Aromatic Halogenation -

Electrophilic aromatic halogenations also occur in the biosynthesis of many naturally occurring molecules, particularly those produced by marine organisms. In humans, the best-known example occurs in the thyroid gland during the biosynthesis of thyroxine, a hormone involved in regulating growth and metabolism. The amino acid tyrosine is first iodinated by thyroid peroxidase, and two of the iodinated tyrosine molecules then couple. The electrophilic iodinating agent is an $\mathrm{I}^{+}$species, perhaps hypoiodous acid (HIO), that is formed from iodide ion by oxidation with $\mathrm{H}_{2} \mathrm{O}_{2}$.
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Aromatic Halogenation -

Thyroxine
(a thyroid hormone)


Aromatic Nitration -

Aromatic rings are nitrated by reaction with a mixture of concentrated nitric and sulfuric acids. The electrophile is the nitronium ion, $\mathrm{NO}_{2}{ }^{+}$, which is formed from $\mathrm{HNO}_{3}$ by protonation and loss of water. The nitronium ion reacts with benzene to yield a carbocation intermediate, and loss of $\mathrm{H}^{+}$from this intermediate gives the neutral substitution product, nitrobenzene (FIGURE 16.5).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0516.jpg?height=255&width=1264&top_left_y=290&top_left_x=422)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0516.jpg?height=259&width=1272&top_left_y=521&top_left_x=421)


Aromatic Nitration -

Nitrobenzene


Aromatic Nitration -

FIGURE 16.5 The mechanism for electrophilic nitration of an aromatic ring. An electrostatic potential map of the reactive electrophile $\mathrm{NO}_{2}{ }^{+}$shows that the nitrogen atom is most positive.


Aromatic Nitration -

Electrophilic nitration of an aromatic ring does not occur in nature but is particularly important in the laboratory because the nitro-substituted product can be reduced by reagents such as iron, tin, or $\mathrm{SnCl}_{2}$ to yield the corresponding arylamine, $\mathrm{ArNH}_{2}$. Attachment of an amino group $\left(-\mathrm{NH}_{2}\right)$ to an aromatic ring by the two-step nitration/reduction sequence is a key part of the industrial synthesis of many dyes and pharmaceutical agents. We'll discuss this reduction and other reactions of aromatic nitrogen compounds in Chapter 24.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0516.jpg?height=218&width=652&top_left_y=1189&top_left_x=734)


Aromatic Sulfonation -

Aromatic rings can be sulfonated by reaction with so-called fuming sulfuric acid, a mixture of $\mathrm{H}_{2} \mathrm{SO}_{4}$ and $\mathrm{SO}_{3}$. The reactive electrophile is either $\mathrm{HSO}_{3}{ }^{+}$or neutral $\mathrm{SO}_{3}$, depending on reaction conditions, and substitution occurs by the same two-step mechanism seen previously for bromination and nitration (FIGURE 16.6). Note, however, that the sulfonation reaction is readily reversible. It can occur either forward or backward, depending on the reaction conditions. Sulfonation is favored in strong acid, but desulfonation is favored in hot, dilute aqueous acid.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0517.jpg?height=692&width=1172&top_left_y=207&top_left_x=474)

FIGURE 16.6 The mechanism for electrophilic sulfonation of an aromatic ring. An electrostatic potential map of the reactive electrophile $\mathrm{HOSO}_{2}{ }^{+}$shows that sulfur and hydrogen are the most positive atoms.


Aromatic Sulfonation -

Aromatic sulfonation does not occur naturally but is widely used in the preparation of dyes and pharmaceutical agents. For example, the sulfa drugs, such as sulfanilamide, were among the first clinically useful antibiotics. Although largely replaced today by more effective agents, sulfa drugs are still used in the treatment of meningitis and urinary tract infections. These drugs are prepared commercially by a process that involves aromatic sulfonation as its key step.
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Aromatic Sulfonation -

Sulfanilamide (an antibiotic)


