Benzene and Aromaticity

Benzene and Aromatic Compounds

Background:
• Benzene (C6H6) is the simplest aromatic hydrocarbon
(aromatic compounds are called arenes).
• Benzene has four degrees of unsaturation, making it
a highly unsaturated hydrocarbon.
• Whereas unsaturated hydrocarbons such as alkenes,
alkynes and dienes readily undergo addition
reactions, benzene does not.

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 Benzene and Aromatic Compounds
Historical:
• August Kekulé proposed that benzene was a rapidly
equilibrating mixture of two compounds, each
containing a six-membered ring with three
alternating  bonds.
• In the Kekulé description, the bond between any two
carbon atoms is sometimes a single bond and
sometimes a double bond.
• These structures are known as Kekulé structures.

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 Benzene and Aromatic Compounds
The Structure of Benzene:

Any structure for benzene must account for the

following facts:
1. It contains a six-membered ring and three additional
degrees of unsaturation.
2. It is planar.
3. All C—C bond lengths are equal.

The Kekulé structures satisfy the first two criteria but

not the third, because having three alternating  bonds
means that benzene should have three short double
bonds alternating with three longer single bonds.

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 Benzene and Aromatic Compounds
The Resonance Structure of Benzene:

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 Benzene and Aromatic Compounds
The Structure of Benzene:
• Because each  bond has two electrons, benzene has
six  electrons.

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 Benzene and Aromatic Compounds
The Structure of Benzene:
• In benzene, the actual bond length (1.39 Å) is
intermediate between the carbon—carbon single bond
(1.53 Å) and the carbon—carbon double bond (1.34 Å).

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Aromatic Compounds
 Aromatic was used to described some fragrant
compounds in early 19th century
 Current: distinguished from aliphatic compounds
by electronic configuration

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 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• To name a benzene ring with one substituent, name
the substituent and add the word benzene.

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 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:

• Common names used for monosubstituted benzenes:

Toluene, Phenol, Aniline, Anisole

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11
 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• There are three different ways that two groups can be
attached to a benzene ring, so the prefixes: ortho,
meta, or para are used to designate the relative
position of the two substituents.

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or or or
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
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 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• If the two groups on the benzene ring are different,
alphabetize the names of the substituents preceding
the word benzene.
• If one substituent is part of a common root, name the
molecule as a derivative of that monosubstituted
benzene.

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 Naming disubstituted Benzene Compounds
• Disubsituted benzenes are also named by the common prefixes
ortho, meta and para

Examples:
Br CH3

Cl

Br

meta-dibromobenzene ortho -chlorotoluene

(1,3-dibromobenzene) (1-chloro-2-methylbenzene)

OH NH2

Br

para-ethylphenol 4-bromo-2-fluoroanaline
(1-hydroxy-4-ethylbenzene) (1-amino-4-bromo-2-fluorobenzene)
 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:

For three or more substituents on a benzene ring:

1. Number to give the lowest possible numbers
around the ring.
2. Alphabetize the substituent names.
3. When substituents are part of common roots,
name the molecule as a derivative of that
monosubstituted benzene. The substituent that
comprises the common root is located at C1.

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 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:

• Other common monosubstituted benzenes:

benzaldehyde, benzoic acid, acetophenone & styrene
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 Nomenclature
• For three or more substituents:
– if one of the substituents imparts a special name, name the
molecule as a derivative of that parent
– if none of the substituents imparts a special name, number
the substituents to give the smallest set of numbers, and
list them in alphabetical order before the ending "benzene"

CH3 OH NO2
1
1
2 NO2 Br 6 2 Br 4
3

2
3 5 3
4 4
1
Br
Cl Br CH2 CH3
4-Ch loro-2- 2,4,6-Trib romoph enol 2-Bromo-1-ethyl-4-
nitrotoluen e n itroben zene
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 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• A benzene substituent is called a phenyl group, and it
can be abbreviated in a structure as “Ph-”.

• Therefore, benzene can be represented as PhH, and

phenol would be PhOH.

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 Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• The benzyl group, another common substituent that
contains a benzene ring, differs from a phenyl group.

• Substituents derived from other substituted aromatic

rings are collectively known as aryl groups.

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 Nomenclature
– phenyl group (C6H5- or Ph-): the substituent
group derived by loss of an H from benzene

4 2
3 1
C6 H5
Ph enyl group 1-Ph enylcyclohexene 4-Phen yl-1-b utene
IUPAC names?

