CHAPTER 9

Aromatic Compounds
Early Days of Organic Chemistry
Aromatic Compounds
Formerly used to describe fragrant substances such as
benzaldehyde (from cherries, peaches, and almonds), toluene
(from Tolu balsam 吐魯香), and benzene (from coal distillate)

Now used to refer to the class of compounds that contain six-

membered benzene-like rings with three double bonds
Present Days of Organic Chemistry
Aromatic Compounds
Benzene
▪ Found to cause bone marrow depression
▪ Leads to leukopenia, or lowered white blood cell count, on
prolonged exposure
Many naturally occurring compounds are aromatic in part
▪ Steroidal hormone estrone
▪ Atorvastatin (Lipitor) – a cholesterol-lowering drug
9-1 Naming Aromatic Compounds
Aromatic substances have acquired nonsystematic names
Nonsystematic names are discouraged but allowed by IUPAC
• Common name for methylbenzene (甲苯) is toluene
• Common name for hydroxybenzene is phenol （酚）
• Common name for aminobenzene （苯胺） is aniline

苯甲酸

苯乙烯
Naming Aromatic Compounds
Monosubstituted Benzenes （單取代苯類）
Systematically named in same manner as other hydrocarbons
benzene used as parent name
1. C6H5Br is bromobenzene 溴化苯
2. C6H5NO2 is nitrobenzene 硝基苯
3. C6H5CH2CH2CH3 is propylbenzene 丙基苯
Naming Aromatic Compounds
Arenes： Alkyl-substituted benzenes
Named depending on the size of the alkyl group
▪ Alkyl substituent smaller than the ring (6 or fewer carbons),
named as an alkyl substituted benzene
▪ Alkyl substituent larger than the ring (7 or more carbons), named
as a phenyl-substituted alkane
Phenyl
Derived from the Greek pheno (“I bear light”)
Michael Faraday discovered benzene in 1825 from the oily residue left by
illuminating gas used in London street lamps
▪ Used for the –C6H5 unit when the benzene ring is considered as a
substituent
▪ Abbreviated as Ph or  (Greek phi)
Benzyl
▪ Used for the C6H5CH2– group
Naming Aromatic Compounds
烷基有7個碳→主要碳鏈→苯被視為取代基(phenyl-substituted alkane)
Naming Aromatic Compounds
Disubstituted benzenes 雙取代苯類
Named using one of the prefixes
1. ortho- (o-)： Ortho-disubstituted benzene has two substituents in a
1,2 relationship
2. meta- (m-)： Meta-disubstituted benzene has its substituents in a
1,3 relationship
3. para- (p-)： Para-disubstituted benzene has its substituents in a
1,4 relationship

鄰 間 對
Naming Aromatic Compounds
Benzenes with more than two substituents
1. Named by numbering the position of each so that the lowest
possible numbers are used
2. The substituents are listed alphabetically when writing the name

Any of the monosubstituted aromatic compounds in Table 9.1

can serve as a parent name, with the principal substituent
(-OH in phenol or –CH3 in toluene) attached to C1 on the ring
9-2 Structure and Stability of Benzene
Benzene
1. Benzene is unsaturated
2. Benzene is much less reactive than typical alkene and
fails to undergo the usual alkene reactions
▪ Cyclohexene reacts rapidly with Br2 and gives the addition
product 1,2-dibromocyclohexane
▪ Benzene reacts only slowly with Br2 and gives the
substitution product C6H5Br
Structure and Stability of Benzene
 A quantitative idea of benzene’s stability is obtained from
heats of hydrogenation (氫化→放熱)
 Benzene is 150 kJ/mol (36 kcal/mol) more stable than
might be expected for “cyclohexatriene”
Structure and Stability of Benzene
Carbon-carbon bond lengths and angles in benzene
All carbon-carbon bonds are 139 pm in length
▪ Intermediate between typical C-C single bond (154 pm) and typical
double bond (134 pm)
▪ Electrostatic potential map shows that the electron density in all six
carbon-carbon bonds is identical
Benzene is planar
▪ All C-C-C bond angles are 120°
▪ All six carbon atoms are sp2-hybridized with p orbital perpendicular
to the plane of the ring
Structure and Stability of Benzene
a) All six carbon atoms and all six p orbitals in benzene
are equivalent
b) Each p orbital overlaps equally well with both neighboring p
orbitals, leading to a picture of benzene in which the six 
electrons are completely delocalized around the ring
c) Benzene is a hybrid of two equivalent resonance forms
▪ Neither form is correct by itself
▪ The true structure of benzene is somewhere in between the
two resonance forms
Structure and Stability of Benzene
d) Six p atomic orbitals combine in a cyclic manner, six
benzene  molecular orbitals result
e) The three lower-energy molecular orbitals, denoted 1, 2,
and 3, are bonding combinations
▪ 2 and 3 have the same energy and are said to be degenerate
Structure and Stability of Benzene
▪ The three higher-energy molecular orbitals, denoted 4,
5, and 6, are antibonding combinations
▪ 4 and 5 have the same energy and are said to be
degenerate
Structure and Stability of Benzene
▪ 3 and 4 have nodes passing through ring carbon atoms,
therefore no  electron density on these carbons
▪ The six p electrons occupy the three bonding molecular orbitals
and are delocalized over the entire conjugated system
9-3 Aromaticity and the Hückel 4n + 2 Rule