Aromatic Hydroxylation -

Direct hydroxylation of an aromatic ring to yield a hydroxybenzene (a phenol) is difficult and rarely done in the laboratory but occurs much more frequently in biological pathways. An example is the hydroxylation of $p$-hydroxyphenylacetate to give 3,4 -dihydroxyphenylacetate. The reaction is catalyzed by $p$-hydroxyphenylacetate-3-hydroxylase and requires molecular oxygen plus the coenzyme reduced flavin adenine dinucleotide, abbreviated $\mathrm{FADH}_{2}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0517.jpg?height=229&width=1087&top_left_y=1799&top_left_x=519)


Aromatic Hydroxylation -

By analogy with other electrophilic aromatic substitutions, you might expect that an electrophilic oxygen species acting as an " $\mathrm{OH}^{+}$equivalent" is needed for the hydroxylation reaction. That is just what happens, with the electrophilic oxygen arising by protonation of FAD hydroperoxide, RO-OH (FIGURE 16.7); that is, $\mathrm{RO}-\mathrm{OH}+\mathrm{H}^{+} \rightarrow \mathrm{ROH}+\mathrm{OH}^{+}$. The FAD hydroperoxide itself is formed by reaction of $\mathrm{FADH}_{2}$ with $\mathrm{O}_{2}$.


FIGURE 16.7 MECHANISM -

Mechanism for the electrophilic hydroxylation of $p$-hydroxyphenylacetate, by reaction with FAD hydroperoxide. The hydroxylating species is an " $\mathrm{OH}^{+}$equivalent" that arises by protonation of FAD hydroperoxide, $\mathrm{RO}-\mathrm{OH}+\mathrm{H}^{+} \rightarrow \mathrm{ROH}+\mathrm{OH}^{+}$. The FAD hydroperoxide itself is formed by reaction of $\mathrm{FADH}_{2}$ with $\mathrm{O}_{2}$.
(1) Reduced flavin adenine dinucleotide reacts with molecular oxygen to give a hydroperoxide intermediate.


FIGURE 16.7 MECHANISM -

FAD hydroperoxide


FIGURE 16.7 MECHANISM -

Protonation of a hydroperoxide oxygen by an acid HA makes the neighboring oxygen electrophilic and allows the aromatic ring to react, giving a carbocation intermediate.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0518.jpg?height=256&width=888&top_left_y=1414&top_left_x=868)


FIGURE 16.7 MECHANISM -


FIGURE 16.7 MECHANISM -

PROBLEM Propose a mechanism for the electrophilic fluorination of benzene with SelectFluor.
16-2
PROBLEM How many products might be formed on chlorination of $o$-xylene ( $o$-dimethylbenzene), $m$-xylene,
16-3 and $p$-xylene?
PROBLEM When benzene is treated with $\mathrm{D}_{2} \mathrm{SO}_{4}$, deuterium slowly replaces all six hydrogens in the aromatic 16-4 ring. Explain.


FIGURE 16.7 MECHANISM - 16.3 Alkylation and Acylation of Aromatic Rings: The Friedel-Crafts Reaction

Among the most useful electrophilic aromatic substitution reactions in the laboratory is alkylation-the introduction of an alkyl group onto the benzene ring. Called the Friedel-Crafts reaction after its founders in 1877, Charles Friedel and James Crafts, the reaction is carried out by treating an aromatic compound with an alkyl chloride, RCl , in the presence of $\mathrm{AlCl}_{3}$ to generate a carbocation electrophile, $\mathrm{R}^{+}$. Aluminum chloride catalyzes the reaction by helping the alkyl halide to generate a carbocation in much the same way that $\mathrm{FeBr}_{3}$ catalyzes aromatic brominations by polarizing $\mathrm{Br}_{2}$ (Section 16.1). Loss of $\mathrm{H}^{+}$then completes the reaction (FIGURE 16.8).