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 Properties of Benzene
 Unusually stable - heat of
hydrogenation 150 kJ/mol less
negative than a cyclic triene
 Planar hexagon: bond angles are
120°, carbon–carbon bond lengths
139 pm
 Undergoes substitution rather
than electrophilic addition
 Resonance hybrid with structure
between two Lewis structures
 These properties (and others) are
labeled “aromatic” or
“aromaticity”. 23
 Benzene and Aromatic Compounds
The Criteria for Aromaticity:
Four structural criteria must be satisfied for a compound
to be aromatic.
[1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with

p orbitals on adjacent atoms.
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 Benzene and Aromatic Compounds
The Criteria for Aromaticity:
[2] A molecule must be planar.
All adjacent p orbitals must be aligned so that the 
electron density can be delocalized.

Since cyclooctatetraene is non-planar, it is not

aromatic, and it undergoes addition reactions just like
those of other alkenes.

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 Benzene and Aromatic Compounds

The Criteria for Aromaticity:

[3] A molecule must be completely conjugated.

Aromatic compounds must have a p orbital on every atom
and each must overlap with adjacent p orbitals.

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 Benzene and Aromatic Compounds
The Criteria for Aromaticity:

[4] A molecule must satisfy Hückel’s rule, which

requires a particular number of  electrons.
Hückel's rule:

Benzene is aromatic and especially stable because it

contains 6  electrons.

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Compounds With 4n  Electrons Are Not
Aromatic (May be Antiaromatic)

 Planar, cyclic molecules with 4n 

electrons are much less stable than
expected (anti-aromatic)
 Cyclobutadiene is so unstable that
it dimerizes by a self-Diels-Alder
reaction even at low temperature

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 Benzene and Aromatic Compounds
Cyclobutadiene is antiaromatic and especially unstable
because it contains 4  electrons.

As the number of fused rings increases, the number of

resonance structures increases. Naphthalene is a
hybrid of three resonance structures whereas
benzene is a hybrid of two.

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 Compounds With 4n  Electrons Are Not
Aromatic (May be Antiaromatic)

 If the ring is larger, it will

distort out of planar and
behave like an ordinary
alkene
 8-electron (and higher)
compounds are not
delocalized (single and
double bonds)
 Cyclooctatetraene has four
double bonds, reacting
with Br2, KMnO4, and HCl
as if it were four alkenes
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 Benzene and Aromatic Compounds
Hückel’s Rule
Note that Hückel’s rule refers to the number of  electrons,
not the number of atoms in a particular ring.

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 Benzene and Aromatic Compounds
Aromatic, Antiaromatic and Nonaromatic Compounds
With regard to aromaticity, a compound can be
classified in one of three ways:

1. Aromatic: A cyclic, planar, completely conjugated

compound with 4n + 2  electrons.
2. Antiaromatic: A cyclic, planar, completely
conjugated compound with 4n  electrons.
3. Nonaromatic: A compound that lacks one (or more)
of the following requirements for aromaticity: being
cyclic, planar, and completely conjugated.

A completely conjugated, monocyclic hydrocarbon is

called an annulene (not necessarily aromatic).
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 Benzene and Aromatic Compounds
Aromatic, Antiaromatic and Nonaromatic Compounds
Note the relationship between each compound type and a similar
open-chained molecule having the same number of  electrons.

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Aromatic Ions
 The 4n + 2 rule applies to ions as well as
neutral species
 Both the cyclopentadienyl anion and the
cycloheptatrienyl cation are aromatic
 The key feature of both is that they contain 6 
electrons in a ring of continuous p orbitals

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Polycyclic Aromatic Compounds:
Naphthalene
 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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 Physical Properties of Aromatic Compounds
• Because aromatic compounds (like benzene) are flat, they
stack well, and so have higher melting and boiling points than
corresponding alkanes and alkenes (similar to cycloalkanes)
• Substituted aromatic compounds can have higher or lower
melting and boiling points than benzene
- para-xylene has a higher m.p. than benzene
- ortho and meta-xylene have lower m.p.’s than benzene
• Aromatic compounds are more dense than other hydrocarbons,
but less dense than water (halogenated aromatics can be more
dense than water, as can haloalkanes)
• Aromatic compounds are insoluble in water, and are
commonly used as solvents for organic reactions
• Aromatic compounds are also flammable, and many are
carcinogenic
 Electrophilic Aromatic
Substitution

• Although benzene’s pi electrons are in a stable aromatic system, they

are available to attack a strong electrophile to give a carbocation.
• This resonance-stabilized carbocation is called a sigma complex
because the electrophile is joined to the benzene ring by a new sigma
bond.
• Aromaticity is regained by loss of a proton.

