the benzylic position is substituted with a

bromine atom, a range of functional group
transformations are possible.
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18-33
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18.6 Reactions at the Benzylic

Position
Give necessary reagents for the reactions below.
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18-35
Section: 18.6 What is the correct order of reagents to

achieve the following synthesis?
Br
a. 1) CH3CH2CH2MgBr 2) H2O
b. NBS, light, CCl4
c. HBr
d. NaBr
e. 1) LAH 2) H2O
1)
2)
3)
4)
5)
A
E, B
E, C
E, D
E, B, C
18.7 Reduction of the Aromatic

Moiety
Under forceful conditions, benzene can be

reduced to cyclohexane.
Is the process endothermic or exothermic? WHY?

WHY are forceful conditions required?
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Vinyl side groups can be selectively reduced.
H is just slightly less than the expected 120 kJ/mol

expected for a C=C CC conversion.
WHY are less forceful conditions required?
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18-38
18.7 Reduction of the Aromatic

Moiety
Note that the BIRCH reduction product has sp3

hybridized carbons on opposite ends of the ring.
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18-39
Like alkenes, benzene can undergo the BIRCH

reduction.
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18-40
Like alkenes, benzene can undergo the BIRCH

reduction.
Draw the final product.
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18-41
The presence of an electron donating alkyl side group

or EWD groups provides different regioselectivity. Why?
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18-42
Section: 18.7 What is the product(s) of the following

reaction.
NO2
A.
B.
NO2
NO2
Na, CH3OH
NH3
C.
NO2
D.
NO2
Section: 18.8
In 1H NMR spectrometry, aromatic C-H bonds show peaks
at _______ ppm.
In C NMR spectrometry, aromatic carbons show peaks at

_______ ppm.
In IR spectroscopy, aromatic C-H bonds show peaks at
_______ cm1.
a. 34, 100150, 14501600
b. 6.5-8.5, 100150, 3000-3100
c. 34, 100150, 2250
d. 6.5-8.5, 100150, 14501600
18.8 Spectroscopy of Aromatic

Compounds
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IR spectra for ethylbenzene:
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NMR of Aromatics
Recall from Section 16.5 how the anisotropic

effects of an aromatic ring affect NMR shifts.
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18-47
NMR of Aromatics
The integration and splitting of protons in the

aromatic region of the 1H NMR (7 ppm) in
often very useful.
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18-48
NMR of Aromatic Compounds
Because of possible ring symmetry, the number

of signals in the 13C NMR (100-150 ppm)
generally provides structural information.
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18-49
For the molecule below, predict the shift for the

13C signals, and predict the shift, integration,
and multiplicity for the 1H NMR signals.
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18-50
Graphite, Buckyballs, and

Nanotubes
Graphite consists of layers of sheets of
fused aromatic rings.
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18-51
Buckyballs are C60 spheres made of

interlocking aromatic rings.
Fullerenes come in other sizes such as C70.

How are Buckyballs aromatic when they are not
FLAT?
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18-52
Fullerenes can also be made into tubes

(cylinders).
Single, double, and multi-walled carbon nanotubes

have many applications:
Conductive Plastics, Energy Storage, Conductive

Adhesives, Molecular Electronics, Thermal Materials,
Fibres and Fabrics, Catalyst Supports, Biomedical
Applications
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18-53

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18.

1 Intro to Aromatic Compounds

Aromatic compounds are quite common.

Klein, Organic Chemistry 1e

8 of the 10 best-selling drugs have aromatic

Copyright 2012 John

Klein, Organic Chemistry 1e

Coal contains aromatic rings fused together and

Copyright 2012 John

Klein, Organic Chemistry 1e

18.2 Nomenclature of Benzene

Copyright 2012 John

Klein, Organic Chemistry 1e

Many benzene derivatives have common names

Copyright 2012 John

Klein, Organic Chemistry 1e

If the substituent is larger than the ring, the

Aromatic rings are often represented with a Ph (for

Copyright 2012 John

Klein, Organic Chemistry 1e

The common name for dimethyl benzene

What do ORTHO, META, and PARA mean?

Copyright 2012 John

Klein, Organic Chemistry 1e

Locants are required for rings with more than 2

Often a common name can be the parent chain.

2. Identify and name the substituents.

Klein, Organic Chemistry 1e

3. Number the parent chain

A substituent that is part of the parent

4. List the numbered substituents

Ignore prefixes (except iso) when

Copyright 2012 John

Klein, Organic Chemistry 1e

Section: 18.2 What is the correct name for the following?

Klein, Organic Chemistry 1e

18.3 Structure of Benzene

In 1866, August Kekul proposed that benzene is

Kekul suggested that the exchange of double and

Copyright 2012 John

Klein, Organic Chemistry 1e

We now know that the aromatic structures are

Sometimes the ring is represented with a circle in

Copyright 2012 John

Klein, Organic Chemistry 1e

18.4 Stability of Benzene

The stability that results from a ring being

Recall that in general, alkenes readily undergo addition

Aromatic rings are stable enough that they do not

Copyright 2012 John

Klein, Organic Chemistry 1e

Heats of hydrogenation can be used to quantify

Copyright 2012 John

Klein, Organic Chemistry 1e

Molecular orbital (MO) theory can help us explain

Copyright 2012 John

Klein, Organic Chemistry 1e

Summary of Critical Points of MO Theory

each orbital has max occupation = 2 electrons

Most likely excitation moves one electron from

18.4 Stability of Benzene

we can use FROST CIRCLES to predict the

Copyright 2012 John

Klein, Organic Chemistry 1e