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John E. McMurry

Why this Chapter?

Aromatic rings are a common part of many
organic structures.

www.cengage.com/chemistry/mcmurry

Chapter 5
Aromatic Compounds

Aromatic Compounds
Aromatic was used to described some fragrant
compounds in early 19th century
Not correct: later they are grouped by chemical
behavior (unsaturated compounds that undergo
substitution rather than addition)

Aromatic compounds are particularly important

in nucleic acid chemistry and the chemistry of
several amino acids.

5.1 Structure of Benzene

Benzene reacts slowly with Br2 to give bromobenzene
(where Br replaces H)
This is substitution rather than the rapid addition
reaction common to compounds with C=C, suggesting
that, in benzene, there is a higher barrier

Current: distinguished from aliphatic compounds by

electronic configuration

Benzenes Unusual Structure

All its C-C bonds are the same length:
139 pm between
single (154 pm) and double (134 pm) bonds

Each C is sp2 and has a p orbital perpendicular to

the plane of the six-membered ring

Electron density in all six C-C bonds is identical

Structure is planar, hexagonal
CCC bond angles 120

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5.2 Naming Aromatic Compounds

Many common names
toluene = methylbenzene;
aniline = aminobenzene
Monosubstituted benzenes systematic names as
hydrocarbons with benzene
C6H5Br = bromobenzene
C6H5NO2 = nitrobenzene,
and C6H5CH2CH2CH3 is propylbenzene

methylbenzene

Common Names of Benzene

Derivatives
OH

CH3

phenol
H
C CH2

styrene

phenyl bromide

OCH3

aniline
O

CH3

benzaldehyde

When a benzene ring is a substituent, the term

phenyl is used (for C6H5)
You may also see Ph or f in place of C6H5

anisole

acetophenone
Br

The Phenyl Group

NH2

toluene

aminobenzene

Benzyl refers to C6H5CH2

OH

benzoic acid

CH2Br

benzyl bromide

Disubstituted Benzenes
Relative positions on a benzene ring
ortho- (o) on adjacent carbons (1,2)
meta- (m) separated by one carbon (1,3)
para- (p) separated by two carbons (1,4)
Describes reaction patterns (occurs at the para
position)

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Naming Benzenes with More Than Two

Substituents
Choose numbers to get lowest possible values
List substituents alphabetically with hyphenated
numbers
Common names, such as toluene can serve as
root name (as in TNT)

5.3 Electrophilic Aromatic Substitution

Reactions: Bromination

Electrophilic aromatic substitution

General Mechanism

Benzene is aromatic: a cyclic conjugated compound

with 6 electrons
Reactions of benzene lead to the retention of the
aromatic core

5.3 Electrophilic Aromatic

Substitution Reactions: Bromination
Benzenes electrons participate as a Lewis base in
reactions with Lewis acids
The product is formed by loss of a proton, which is
replaced by bromine

Formation of Product from Intermediate

The cationic addition intermediate transfers a
proton to FeBr4- (from Br- and FeBr3)
This restores aromaticity (in contrast with
addition in alkenes)

FeBr3 is added as a
catalyst to polarize the
bromine reagent

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5.4 Other Aromatic Substitutions

Chlorine and iodine (but not fluorine, which is too
reactive) can produce aromatic substitution with the
addition of other reagents to promote the reaction
Chlorination requires FeCl3

Aromatic Nitration
Iodine must be oxidized to form a more powerful I +
species (with Cu+ or peroxide)

Aromatic Sulfonation
Substitution of H by SO3H (sulfonation)
Reaction with a mixture of sulfuric acid and
SO3

The combination of nitric acid and sulfuric acid

produces NO2+ (nitronium ion)
The reaction with benzene produces nitrobenzene

5.5 The FriedelCrafts Alkylation and

Acylation Reactions
Alkylation among most useful electrophilic
aromatic subsitution reactions
Aromatic substitution of R+ for H+

Reactive species is sulfur trioxide or its conjugate acid

Aluminum chloride promotes the formation of

the carbocation

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Limitations of the Friedel-Crafts

Alkylation
Only alkyl halides can be used (F, Cl, I, Br)
Aryl halides and vinylic halides do not react (their
carbocations are too hard to form)
Will not work with rings containing an amino group
substituent or a strongly electron-withdrawing group