Benzene and other benzene-like aromatic molecules

share similar characteristics:
▪ Benzene is cyclic and conjugated
▪ Benzene is unusually stable; it is 150 kJ/mol (36 kcal/mol)
more stable than might be expected
▪ Benzene is planar and has the shape of a regular hexagon.
All bond angles are 120º, all carbon atoms are sp2-
hybridized, and all carbon-carbon bond lengths are 139 pm
▪ Benzene undergoes substitution reactions that retain the
cyclic conjugation rather than electrophilic addition reactions
that would destroy the conjugation
▪ Benzene is a resonance hybrid whose structure is
intermediate between two line-bond structures
Aromaticity and the Hückel 4n + 2 Rule
The Hückel 4n + 2 rule devised in 1931 by the German
physicist Erich Hü ckel
1. A molecule is aromatic (芳香族的) only if it has a planar,
monocyclic system of conjugation and contains a total of
4n + 2  electrons, where n is an integer (n = 0, 1, 2,
3,…)
2. Only molecules with 2, 6, 10, 14, 18,…  electrons can be
aromatic
3. Molecules with 4n  electrons (4, 8, 12, 16,…) can not be
aromatic, said to be antiaromatic because delocalization
of their  electrons would lead to their destabilization
Aromaticity and the Hückel 4n + 2 Rule
Examples of the Hückel 4n + 2 rule
 Cyclobutadiene
▪ Contains four  electrons localized into two double bonds
rather than delocalized around the ring
▪ Antiaromatic
▪ Highly reactive
▪ Shows none of the properties associated with aromaticity
▪ Not prepared until 1965
Aromaticity and the Hückel 4n + 2 Rule
 Benzene
▪ Contains six  electrons (4n + 2 = 6 when n = 1)
▪ Aromatic
Aromaticity and the Hückel 4n + 2 Rule
 Cyclooctatetraene
▪ Contains eight  electrons
▪ The  electrons are localized onto four double bonds rather than
delocalized around the ring
▪ Not aromatic
▪ The molecule is tub-shaped rather than planar
▪ It has no cyclic conjugation because neighboring p orbitals do
not have the necessary parallel alignment for overlap
▪ Resembles an open-chain polyene in its reactivity
Aromaticity and the Hückel 4n + 2 Rule
Energy Levels of Cyclic Conjugated Molecules (4n + 2
Electrons)
a) There is always a single lowest-lying MO, above which the
MOs come in degenerate pairs.
b) When electrons fill the various molecular orbitals, one pair
of electrons fills the lowest-lying orbital and two pairs of
electrons fill each of the n successive energy levels – a
total of 4n + 2.
c) Any other number would leave a bonding energy level
partially unfilled
Aromaticity and the Hückel 4n + 2 Rule
Energy levels of the six benzene  molecular orbitals
✓ The lowest-energy MO, 1, occurs single and contains a pair
of electrons
✓ 2 and 3, are degenerate, and it takes two pairs of electrons
to fill them
✓ The result is a stable six--electron aromatic molecule with
filled bonding orbitals
9-4 Aromatic Ions and Aromatic Heterocycles