FIGURE 16.8 MECHANISM
Mechanism for the Friedel-Crafts alkylation reaction of benzene with 2-chloropropane to yield isopropylbenzene (cumene). The electrophile is a carbocation, generated by $\mathbf{A l C l}_{\mathbf{3}}$-assisted dissociation of an alkyl halide.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0519.jpg?height=104&width=730&top_left_y=834&top_left_x=887)
(1) An electron pair from the aromatic ring attacks the carbocation, forming a $\mathrm{C}-\mathrm{C}$ bond and yielding a new carbocation intermediate.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0519.jpg?height=131&width=519&top_left_y=967&top_left_x=1096)
(1)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0519.jpg?height=280&width=358&top_left_y=1237&top_left_x=1076)


Despite its utility, the Friedel-Crafts alkylation has several limitations. For one thing, only alkyl halides can be used. Aromatic (aryl) halides and vinylic halides don't react because aryl and vinylic carbocations are too high in energy to form under Friedel-Crafts conditions.


A vinylic halide


Not reactive
Another limitation is that Friedel-Crafts reactions don't succeed on aromatic rings that are substituted either by a strongly electron-withdrawing group such as carbonyl $(\mathrm{C}=0)$ or by a basic amino group that can be protonated. We'll see in the next section that the presence of a substituent group already on a ring can have a dramatic effect on that ring's reactivity to further electrophilic substitution. Rings that contain any of the substituents listed in FIGURE 16.9 do not undergo Friedel-Crafts alkylation.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0520.jpg?height=356&width=1186&top_left_y=185&top_left_x=464)

FIGURE 16.9 Limitations on the aromatic substrate in Friedel-Crafts reactions. No reaction occurs if the substrate has either an electronwithdrawing substituent or a basic amino group.


A third limitation to the Friedel-Crafts alkylation is that it's often difficult to stop the reaction after a single substitution. Once the first alkyl group is on the ring, a second substitution reaction is facilitated for reasons we'll discuss in the next section. Thus, we often observe polyalkylation. Reaction of benzene with 1 mol equivalent of 2 -chloro-2-methylpropane, for example, yields $p$-di-tert-butylbenzene as the major product, along with small amounts of tert-butylbenzene and unreacted benzene. A high yield of mono-alkylation product is obtained only when a large excess of benzene is used.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0520.jpg?height=329&width=1278&top_left_y=903&top_left_x=418)

A final limitation to the Friedel-Crafts reaction is that a skeletal rearrangement of the alkyl carbocation electrophile sometimes occurs during reaction, particularly when a primary alkyl halide is used. Treatment of benzene with 1 -chlorobutane at $0^{\circ} \mathrm{C}$, for instance, gives an approximately $2: 1$ ratio of rearranged (sec-butyl) to unrearranged (butyl) products.

The carbocation rearrangements that accompany Friedel-Crafts reactions are like those that accompany electrophilic additions to alkenes (Section 7.11) and occur either by hydride shift or alkyl shift. For example, the relatively unstable primary butyl carbocation produced by reaction of 1-chlorobutane with $\mathrm{AlCl}_{3}$ rearranges to the more stable secondary butyl carbocation by the shift of a hydrogen atom and its electron pair (a hydride ion, $\mathrm{H}:^{-}$) from C 2 to C 1 . Similarly, alkylation of benzene with 1-chloro-2,2-dimethylpropane yields (1,1-dimethylpropyl)benzene. The initially formed primary carbocation rearranges to a tertiary carbocation by shift of a methyl group and its electron pair from C 2 to C 1 .
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0521.jpg?height=717&width=1166&top_left_y=192&top_left_x=477)


Benzene
(1,1-Dimethylpropyl)benzene
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0521.jpg?height=181&width=650&top_left_y=988&top_left_x=483)


Just as an aromatic ring is alkylated by reaction with an alkyl chloride, it is acylated by reaction with a carboxylic acid chloride, RCOCl , in the presence of $\mathrm{AlCl}_{3}$. That is, an acyl group ( -COR ; pronounced a-sil) is substituted onto the aromatic ring. For example, reaction of benzene with acetyl chloride yields the ketone acetophenone.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0521.jpg?height=261&width=801&top_left_y=1363&top_left_x=662)


The mechanism of Friedel-Crafts acylation is similar to that of Friedel-Crafts alkylation, and the same limitations on the aromatic substrate noted previously in FIGURE 16.9 for alkylation also apply to acylation. The reactive electrophile is a resonance-stabilized acyl cation, generated by reaction between the acyl chloride and $\mathrm{AlCl}_{3}$ (FIGURE 16.10). As the resonance structures in the figure indicate, an acyl cation is stabilized by interaction of the vacant orbital on carbon with lone-pair electrons on the neighboring oxygen. Because of this stabilization, no carbocation rearrangement occurs during acylation.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0521.jpg?height=554&width=1483&top_left_y=1908&top_left_x=321)

FIGURE 16.10 Mechanism of the Friedel-Crafts acylation reaction. The electrophile is a resonance-stabilized acyl cation, whose electrostatic potential map indicates that carbon is the most positive atom.


