Organic Chemistry Chapter 15

6th Edition
Paula Yurkanis Bruice
Aromaticity •
Reactions of
Benzene

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Aromatic Compounds Are Unusually Stable

Benzene is an aromatic compound

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Benzene is unusually stable because of electron
delocalization
Compounds with unusually large resonance energies,
such as benzene, are called aromatic compounds

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 Criteria for Aromaticity
1. A compound must have an uninterrupted cyclic cloud
of π electrons above and below the plane of the
molecule:

2. The π cloud must contain an odd number of pairs

of π electrons, or 4n + 2 (n = 0, 1, 2 …) total
electrons.
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 Hückel’s Rule
For a planar, cyclic compound to be aromatic, its
uninterrupted π cloud must contain (4n + 2) π electrons,
where n is any whole number

Why?

Pattern of bonding orbitals of planar cyclic π systems (e.g.,

benzene):

Needs 4n + 2 (n = 0, 1, 2,
3…) electrons to fill orbitals

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Monocyclic hydrocarbons with alternating single and
double bonds are called annulenes:

Cyclobutadiene and cyclooctatetraene are not aromatic,

because they have an even number of π electron pairs
Cyclooctatetraene is a stable compound because it is
large enough to form a tub shape, thereby removing
degenerate orbitals
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 not not
aromatic
aromatic aromatic

Cyclopentadiene does not have an uninterrupted ring of

p orbital-bearing atoms

Cyclopentadienyl cation has an even number of π

electron pairs

Cyclopentadienyl anion has an uninterrupted ring of π

orbital-bearing atoms and an odd number of π electron
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The resonance hybrid shows that all the carbons in the
cyclopentadienyl anion are equivalent

Each carbon has exactly one-fifth of the negative charge

associated with the anion

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These compounds consist of fused benzene rings and
are aromatic:

Any compound consisting of fused benzene rings is

aromatic

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 Aromatic Heterocyclic Compounds
Heteroatom donates Heteroatom donates two electrons
one electron

A heterocyclic compound has ring atoms other than

carbon
The heteroatom donates either one or two electrons to
the π system
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Pyridine Is Aromatic

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 Pyrrole Is Aromatic
The lone-pair electrons on the nitrogen atom of pyrrole
are π electrons

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Furan and thiophene are aromatic compounds like
pyrrole

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Examples of Heterocyclic
Aromatic Compounds

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 DNA & RNA Bases Are
Aromatic
Purine bases Pyrimidine bases

These heterocycles are aromatic because of amide

resonance:

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The Effect of Aromaticity on the pKa
Values of Some Compounds

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Why is the pKa of cyclopentadiene so much lower than
that of ethane?

The conjugate base is aromatic:

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Aromaticity influences chemical reactivity:

The cycloheptatrienyl cation is aromatic:

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 Antiaromaticity
A compound is antiaromatic if it is a planar, cyclic,
continuous loop of p orbitals with an even number of
pairs of π electrons:

Antiaromatic compounds are highly unstable, but the

nonplanar versions are stable
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 A Molecular Orbital Description of
Aromaticity and Antiaromaticity
Aromatic compounds are stable because they have filled
bonding π molecular orbitals:

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Nomenclature of Monosubstituted Benzenes

Some are named by attaching “benzene” after the name

of the substituent:

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Some have to be memorized:

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A benzene substituent is called phenyl.
A benzene substitutuent with a methylene group is
called benzyl.

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Benzene is either the base name or the substituent
(phenyl):

Aryl group (Ar) is the general term for either an

unsubstituted or a substituted phenyl group

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Aromatic compounds such as benzene undergo
electrophilic aromatic substitution reactions:

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Benzene is a nucleophile that reacts with an electrophile
An electrophilic substitution yields an aromatic product,
which is significantly more stable than the addition
reaction

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Reaction Coordinate Diagrams for the
Two Benzene Reactions

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There are five common electrophilic aromatic substitution
reactions:

1. Halogenation

2. Nitration

3. Sulfonation

4. Friedel–Crafts acylation

5. Friedel–Crafts alkylation 28
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General Mechanism for Electrophilic
Aromatic Substitution of Benzene

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Halogenation of Benzene

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Lewis acid weakens the Br–Br (or Cl–Cl) bond, which
makes the halogen a better electrophile:

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Mechanism for bromination:
B: Bromide or Benzene

The catalyst is regenerated:

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Nitration of Benzene

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Nitronium ion formation:

Electrophilic aromatic substitution:

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Sulfonation of Benzene

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Sulfonic acid is a strong acid:

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Sulfonation is reversible:

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Reaction coordinate diagram for electrophilic
aromatic substitution:

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 Friedel–Crafts Acylation Reactions

The electrophile is an acylium ion:

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Mechanism for Friedel–Crafts acylation:

Must be carried out with more than one equivalent of

AlCl3:

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Friedel–Crafts Alkylation of Benzene

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Mechanism for Friedel–Crafts alkylation:

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The carbocation will rearrange to a more stable species:

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However, 100% of the 2-methyl-2-phenylbutane
product can be obtained if a bulky alkyl halide is used:

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Friedel–Crafts alkylation will not produce a good yield
of an alkylbenzene containing a straight-chain group,
because the carbocation will rearrange:

Acylium ions, however, do not rearrange:

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Methodologies Used for
the Reduction Step

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Chemical Modification of Substituents of Benzene

Reactions of alkyl substituents:

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The resulting halide product can undergo a nucleophilic
substitution reaction:

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Remember that halo-substituted alkyl groups can also
undergo E2 and E1 reactions (Section 9.8)

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Substitutions with double and triple bonds can undergo
catalytic hydrogenation (Sections 4.11 and 6.9)

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Oxidation of an alkyl group bonded to a benzene ring…

Provided that a hydrogen is bonded to the benzylic

carbon,

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The same reagent that oxidizes alkyl substituents will
oxidize benzylic alcohols:

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However, aldehydes or ketones can be generated if a
milder oxidizing agent is used:

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Reducing a Nitro Substituent

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It is possible to selectively reduce just one of the two
nitro groups:

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Summary of Electrophilic Aromatic
Substitution Reactions

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Summary of Friedel–Crafts
Reactions

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