 Ions and heterocyclic compounds can also be aromatic

Q: 這四個離子有甚麼共同特徵可被視為芳香族?
Aromatic Ions and Aromatic Heterocycles
 Aromatic Ions
There are three ways in which the hydrogen might be removed
from cyclopenta-1,3-diene and cyclohepta-1,3,5-triene
▪ The hydrogen can be removed with both electrons (H:-)
leaving a carbocation
▪ The hydrogen can be removed with one electron (H.) leaving
a carbon radical
▪ The hydrogen can be removed with no electrons (H+)
leaving a carbon anion, or carbanion
Aromatic Ions and Aromatic Heterocycles
4n + 2 rule predicts cyclopentadienyl anion and
cycloheptatrienyl cation to be aromatic

6/3甲
Aromatic Ions and Aromatic Heterocycles
a) Aromatic cyclopentadienyl anion, showing the cyclic conjugation and six
 electrons in five p orbitals
b) Aromatic cycloheptatrienyl cation, showing the cyclic conjugation and
six  electrons in seven p orbitals
Aromatic Ions and Aromatic Heterocycles

 Aromatic Heterocycles 芳香雜環化合物

A cyclic compound that contains atoms of two or more
different elements in its ring, usually carbon along with
nitrogen, oxygen, or sulfur

▪ Pyridine (吡啶) is much like benzene in its  electron

structure
▪ A six-membered heterocycle with nitrogen in its ring
▪ Each of the five sp2-hybridized carbons has a p orbital
perpendicular to the plane of the ring, and each p orbital
contains one  electron
Aromatic Ions and Aromatic Heterocycles
▪ The nitrogen atom is also sp2-hybridized and has one
electron in a p orbital, bringing the total to six  electrons
▪ The nitrogen lone pair electrons are in an sp2 orbital in
the plane of the ring and are not involved with the
aromatic  system

吡啶
Aromatic Ions and Aromatic Heterocycles
▪ Pyrimidine is much like benzene in its  electron structure
▪ Has two nitrogen atoms in a six-membered, unsaturated ring
▪ Both nitrogens are sp2-hybridized, and each contributes one
electron to the aromatic  system
Aromatic Ions and Aromatic Heterocycles
▪ Pyrrole is a five membered heterocycle with six  electrons
▪ Aromatic
▪ Each of the sp2-hybridized carbons contributes one  electron
▪ The sp2-hybridized nitrogen atom contributes the two electrons
from its lone pair, which occupies a p orbital

6/3甲
Aromatic Ions and Aromatic Heterocycles
▪ Imidazole is an analog of pyrrole that has two nitrogen
atoms in a five-membered, unsaturated ring
▪ Both nitrogens are sp2-hybridized
▪ One nitrogen is in a double bond and contributes only one
electron to the aromatic  system
▪ The other nitrogen is not in a double bond and contributes
two from its lone pair
Aromatic Ions and Aromatic Heterocycles

Nitrogen atoms have different roles depending

on the structure of the molecule
▪ In pyridine and pyrimidine, the nitrogen atoms are
both in double bonds and contribute only one 
electron to the aromatic sextet, like a carbon atom
in benzene does
▪ In pyrrole, the nitrogen atom is not in a double bond
and contributes two  electrons (the lone pair) to
the aromatic sextet
▪ In imidazole, both a double-bonded “pyridine-like”
nitrogen that contributes one  electron and a
“pyrrole-like” nitrogen that contributes two 
electrons are present in the same molecule
雜環芳香族中含氮的分子：pyridine, pyrimidine, pyrrole, imidazole
Aromatic Ions and Aromatic Heterocycles
 Pyrimidine and imidazole rings are important in biological
chemistry
▪ Pyrimidine is the parent ring system in cytosine, thymine, and uracil,
three of the five heterocycle amine bases found in nucleic acids
▪ An aromatic imidazole ring is present in histidine, one of the twenty
amino acids found in proteins
Worked Example 9.1
Accounting for the Aromaticity of a Heterocycle
Thiophene, a sulfur-containing heterocycle, undergoes
typical aromatic substitution reaction rather than addition
reactions. Why is thiophene aromatic?
Worked Example 9.1
Accounting for the Aromaticity of a Heterocycle