Acylation of Aromatic Rings

Reaction of an acid chloride (RCOCl) and an
aromatic ring in the presence of AlCl3 introduces
acyl group, COR
Benzene with acetyl chloride yields
acetophenone

5.8 Oxidation and Reduction of Aromatic

Compounds
Alkyl side chains can be oxidized to CO2H by
strong reagents such as KMnO4 and Na2Cr2O7 if they
have a CH next to the ring
Converts an alkylbenzene into a benzoic acid, ArR
ArCO2H

5.8 Oxidation and Reduction of Aromatic

Compounds
Just as aromatic rings are inert to oxidation, they are
also inert to reduction under typical alkene conditions
High temperatures and pressures are required in
order to reduce aromatic rings.

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5.7 An Explanation of Substituent Effects

O

Br

Fe
Br

-C

-C

Cl 3
Al

SO

H2

CH
3 Cl
AlCl

NO 3
2 SO
4

H-C
Cl

Deactivating groups withdraw electrons from the

ring, destabilizing the Wheland intermediate
Substituents can cause a compound to be (much)
more or (much) less reactive than benzene

Cl 3
Al

CH 3

H2

Activating groups donate electrons to the ring,

stabilizing the Wheland intermediate (carbocation)

CH 3

Summary Table: Effect of Substituents

in Aromatic Substitution
Substituents affect the orientation of the
reaction the positional relationship is
controlled
ortho- and para-directing activators,
ortho- and para-directing deactivators,
and meta-directing deactivators
(Table 16.1)

5.6 Substituent Effects in Electrophilic

Aromatic Substitution, Summary Graph

5.7 An Explanation of Substituent Effects

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SO

Br 3
Fe

B
r

Br

R
-C
Al - Cl
Cl

Fe
Br

Cl 3
Al

2 SO
4

H-C
Cl

CH
3 Cl
AlCl

CH 3

SO 4
H2 O3
N
H2

Synthesis as a Tool for Learning Organic

Chemistry
In order to propose a synthesis you must be familiar
with reactions
What they begin with
What they lead to
How they are accomplished
What the limitations are

3 Cl

CH

AlC

nO 4
KM O
H2

CH 3

A synthesis combines a series of proposed steps to

go from a defined set of reactants to a specified
product

Synthesizing a Substituted Aromatic

Compound
Synthesize p-bromobenzoic acid starting from benzene.
Questions related to synthesis can include partial
information about a reaction of series that the
student completes
Compare the target and the starting material
Consider reactions that efficiently produce the outcome.
Look at the product and think of what can lead to it

Synthesizing a Substituted Aromatic

Compound: Solution
Two workable routes are possible.

Strategy:
Work backward by first asking, What is an
immediate precursor of p-bromobenzoic acid?.
Continue this process until benzene is the starting
material.
Note: This is usually more than one synthetic route
possible.

5.9 Other Aromatic Compounds

Aromatic compounds can have rings that share a set of
carbon atoms (fused rings)
Compounds from fused benzene or aromatic heterocycle
rings are themselves aromatic

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Naphthalene Orbitals
Three resonance forms and delocalized electrons

5.9 Other Aromatic Compounds

heterocyclic aromatic compounds contain elements
other than carbon in a ring, such as N,S,O,P
Cyclic compounds that contain only carbon are called
carbocycles (not homocycles)
Nomenclature is specialized

Pyridine
A six-membered heterocycle with a nitrogen atom in
its ring
electron structure resembles benzene (6 electrons)
The nitrogen lone pair electrons are not part of the
aromatic system (perpendicular orbital)
Pyridine is a relatively weak base compared to
normal amines but protonation does not affect
aromaticity

Pyrrole
A five-membered heterocycle with one nitrogen
electron system similar to that of cyclopentadienyl
anion
Four sp2-hybridized carbons with 4 p orbitals
perpendicular to the ring and 4 p electrons
Nitrogen atom is sp2-hybridized, and lone pair of
electrons occupies a p orbital (6 electrons)
Since lone pair electrons are in the aromatic ring,
protonation destroys aromaticity, making pyrrole a
very weak base