CHAPTER 6

6. Addition reactions
6.1. Mechanism
• Because of unsaturation, alkenes undergo
addition reaction, which involves breaking of a
weak π bond and formation of two new σ bonds.
• The relatively loosely held π electrons of the
carbon–carbon double bond are attracted to an
electrophile.
• Thus, each reaction starts with the addition of an
electrophile to one of the sp2 carbons of the
alkene and concludes with the addition of a
nucleophile to the other sp2 carbon.
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• The end result is that the π bond breaks and
the sp2 carbons form new bonds with the
electrophile and the nucleophile.

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 6.2. Reactivity of alkenes
• Reactivity makes alkenes an important class of
organic compounds because they can be used to
synthesize a wide variety of other compounds.

• For example, alkyl halides, alcohols, ethers, and

alkanes all can be synthesized from alkenes by
electrophilic addition reactions.

• The particular product obtained depends only on

the electrophile and the nucleophile used in the
addition reaction.
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 6.3. Markovnikov addition reactions.

• Markovnikov’s rule: ―When a hydrogen

halide adds to an unsymmetrical alkene, the
addition occurs in such a manner that the
halogen attaches itself to the double-bonded
carbon atom of the alkene bearing the lesser
number of hydrogen atoms.‖

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• Because H+ is the first species that adds to the
alkene, most chemists rephrase Markovnikov’s rule
as follows:

• “The hydrogen adds to the sp2 carbon that is

bonded to the greater number of hydrogens.”

• Those that do not follow Markovnikov’s rule—

that is, the hydrogen does not add to the sp2
carbon that is bonded to the greater number of
hydrogens are called anti-markovnikov addition.
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Practice problem: What major product would you
expect from the addition of HBr to each of the
following compounds?

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 6.4. Radical addition

• The addition of HBr to 1-butene forms 2-

bromobutane. But what if you wanted to
synthesize 1-bromobutane?
• The formation of 1-bromobutane requires the
anti-Markovnikov addition of HBr.

• If an alkyl peroxide (ROOR) is added to the

reaction mixture, the product of the addition
reaction will be the desired 1-bromobutane.
• Thus, the presence of a peroxide causes the
anti-Markovnikov addition of HBr.
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• Peroxide reverses the order of addition
because it changes the mechanism of the reaction
in a way that causes Br to be the electrophile.
Markovnikov’s rule is not followed because it
applies only when the electrophile is a hydrogen.

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• The general rule— that the electrophile adds
to the sp2 carbon bonded to the greater
number of hydrogens—is followed, however,
because Br is the electrophile when HBr adds
to an alkene in the presence of a peroxide.

• The mechanism for the formation of 1-

bromobutane is as follows.

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• Problem: Write out the propagation steps that occur
when HBr adds to 1-methylcyclohexene in the presence
of peroxide. 10
 6.5. Alkylation of the β-Carbon:
The Michael Reaction

• When the nucleophile is an enolate, the

addition reaction has a special name—it is
called a Michael reaction.

• The enolates that work best in Michael

reactions are those that are flanked by two
electron-withdrawing groups: enolates of
β-diesters,
β-diketones,
β-keto esters, and
β-keto nitriles.
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• Because these enolates are relatively weak
bases, addition occurs at the β-carbon of α,β-
unsaturated aldehydes and ketones.

• The enolates also add to the β-carbon of α,β-

unsaturated esters and amides because of the low
reactivity of the carbonyl group.

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• All these reactions take place by the same
mechanism:
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• A base removes a proton from the α-
carbon of the carbon acid, the enolate adds
to the β-carbon of an α,β-unsaturated
carbonyl compound, and the α-carbon
obtains a proton from the solvent.

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 CHAPTER 7
7. AROMATIC SUBSTITUTION REACTIONS
• Aromatic compounds: unsaturated ring compounds
that are far more stable than they should be and
resist the addition reactions typical of unsaturated
aliphatic compounds. Examples are Benzene
The Criteria for Aromaticity
7.1. Aromaticity: is an extra stability possessed by a
molecule that meets the following specific criteria:
• Benzene is not the only compound that exhibits
aromatic stabilization. A compound will be
aromatic if it satisfies the following two criteria.
1. The compound must contain a ring comprised of
continuously overlapping p orbitals.
2. The number of π electrons in the ring must be a
Hückel number.
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 Hückel’s Rule: states that for a planar, cyclic
compound to be aromatic, its uninterrupted 
cloud must contain (4n + 2) resonating electrons
(n = 0, 1, 2, 3, ... or whole number).
Example, benzene
Total  electrons of benzene are 2x3=6,
then
4n+2=6
4n=4 and therefore, n=1

Since 1 is a whole number; benzene is an aromatic

compound. 16
• Compounds that fail the first criterion are called
nonaromatic.
• Compounds that satisfy the first criterion but
have 4n electrons (rather than 4n + 2) are
antiaromatic.

