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Aromaticity

Electrophilic Aromatic Substitution


The characteristic reaction of benzene is substitution, in which the resonance-
stabilized ring system is preserved. Above and below the plane of the benzene ring
there is a cloud of π electrons. Because of resonance, these π electrons are more
involved in holding together carbon nuclei than are the π electrons of a carbon-carbon
double bond. Still, in comparison with σ electrons, these π electrons are loosely held
and are available to a reagent that is seeking electrons.
It is not surprising that in its typical reactions the benzene ring serves as a source of
electrons, that is, as a base. The compounds with which it reacts are deficient in
electrons, that is, are electrophilic reagents or acids. Just as the typical reactions of
the alkenes are electrophilic addition reactions, so the typical reactions of the benzene
ring are electrophilic substitution reactions.

These reactions are characteristic not only of benzene itself, but of the benzene ring
wherever it is found and, indeed, of many aromatic rings, benzenoid and non-
benzenoid.

Electrophilic aromatic substitution includes a wide variety of reactions: nitration,


halogenation, sulfonation, and Friedel-Crafts reactions, undergone by nearly all
aromatic rings; reactions like nitrosation and diazo coupling, undergone only by rings
of high reactivity; and reactions like desulfonation, isotopic exchange, and many ring
closures which, although apparently unrelated, are found on closer examination to be
properly and profitably viewed as reactions of this kind. In synthetic importance
electrophilic aromatic substitution is permits the direct introduction of certain
substituent groups which can then be converted, by replacement or by transformation,
into other substituents, including even additional aromatic rings.

ELECTROPHILIC AROMATIC SUBSTITUTION

Ar = aryl, any aromatic group with attachment directly to ring carbon


1. Nitration.

2. Sulfonation.

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3. Halogenation.

4. Friedel-Crafts alkylation.

5. Friedel-Crafts acylation.

6. Protonation.

7. Thallation.

8. Nitrosation.

9. Diazo coupling.

10. Kolbe reaction. Only for phenols.


11. Reimer-Tiemann reaction. Only for phenols.

Effect of substituent groups


Like benzene, toluene undergoes electrophilic aromatic substitution: sulfonation, for
example. Although there are three possible monosulfonation products, this reaction
actually yields appreciable amounts of only two of them: the o- and p isomers.

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Benzene and toluene are insoluble in sulfuric acid, whereas the sulfonic acids are
readily soluble; completion of reaction is indicated simply by disappearance of the
hydrocarbon layer. When shaken with fuming sulfuric acid at room temperature,
benzene reacts completely within 20 to 30 minutes, whereas toluene is found to react
within only a minute or two. Studies of nitration, halogenation, and Friedel-Crafts
alkylation of toluene give analogous results. In some way the methyl group makes the
ring more reactive than unsubstituted benzene, and directs the attacking reagent to
the ortho and para positions of the ring.
On the other hand, nitrobenzene has been found to undergo substitution more slowly
than benzene, and to yield chiefly the meta isomer.
Like methyl or nitro, any group attached to a benzene ring affects the reactivity of the
ring and determines the orientation of substitution. When an electrophilic reagent
attacks an aromatic ring, it is the group already attached to the ring that determines
how readily the attack occurs and where it occurs.
A group that makes the ring more reactive than benzene is called an activating group.
A group that makes the ring less reactive than benzene is called a deactivating group.
A group that causes attack to occur chiefly at positions ortho and para to it is called an
ortho, para director. A group that causes attack to occur chiefly at positions meta to it
is called a meta director. The reactivity and orientation of substitution is based on
mechanism for electrophilic aromatic substitution.

Determination of orientation
To determine the effect of a group on orientation is, in principle, quite simple: the
compound containing this group attached to benzene is allowed to undergo
substitution and the product is analyzed for the proportions of the three isomers.
Identification of each isomer as ortho, meta, or para generally involves comparison
with an authentic sample of that isomer prepared by some other method from a
compound whose structure is known.
In this way it has been found that every group can be put into one of two classes:
ortho, para directors or meta directors. The orientation of nitration in a number of
substituted benzenes show that of the five positions open to attack, three (60%) are
ortho and para to the substituent group, and two (40%) are meta to the group; if there
were no selectivity in the substitution reaction, we would expect the ortho and para
isomers to make up 60% of the product, and the meta isomer to make up 40%. We see
that seven of the groups direct 96-100% of nitration to the ortho and para positions;
the other six direct 72-94% to the meta positions.

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A given group causes the same general kind of orientation predominantly ortho, para
or predominantly meta whatever the electrophilic reagent involved.
The actual distribution of isomers may vary, however, from reaction to reaction. For
example, compare the distribution of isomers obtained from toluene by sulfonation or
bromination with that obtained by nitration.

Determination of relative reactivity


A group is classified as activating if the ring it is attached to is more reactive than
benzene, and is classified as deactivating if the ring it is attached to is less reactive than
benzene. The reactivity's of benzene and substituted benzene are compared in one of
the following ways.
• The time required for reactions to occur under identical conditions can be
measured. Example, toluene is found to react with fuming sulfuric acid in about
one-tenth to one-twentieth the time required by benzene. Toluene is more
reactive than benzene, and ̶ CH3 is therefore an activating group.
• The severity of conditions required for comparable reaction to occur within the
same period of time can be observed. For example, benzene is nitrated in less
than an hour at 60˚ by a mixture of concentrated sulfuric acid and concentrated
nitric acid; comparable nitration of nitrobenzene requires treatment at 90˚ with

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fuming nitric acid and concentrated sulfuric acid. Nitrobenzene is evidently less
reactive than benzene, and the nitro group, NO2, is a deactivating group.
• Quantitative comparison under identical reaction conditions, competitive
reactions can be carried out, in which the compounds to be compared are
allowed to compete for a limited amount of a reagent. For example, if equimolar
amounts of benzene and toluene are treated with a small amount of nitric acid
(in a solvent like nitromethane or acetic acid, which will dissolve both organic
and inorganic reactants), about 25 times as much nitrotoluene as nitrobenzene
is obtained, showing that toluene is 25 times as reactive as benzene. On the
other hand, a mixture of benzene and chlorobenzene yields a product in which
nitrobenzene exceeds the nitrochlorobenzenes by 30: 1, showing that
chlorobenzene is only one-thirtieth as reactive as benzene. The chloro group is
therefore classified as deactivating, the methyl group as activating.

The activation or deactivation caused by some groups is extremely powerful: aniline,


C6H5NH2, is roughly one million times as reactive as benzene, and nitrobenzene,
C6H5NO2, is roughly one-millionth as reactive as benzene.

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