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 Chemical Reactivity of Aromatic Compounds
• Aromatic compounds do not undergo addition reactions because
they would lose their special stability (aromaticity)
• Instead, they undergo substitution reactions, which allow them
to retain their aromaticity
• We will study three types of substitution reactions of benzene:
halogenation, nitration and sulfonation
Addition:
Br

+ Br 2
Br

Aromatic Loses aromaticity

Substitution:
Br
FeBr3
+ Br 2 + HBr

Aromatic Retains Aromaticity

Mechanism for the Bromination
of Benzene: Step 1
+ -
Br Br FeBr3 Br Br FeBr3
(stronger electrophile than Br2)

 Before the electrophilic aromatic substitution can take

place, the electrophile must be activated.
 A strong Lewis acid catalyst, such as FeBr3, should
be used.

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 Mechanism for the Bromination
of Benzene: Steps 2 and 3
Step 2: Electrophilic attack and formation of the sigma complex.
H H
H H H
H
Br Br FeBr3 Br
+ FeBr4-
H H H H
H H

Step 3: Loss of a proton to give the products.

H H
H FeBr4-
H H Br
Br
+ FeBr3 + HBr
H H H H
H H
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 Chlorination and Iodination

 Chlorination is similar to bromination.

AlCl3 is most often used as catalyst, but
FeCl3 will also work.
 Iodination requires an acidic oxidizing
agent, like nitric acid, to produce iodide
cation.
H+ + HNO3 + ½ I2 I+ + NO2 + H2O

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 Nitration of Benzene

NO2
HNO3
H2SO4 + H2O

 Sulfuric acid acts as a catalyst, allowing the reaction

to be faster and at lower temperatures.
 HNO3 and H2SO4 react together to form the
electrophile of the reaction: nitronium ion (NO2+).

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Mechanism for the Nitration of
Benzene

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 Ortho and Para Substitution

 Ortho and para attacks are preferred because their

resonance structures include one tertiary carbocation.
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 Meta Substitution

 When substitution occurs at the meta position, the

positive charge is not delocalized onto the tertiary
carbon, and the methyl groups has a smaller effect
on the stability of the sigma complex.
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 Reduction of the Nitro Group
NO2 NH2
Zn, Sn, or Fe
aq. HCl

 Treatment with zinc, tin, or iron in dilute acid

will reduce the nitro to an amino group.
 This is the best method for adding an amino
group to the ring.
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 Sulfonation of Benzene

SO3H
H2SO4
+ SO3

 Sulfur trioxide (SO3) is the electrophile in the

reaction.
 A 7% mixture of SO3 and H2SO4 is commonly
referred to as “fuming sulfuric acid”.
 The —SO3H groups is called a sulfonic acid.
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 Mechanism of Sulfonation

 Benzene attacks sulfur trioxide, forming a sigma

complex.
 Loss of a proton on the tetrahedral carbon and
reprotonation of oxygen gives benzenesulfonic acid.
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 Desulfonation Reaction

SO3H +
H
H , heat
+ H2O + H2SO4

 Sulfonation is reversible.
 The sulfonic acid group may be removed
from an aromatic ring by heating in dilute
sulfuric acid.
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 Nitration of Toluene

 Toluene reacts 25 times faster than benzene.

 The methyl group is an activator.
 The product mix contains mostly ortho and
para substituted molecules.
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 Friedel–Crafts Alkylation

 Synthesis of alkyl benzenes from alkyl halides

and a Lewis acid, usually AlCl3.
 Reactions of alkyl halide with Lewis acid
produces a carbocation, which is the
electrophile.
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 Friedel–Crafts Acylation

 Acyl chloride is used in place of alkyl chloride.

 The product is a phenyl ketone that is less
reactive than benzene.

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 Clemmensen Reduction

 The Clemmensen reduction is a way to

convert acylbenzenes to alkylbenzenes by
treatment with aqueous HCl and
amalgamated zinc.
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 Birch Reduction
H H H
H H H H
Na or Li
NH3 (l), ROH
H H H H
H H H

 This reaction reduces the aromatic ring to a

nonconjugated 1,4-cyclohexadiene.
 The reducing agent is sodium or lithium in a
mixture of liquid ammonia and alcohol.
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