Exercise
1. Determine whether each of following ions is
aromatic, nonaromatic, or antiaromatic.

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2. For each of the following compounds determine
which (if any) lone pairs are participating in
aromaticity.

3. Evaluate the aromaticity of the following

a)

cycloheptatriene

b) cyclobutadiene
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 7.2. Aromatic Electrophilic Substitution
Reactions and their Mechanism.

• Because electrophilic substitution of benzene

involves the reaction of an electrophile with an
aromatic compound, it is more precisely called an
electrophilic aromatic substitution reaction. It is
the most common aromatic reaction.

• Notice that the proton is always removed from

the carbon that has formed the new bond with the
electrophile. 19
Halogenation: bromine (Br), chlorine (Cl), or an
iodine (I) substitutes for a hydrogen.
• The bromination or chlorination of benzene
requires a Lewis acid such as ferric bromide or
ferric chloride. Recall that a Lewis acid is a
compound that shares a pair of electrons.

Bromination

Mechanism
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• Hence, on the product the left bromine can act
as electrophile. Because the positively charged
bromine attracts the bonding electrons towards
itself strongly.

• Where, :B is a base in the reaction mixture.

Since the use of ferric bromide catalysis it will
be reformed as follow.

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• Nitration: A nitro (NO2) group substitutes for a
hydrogen. Nitration of benzene with nitric acid
requires sulfuric acid as a catalyst.

• To generate the necessary electrophile, sulfuric

acid protonates nitric acid. Loss of water from
protonated nitric acid forms a nitronium ion, the
electrophile required for nitration.
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• Remember that any base (:B) present in the
reaction mixture (H2O, HSO4-, solvent) can
remove the proton in the second step of the
aromatic substitution reaction.

Then

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• Sulfonation: A sulfonic acid (-SO3H) group
substitutes for a hydrogen.
• Fuming sulfuric acid (a solution of SO3 in sulfuric
acid) or concentrated sulfuric acid is used to
sulfonate aromatic rings.

Sulfonation

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Mechanism for sulfonation

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 Friedel–Crafts Reactions

• Two electrophilic substitution reactions bear the

names of chemists Charles Friedel and James
Crafts. Friedel–Crafts acylation places an acyl
group on a benzene ring, and Friedel–Crafts
alkylation places an alkyl group on a benzene ring.
• Friedel–Crafts acylation: An acyl group (RC=O)
substitutes for a hydrogen.
• General representation of the reaction

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• An acylium ion is the electrophile required for a
Friedel–Crafts acylation reaction. This ion is formed
by the reaction of an acyl chloride or an acid
anhydride with a Lewis acid.

• Because the product of a Friedel–Crafts acylation

reaction contains a carbonyl group that can complex
with AlCl3,
• Friedel–Crafts acylation reactions must be carried
out with more than one equivalent of AlCl3. When the
reaction is over, water is added to the reaction
mixture to liberate the product from the complex.
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28
 7.3. Directing effects of substituents

• A problem arises when substitution occurs on a

benzene ring that already bears a substituent. In
such a compound there are three nonequivalent
positions on the ring (ortho, meta and para). It is
therefore important to be able to predict the
predominant substitution site(s) so that one can
design a rational synthesis of polysubstituted
aromatic compounds. Fortunately this is usually
not a difficult task.

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There are three classes of substituents.

1) Meta directing and deactivating. Examples:

NO2 CN
nitro nitrile
ammonium NR3 aldehyde CHO

2) Ortho-para directing and activating. Examples:

hydroxyl OH phenyl C6H5

alkoxyl OR amino NH2

alkyl R

3) Ortho-para directing and deactivating. Examples:

halogens Cl , Br , I 30
 Relative rates of electrophilic substitution

• Substituents that are capable of donating

electrons into the benzene ring will stabilize both
the carbocation intermediate and the transition
state leading to its formation, thereby increasing
the rate of electrophilic aromatic substitution.

• In contrast, substituents that withdraw

electrons from the benzene ring will destabilize
the carbocation intermediate and the transition
state leading to its formation, thereby decreasing
the rate of electrophilic aromatic substitution.
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• There are two ways in which substituents
can donate electrons into a benzene ring:
inductive electron donation and electron
donation by resonance.

• There are also two ways substituents can

withdraw electrons from a benzene ring:
inductive electron withdrawal and electron
withdrawal by resonance.
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 Electron-donating substituents increase the
reactivity of the benzene ring toward
electrophilic aromatic substitution.
 Electron-withdrawing substituents decrease the
reactivity of the benzene ring toward
electrophilic aromatic substitution.
• For the substituents Y and Z below the
reactivity can be written as:

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Directing effect & reaction effect justification examples

• Methoxy group on anisole is ortho-para director &

activator b/c of the following possible resonance
structures

• Nitro group on nitrobenzene is also meta director &

deactivator b/c of

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