240 Chem
Aromatic Compounds
Chapter 6
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• The expressing aromatic compounds came to mean benzene
and derivatives of benzene.
Structure of Benzene: Resonance Description
C6H6
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.
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The Kekule Structure for Benzene
Kekule was the first to formulate a reasonable representation
of benzene:
The Kekule structure suggests alternating double and single
carbon-carbon bonds.
Based on the Kekule structure one would expect there to be
two different 1,2-dibromobenzenes but there is only one.
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The Kekule 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.
The true structure of benzene is a resonance hybrid of the two
Lewis structures, with the dashed lines of the hybrid indicating the
position of the bonds.
Or
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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).
Benzene-Molecular Orbital Description:
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Stability of Benzene:
• This energy difference ( 36 kcal/mol ) is the stabilization of benzene. It is 6
commonly referred as the resonance stabilization of benzene.
• The low heat of hydrogenation of benzene means that benzene
is especially stable even more so than conjugated polyenes. This
unusual stability is characteristic of aromatic compounds.
• Benzene’s unusual behavior is not limited to hydrogenation.
Benzene does not undergo addition reactions typical of other
highly unsaturated compounds, including conjugated dienes.
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Aromatic Character: The (4n + 2 ) π Rule
Hückel’s Rule
A molecule must be cyclic.
A molecule must be planar.
A molecule must be completely conjugated.
A molecule must satisfy Hückel’s rule, and contain a particular
number of electrons.
4n+2 π electrons ( n= 0, 1, 2, 3, ….= 2, 6, 10, 14, ….)
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Examples:
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Nomenclature of Aromatic compounds
• 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”
• “Benzyl” refers to “C6H5CH2-”
CH2Cl
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• Benzene is the parent name for some monosubstituted benzenes;
the substituent name is added as a prefix.
• The C6H5- group is called phenyl when it is a substituent
A hydrocarbon with a saturated chain and a benzene ring is
named by choosing the larger structural unit as the parent
If the chain is unsaturated then it must be the parent and the
benzene is then a phenyl substituent
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• For other monosubstituted benzenes, the presence of the
substituent results in a new parent name.
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• When two substituents are present their position may be indicated
by the prefixes ortho, meta, and para (o, m and p) or by the
corresponding numerical positions.
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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1-Bromo-2-chlorobenzene 1-Fluoro-3-nitrobenzene
o-Bromochlorobenzene m-Fluoronitrobenzene
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• For three or more substituents on a benzene ring:
Number to give the lowest possible numbers around the ring.
Alphabetize the substituent names.
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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• Polynuclear Aromatic Hydrocarbons:
1-Nitronaohthalene 2-Nitronaohthalene
α-Nitronaohthalene β-Nitronaohthalene 20
Electrophilic Aromatic Substitution
1- Specific Electrophilic Aromatic Substitution Reactions
Benzene does not undergo addition reactions like other
unsaturated hydrocarbons, because addition would yield a
product that is not aromatic.
Substitution of a hydrogen keeps the aromatic ring intact.
Halogenation, Alkylation, Nitration, and Sulfonation
are the typical electrophilic aromatic substitution reactions. 21
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General Mechanism-Electrophilic Aromatic Substitution
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Formation of the Electrophile for Bromination
Formation of the Electrophile NO2+ for Nitration
Formation of the Electrophile SO3H+ for Sulfonation
Formation of the Electrophile in Friedel-Crafts Acylation
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Formation of the Electrophile in Friedel-Crafts Alkylation
Friedel-Crafts Alkylation involving Carbocation rearrangement
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Examples:
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2- Side-Chain Reactions of Aromatic Compounds
A) Halogenation of an Alkyl Side-Chain
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B) Oxidation of an Alkyl Side-
Chain
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Disubstituted Benzenes: Orientation
Product ratio conclusion:
40% ortho, 40% meta, 20% para
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Orientation and Reactivity Effects of Substitutions Y in Electrophilic
Aromatic Substitution
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Examples:
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