Unlike the multiple substitutions that often occur in Friedel-Crafts alkylations, acylations never occur more than once on a ring because the product acylbenzene is less reactive than the nonacylated starting material. We'll account for this reactivity difference in the next section.


Aromatic alkylations occur in numerous biological pathways, although there is of course no $\mathrm{AlCl}_{3}$ present in living systems to catalyze the reaction. Instead, the carbocation electrophile is typically formed by dissociation of an organodiphosphate, as we saw in Section 11.6. The dissociation is usually assisted by complexation to a divalent metal cation such as $\mathrm{Mg}^{2+}$, just as dissociation of an alkyl chloride is assisted by $\mathrm{AlCl}_{3}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0522.jpg?height=183&width=823&top_left_y=537&top_left_x=648)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0522.jpg?height=248&width=1025&top_left_y=792&top_left_x=542)


An example of a biological Friedel-Crafts reaction occurs during the biosynthesis of phylloquinone, or vitamin $\mathrm{K}_{1}$, the human blood-clotting factor. Phylloquinone is formed by reaction of 1,4-dihydroxynaphthoic acid with phytyl diphosphate. Phytyl diphosphate first dissociates to a resonance-stabilized allylic carbocation, which then substitutes onto the aromatic ring in the typical way. Several further transformations lead to phylloquinone (FIGURE 16.11).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0522.jpg?height=1151&width=1535&top_left_y=1273&top_left_x=292)

FIGURE 16.11 Biosynthesis of phylloquinone (vitamin $\mathbf{K}_{\mathbf{1}}$ ) from 1,4-dihydroxynaphthoic acid. The key step that joins the 20-carbon phytyl side chain to the aromatic ring is a Friedel-Crafts-like electrophilic substitution reaction with a diphosphate ion as the leaving group.


WORKED EXAMPLE 16.1 -


Predicting the Product of a Carbocation Rearrangement -

The Friedel-Crafts reaction of benzene with 2 -chloro-3-methylbutane in the presence of $\mathrm{AlCl}_{3}$ occurs with a carbocation rearrangement. What is the structure of the product?


Strategy -

A Friedel-Crafts reaction involves initial formation of a carbocation, which can rearrange by either a hydride shift or an alkyl shift to give a more stable carbocation. Draw the initial carbocation, assess its stability, and see if the shift of a hydride ion or an alkyl group from a neighboring carbon will result in increased stability. In the present instance, the initial carbocation is a secondary one that can rearrange to a more stable tertiary one by a hydride shift.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0523.jpg?height=207&width=1028&top_left_y=764&top_left_x=546)


Strategy -

Secondary
carbocation
Tertiary carbocation


Strategy -

Use this more stable tertiary carbocation to complete the Friedel-Crafts reaction.


Solution -


Solution -

PROBLEM Which of the following alkyl halides would you expect to undergo Friedel-Crafts reaction with 16-5 rearrangement and which without? Explain.
(a) $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{Cl}$
(b) $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}(\mathrm{Cl}) \mathrm{CH}_{3}$
(c) $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{Cl}$
(d) $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CCH}_{2} \mathrm{Cl}$
(e) Chlorocyclohexane


Solution -

PROBLEM What is the major monosubstitution product from the Friedel-Crafts reaction of benzene with 16-6 1-chloro-2-methylpropane in the presence of $\mathrm{AlCl}_{3}$ ?


Solution - 16.4 Substituent Effects in Electrophilic Substitutions

Only one product can form when an electrophilic substitution occurs on benzene, but what would happen if we were to carry out a reaction on an aromatic ring that already has a substituent? The initial presence of a substituent on the ring has two effects.