Strategy
▪ Recall the requirements for aromaticity
▪ A planar, cyclic, conjugated molecule with
4n + 2  electrons
▪ See how requirements for aromaticity apply to
thiophene
Worked Example 9.1
Accounting for the Aromaticity of a Heterocycle
Solution
▪ Thiophene is the sulfur analog of pyrrole
▪ The sulfur atom is sp2-hybridized and has a lone pair of
electrons in a p orbital perpendicular to the plane of the ring
▪ Sulfur also has a second lone pair of electrons in the ring
plane
9-5 Polycyclic Aromatic Compounds
The general concept of aromaticity can be extended to
include polycyclic aromatic compounds
多環芳香族

▪ Benzo[a]pyrene is one of the cancer-causing substances found

in tobacco smoke
Polycyclic Aromatic Compounds
All polycyclic aromatic hydrocarbons can be represented by a
number of different resonance forms
▪ Naphthalene （萘丸/樟腦丸） has three

▪ Naphthalene shows many of the chemical properties associated with

aromaticity
▪ Heat of hydrogenation measurements show an aromatic
stabilization energy of approximately 250 kJ/mol (60 kcal/mol)
▪ Naphthalene reacts slowly with electrophiles to give substitution
products rather than double-bond addition products
Polycyclic Aromatic Compounds
 Aromaticity of Naphthalene
▪ Naphthalene has a cyclic, conjugated  electron system, with p
orbital overlap both around the ten-carbon periphery of the
molecule and across the central bond
▪ 10 is a Hückel number (4n + 2 when n = 2) so there is 
electron delocalization and consequent aromaticity in
naphthalene
Polycyclic Aromatic Compounds
There are many heterocyclic analogs of naphthalene：
Quinoline, isoquinoline, indole, and purine
Quinoline, isoquinoline, and purine all contain pyridine-like
nitrogens that are part of a double bond and contribute one
electron to the aromatic  system
Indole and purine contain pyrrole-like nitrogens that contribute
two  electrons

腸道桿菌鑑定用的染劑
Polycyclic Aromatic Compounds
Biological molecules that contain polycyclic aromatic rings
▪ The amino acid tryptophan contains an indole ring and the
anti-malarial drug quinine contains a quinoline ring
Polycyclic Aromatic Compounds
▪ Adenine and guanine, two of the five heterocyclic amine
bases found in nucleic acids, have rings based on purine
9-6 Reactions of Aromatic Compounds:
Electrophilic Substitution
Electrophilic aromatic substitution 親電子芳香族取代反應
▪ A process in which an electrophile (E+) reacts with an
aromatic ring and substitutes for one of the hydrogens
▪ The most common reaction of aromatic compounds
▪ This reaction is characteristic of all aromatic rings
▪ The ability of a compound to undergo electrophilic
substitution is a good test of aromaticity
Reactions of Aromatic Compounds: Electrophilic
Substitution
Many substituents can be introduced onto an aromatic ring
through electrophilic substitution reactions
▪ Halogen (-Cl, -Br, -I)
▪ Nitro group (-NO2)
▪ Sulfonic acid
group (-SO3H)
▪ Hydroxyl group
(-OH)
▪ Alkyl group (-R)
▪ Acyl group (-COR)

磺胺化
Reactions of Aromatic Compounds: Electrophilic
Substitution
Electrophilic alkene addition
▪ Addition of a reagent such as HCl to an alkene
▪ The electrophilic hydrogen approaches the  electrons of
the double bond and forms a bond to one carbon, leaving a
positive charge at the other carbon
▪ The carbocation intermediate then reacts with the
nucleophilic Cl- ion to yield the addition product
Reactions of Aromatic Compounds: Electrophilic
Substitution
 One difference between electrophilic aromatic
substitution reactions and electrophilic alkene
addition reactions is that aromatic rings are less
reactive toward electrophiles than alkenes

