Isolated and Conjugated Dienes

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 Reactions of Isolated Dienes

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 The Mechanism

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 Double Bonds can have
Different Reactivities

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 Reactions of Conjugated Dienes

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 1,2-Addition and 1,4-Addition

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 Mechanism for the
Reaction of a Conjugated Diene

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 The Diels–Alder Reaction
forms a Six-Membered Ring

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 The Mechanism

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 Faster if there is an Electron Withdrawing
Group on the Dienophile

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The Electron Withdrawing Group makes the
Electrophile a better Electrophile

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 Another Diels–Alder Reaction

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 Alkynes can also be Dienophiles

The cyclic product has two double bonds.

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 The Stereochemistry of the
Diels–Alder Reaction

The product will be a racemic mixture.

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 How to Determine the Reactants
of a Diels–Alder Reaction

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 Benzene is an Aromatic Compound

The delocalization energy of benzene is 36 kcal/mol.

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 Criteria for a Compound to be Aromatic

• It must have an uninterrupted cloud of π electrons.(cyclic,

planar, every ring atom must have a p orbital).

• The π cloud must have an odd number of pairs of π

electrons.
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 Criteria for Aromaticity

• Uninterrupted arrangement of p cloud

• Cyclic molecule
• Every atom in the ring must have a p
orbital
• Molecule has to be planar
• Total number of p-electron pairs is odd
(1,3,5…)
• Exceptionally stable molecules
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 Examples of Compounds
that are not Aromatic

Cyclobutadiene has an even number of pairs of π electrons.

Cyclooctatetraene has an even number of pairs of π

electrons and it is not planar.

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Nonaromatic and Aromatic Compounds

2 pairs of p electrons 2 pairs of p electrons 3 pairs of p electrons

planar nonplanar planar

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 Resonance Contributors and
the Resonance Hybrid

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 Cyclopentadienyl anion

Resonance contributors.
Overall every C atom has the same amount of negative charge

charge equally
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 Benzene

Benzene: planar, ring, all atoms have p

orbitals, 3 pairs of p electrons.

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 Aromatic Compounds

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 Nomenclature of Monosubstituted
Benzenes
• State the name of substituent and add
the word “benzene”

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 Nomenclature

• Many trivial names in use

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 Nomenclature

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 How Benzene Reacts

Aromatic compounds such as benzene undergo

electrophilic aromatic substitution reactions.

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 Benzene Reacts with Electrophiles

The π electrons above and below the ring make benzene a

nucleophile.

Benzene attacking an electrophile is like an alkene attacking

an electrophile.
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 Benzene undergoes Substitution,
not Addition

Aromaticity is restored in the product from electrophilic

substitution.
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 Benzene undergoes Substitution,
not Addition

The reaction of benzene with an electrophile forms the

aromatic substitution product, not the nonaromatic addition
product.
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 An Electrophilic Aromatic
Substitution Reaction

An electrophile (Y+) substitutes for H+.

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 The Mechanism for
Electrophilic Aromatic Substitution

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 Generating the Electrophile:
Halogenation

Donating a lone pair to a Lewis acid weakens the Br—Br or

Cl—Cl bond.

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Halogenation of Benzene
 Halogenation of Benzene
Halogenation:
1st step is generating an electrophile:

FeBr3 is a Lewis acid that coordinates with Br2 and

polarizes it, generating an electrophilic Br+
Halogenation of Benzene
 Generating the Electrophile:
Nitration

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 Nitration of Benzene

Nitration:
 Nitration of Benzene
Nitration:
 Generating the Electrophile:
Sulfonation

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Sulfonation of Benzene
Sulfonation of Benzene
 Generating the Electrophile:
Friedel–Crafts Acylation and Alkylation

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Friedel-Crafts Acylation of Benzene
Friedel-Crafts Acylation of Benzene
Friedel-Crafts Alkylation of Benzene
Friedel-Crafts Alkylation of Benzene
How Some Substituents on a Benzene Ring
Can be Chemically Changed
How Some Substituents on a Benzene Ring
Can be Chemically Changed
Nomenclature of Disubstituted
Benzenes
 The Effect of Substituents on
Reactivity
• Monosubstituted benzenes undergo
electrophilic aromatic substitution.
• Substituents influence reactivity.
• Substituents determine position of second
electrophilic substitution.
• Substituents that increase electron density
increase reactivity.
• Substituents that decrease electron
density decrease reactivity.
The Effect of Substituents on
Reactivity
Donating and Withdrawing
Electrons by Resonance
 Electron-donating Substituents
CH3 H3C H3C
O O O

O CH3 O CH3

Resonance contributors increase electron density in ortho

and para positions. Overall electron density is bigger.
Donating and Withdrawing
Electrons by Resonance
 Electron-withdrawing Substituents
O O O O O O
N N N

O O O O
N N

Resonance contributors decrease electron density in ortho and

para positions. Overall electron density is lower.
 Substituent Effects
D W

   

 
CH3 O O
O N

Both types of substituents, electron Donating and electron Withdrawing,

act on the same positions, namely ortho and para, however, in opposite
directions.
 Relative Reactivity of Substituted
Benzenes
Activating

Deactivating
 Classification of Substituents
• Activating Substituents
(ortho/para directing):
– NH2 prim. Amines
Strongly
– NHR sec. Amines activating
– NR2 tertiary amines
– OH phenolic OH
– OR phenol ethers
O
– NH CR' amides
phenolic esters weakly
O
– O CR' activating
– R alkyl substituents
– halides deactivating
X
 Classification of Substituents
• Deactivating Substituents (meta directing):
O
+

– CH aldehydes
O weakly
+

– COR esters deactivating

O
+
COH
– carboxylic acid
+
C N
– nitrile
+
SO3H
– sulfonic acid strongly
O
N O deactivating
– nitro
NR3
– ammonium
 The Effect of Substituents on
Orientation

1. All activating substituents direct an incoming

electrophile to the ortho and para positions.
 The Effect of Substituents on
Orientation
2. The weakly deactivating halogens also direct an
incoming electrophile to the ortho and para
positions.
 The Effect of Substituents on
Orientation
3. All moderately deactiating and strongly deactivating
substituents direct an incoming electrophile to the
meta position.
 Organizing what we know about the
Reactions of Organic Compounds

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