Aromaticity

Eslam B. Elkaeed, PhD

Lecturer of Organic Chemistry
Faculty of Pharmacy, Al-Azhar University
Cairo, Egypt
 Aromaticity
• Many derivatives of benzene were originally isolated from
the fragrant balsams, therefore they are called aromatic
in reference to their pleasant odors.

• 8 of the 10 best-selling drugs in 2007 contained the

benzene-like aromatic moiety (highlighted in red).

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 Aromaticity

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 Nomenclature of Benzene Derivatives
• Using benzene as the parent and listing the substituent
as a prefix

• common names accepted by IUPAC.

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 Nomenclature of Benzene Derivatives

• If the substituent is larger than the benzene ring, then the

benzene ring is treated as a substituent and is called a
phenyl group

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Nomenclature of Benzene Derivatives
Disubstituted Derivatives of Benzene

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Nomenclature of Benzene Derivatives
Polysubstituted Derivatives of Benzene
• Follow the four-step process:
1. Identify and name the parent.
2. Identify and name the substituents.
3. Assign a locant to each substituent.
4. Arrange the substituents alphabetically.

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 Structure of Benzene
• In 1825, Michael Faraday isolated benzene from the oily
residue left by illuminating gas in London street lamps.

• Further investigation showed that the molecular formula

of this compound was C6H6

• In 1866, August Kekulé proposed benzene structure as a

ring comprised of alternating double and single bonds.

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 Structure of Benzene
• The two drawings are now viewed as resonance
structures, not as an equilibrium process.

• The p orbitals of benzene

overlap continuously around
the ring.

• This is the source of benzene

stability
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 Stability of Benzene
• Benzene is much more stable than expected
• Benzene does NOT undergo a similar reactions of alkenes

• Recall that hydrogenation of a π bond proceeds in the

presence of a metal catalyst.

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 Stability of Benzene
• Under forcing conditions, benzene also undergoes
hydrogenation and reacts with 3 equivalents of molecular
hydrogen to form cyclohexane.

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 Stability of Benzene

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 Stability of Benzene
Hückel’s Rule
• Cyclobutadiene (C4H4) and Cyclooctatetraene (C8H8) do
not exhibit aromatic stability.

• Benzene has a total of six π electrons, or three electron

pairs.
• With an odd number of electron pairs, benzene is
aromatic.
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 Stability of Benzene
Hückel’s Rule
• The requirement for an odd number of electron pairs is
called Hückel’s rule.

• Expressed mathematically as 4n+2 = π electrons, where n

is a whole number.

• For benzene: 4n+2 = 6

4n = 4
n=1 so, benzene is aromatic

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 Stability of Benzene
Hückel’s Rule
Q. Predict whether each of the following compounds should
be aromatic:

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 The Criteria for Aromaticity
• A compound will be aromatic if it satisfies the following
four criteria:
1. Cyclic
2. Planar
3. Sp2 hybridized carbons (the ring contains
continuously overlapping p orbitals)

4. Obey Hückel rule

• Compounds that fail the 1st, 2nd, or 3rd criterion are called
nonaromatic.
• Compounds that fail the 4th criterion are called
antiaromatic.
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 The Criteria for Aromaticity

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 Annulenes
• Annulenes are compounds consisting of a single ring
containing a fully conjugated p system.

• [6]Annulene is benzene, which is aromatic.

• [10]Annulene nonaromatic: the hydrogen atoms inside the

ring (shown in red) experience a steric interaction that
forces the compound out of planarity.

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 Aromatic ions
• Cyclopentadienyl anion is a five-membered ring contains
six π electrons (a Hückel number); in which one of the
carbon atoms possess two electrons (a carbanion)

• Cyclopentadienyl anion has a continuous system of

overlapping p orbitals.

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 Aromatic ions
• tropylium cation is a 7-membered ring contains six π
electrons (a Hückel number); in which one of the carbon
atoms possess an empty p orbital (a carbocation)

• Cyclopentadienyl anion has a continuous system of

overlapping p orbitals.

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 Aromatic ions
Q. Determine whether each of the following ions is aromatic,
nonaromatic, or antiaromatic:

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 Reactions at the Benzylic Position
• Any carbon atom attached directly to a benzene ring is
called a benzylic position:

Oxidation
• Chromic acid (H2CrO4) is a strong oxidizing agent,
selectively, oxidize the alkylbenzenes at the benzylic
position:

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 Reactions at the Benzylic Position
• The benzylic position must have at least one proton. If
the benzylic position lacks a proton, then oxidation does
not occur.

• Oxidation can also be accomplished with potassium

permanganate (KMnO4).

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 Reactions at the Benzylic Position
Q. Draw the expected product when each of the following
compounds is treated with chromic cid:

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 Reactions at the Benzylic Position
Substitution/Elimination Reactions of Benzylic Halides

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