 Br2 in CH2Cl2 solution reacts instantly with

most alkenes but does not react with benzene at
room temperature
Reactions of Aromatic Compounds: Electrophilic
Substitution
Electrophilic aromatic substitution reaction begins in a similar
way to electrophilic alkene addition reaction
FeBr3 catalyst is needed for bromination of benzene to occur
a) FeBr3 polarizes Br2 molecule, making it more electrophilic
b) Polarization makes FeBr4-Br+ species that reacts as if it were Br+
c) The polarized Br2 molecule reacts with the nucleophilic benzene ring to
yield a nonaromatic carbocation intermediate which is doubly allylic and
has three resonance forms
Reactions of Aromatic Compounds: Electrophilic
Substitution
 The intermediate carbocation in electrophilic aromatic
substitution is more stable than a typical alkyl carbocation
because of resonance but much less stable than the starting
benzene ring
 Comparison of alkene addition and aromatic substitution
Instead of adding Br- to give an addition product, the carbocation
intermediate loses H+ from the bromine-bearing carbon
a) If addition occurred, the 150 kJ/mol stabilization energy of the
aromatic ring would be lost and the overall reaction would be
endergonic (Ｇ>0)
b) When substitution occurs, the stability of the aromatic ring is
retained and the reaction is exergonic (Ｇ<0)
▪ Loss of H+ restores aromaticity to ring
▪ The net effect is the substitution of H+ by Br+
Reactions of Aromatic Compounds: Electrophilic
Substitution
The mechanism of the electrophilic bromination of benzene
▪ The reaction occurs in two steps and involves a resonance-
stabilized carbocation intermediate
Reactions of Aromatic Compounds: Electrophilic
Substitution
Energy diagram for the electrophilic bromination of benzene
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Aromatic Fluorination
a) Fluorine is too reactive to be inroduced into aromatic rings by
direct fluorination.
b) F-TEDA-BF4 is the most common reagent used for fluorination
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Aromatic Fluorination
Currently approximately 80 pharmaceuticals now on the market
contain fluorine
a) Sitagliptin (Januvia) is used to treat type 2 diabetes (第二型糖尿病)
b) Fluoxetine (Prozac) is an antidepressant (抗憂鬱藥)
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Aromatic Halogenation
Electrophilic substitution reactions can introduce halogens into
aromatic rings
Aromatic rings react with Cl2 in the presence of FeCl3 catalyst to yield
chlorobenzenes
a) Reaction mechanism is the same for Br2 in the presence of FeBr3
b) Used to synthesize the anti-allergy medication loratadine (Claritin)
Reactions of Aromatic Compounds: Electrophilic
Substitution
Fluorine is too reactive to give mono-fluorinated products
Iodine itself is unreactive toward aromatic rings
▪ An oxidizing agent such as hydrogen peroxide or a copper salt
such as CuCl2 must be added to the reaction
▪ These substances oxidize I2 to a more powerful electrophilic species
that reacts as if it were I+
▪ The aromatic ring reacts with the I+ to yield a substitution product
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Electrophilic aromatic halogenations occur in the
biosynthesis of numerous naturally occurring molecules,
particularly those produced by marine organisms

甲狀腺荷爾蒙
▪ Thyroxine, synthesized in the
thyroid gland in humans, is a
thyroid hormone involved in
regulating growth and metabolism
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Aromatic Nitration
▪ Aromatic rings can be nitrated with a mixture of concentrated
nitric and sulfuric acids
▪ The electrophile is the nitronium ion, NO2+ which is generated from HNO3
by protonation and loss of water

硝基苯
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Aromatic nitration: Does not occur in nature, Important in the
laboratory
a) The nitro-substituted product can be reduced by reagents such as
iron or tin metal or to yield an arylamine, ArNH2
b) Attachment of an amino group 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
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Aromatic Sulfonation
Aromatic rings can be sulfonated in the laboratory by reaction with
fuming sulfuric acid(發煙硫酸), a mixture of H2SO4 and SO3
▪ The reactive electrophile： HSO3+ or neutral SO3
▪ Substitution occurs by the same two-step mechanism seen for
bromination and nitration
▪ Aromatic sulfonation does not occur naturally
▪ Aromatic sulfonation is widely used in the preparation of dyes and
pharmaceutical agents
▪ The sulfa drugs, such as sulfanilamide, were among the first
clinically useful antibiotics
Reactions of Aromatic Compounds: Electrophilic
Substitution
The mechanism of electrophilic sulfonation of an aromatic ring
Reactions of Aromatic Compounds: Electrophilic
Substitution
 Aromatic Hydroxylation： Direct hydroxylation of an aromatic
ring to yield a hydroxybenzene (a phenol)
a) Difficult and rarely done in the laboratory
b) Occurs much more freely in biological pathways
▪ Hydroxylation of p-hydroxyphenyl acetate to give 3,4-
dihydroxyphenyl acetate
▪ The reaction is catalyzed by p-hydroxyphenylacetate-3-
hydroxylase and requires molecular O2 plus the coenzyme
reduced flavin adenine dinucleotide (FADH2)
Reactions of Aromatic Compounds: Electrophilic
Substitution
▪ Reaction Mechanism:
The hydroxylating species
is an OH+ equivalent that
arises by protonation of
FAD hydroperoxide,
RO-OH + H+ → ROH +
OH+
9-7 Alkylation and Acylation of Aromatic
Rings: The Friedel-Crafts Reaction
 Alkylation
▪ The introduction of an alkyl group onto the benzene ring
▪ Called the Friedel-Crafts reaction after its discoverers
▪ Among the most useful electrophilic aromatic substitution
reactions in the laboratory
▪ The reaction is carried out by treating the aromatic
compound with an alkyl chloride, RCl, in the presence of
AlCl3 to generate a carbocation electrophile, R+
▪ Aluminum chloride catalyzes the reaction by helping the alkyl
halide to dissociate
▪ Loss of H+ completes the reaction
Alkylation and Acylation of Aromatic Rings:
The Friedel-Crafts Reaction
Mechanism of the Friedel-Crafts alkylation reaction

▪ The electrophile is
a carbocation,
generated by
AlCl3-assisted
dissociation of an
alkyl halide
Alkylation and Acylation of Aromatic Rings:
The Friedel-Crafts Reaction
Friedel-Crafts alkylation has several limitations
1. Only alkyl halides can be used as electrophiles
▪ Aromatic (aryl) halides and vinylic halides do not react
because aryl and vinylic carbocations are too high in energy to
form under Friedel-Crafts conditions
▪ Vinylic means that a substituent is attached directly to a
double bond, C=C-Cl
Alkylation and Acylation of Aromatic Rings:
The Friedel-Crafts Reaction
2. Friedel-Crafts reactions do not succeed on aromatic rings
that are substituted either by a strongly electron-
withdrawing group such as carbonyl (C=O) or by an amino
group (-NH2, NHR, -NR2)
▪ The presence of a substituent group already on a ring can
have a dramatic effect on that ring’s subsequent reactivity
toward further electrophilic substitution
Alkylation and Acylation of Aromatic Rings:
The Friedel-Crafts Reaction
3. It is often difficult to stop the reaction after a single
substitution
▪ Polyalklation is observed
▪ High yield of monoalkylation product is obtained only when a
large excess of benzene is used

6/10 ending
Alkylation and Acylation of Aromatic Rings:
The Friedel-Crafts Reaction
An aromatic ring is acylated by reaction with a carboxylic acid
chloride, RCOCl, in the presence of AlCl3
▪ An acyl group, -COR, is substituted onto an aromatic ring
▪ The reactive electrophile is a resonance-stabilized acyl cation
▪ An acyl cation is stabilized by interaction of the vacant orbital
on carbon with lone-pair electrons on the neighboring oxygen
▪ Because of stabilization, no carbocation rearrangement occurs
during acylation
Alkylation and Acylation of Aromatic Rings:
The Friedel-Crafts Reaction
Aromatic alkylations occur in numerous biological pathways
▪ The carbocation electrophile is typically formed by dissociation of an
organo diphosphate
▪ A diphosphate group is a common structural feature of many
biological molecules
▪ It can be expelled as a stable diphosphate ion
▪ The dissociation of an organo diphosphate in a biological reaction is
typically assisted by complexation to a divalent metal cation such as
Mg2+ to help neutralize charge
Alkylation and Acylation of Aromatic Rings:
The Friedel-Crafts Reaction
Biosynthesis of phylloquinone, or vitamin K1, the human blood-clotting factor
▪ The key step that joins the 20-carbon phytyl side chain to the aromatic
ring is an electrophilic substitution reaction
Worked Example 9.2
Predicting the Product of a Carbocation Rearrangement

The Friedel-Crafts reaction of benzene with 2-chloro-

3-methylbutane in the presence of AlCl3 occurs with
a carbocation rearrangement. What is the structure
of the product?
Worked Example 9.2
Predicting the Product of a Carbocation Rearrangement

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 an
increased stability
▪ The initial carbocation is a secondary one that can rearrange to a more
stable tertiary one by a hydride shift
▪ Use the more stable tertiary carbocation to complete the Friedel-Crafts
reaction
Worked Example 9.2
Predicting the Product of a Carbocation Rearrangement

Solution