Chapter 8

Delocalized
Electrons:
Their Effect on Stability,
pKa, and the Products
of a Reaction

Aromaticity and
Electronic Effects:
An Introduction to the
Reactions of Benzene

Paula Yurkanis Bruice

University of California,
Santa Barbara

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 Localized Electrons versus
Delocalized Electrons
Localized electrons belong to a single atom
or are shared by two atoms:

Delocalized electrons are shared by

three or more atoms:

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 What is the Structure of Benzene?

Molecular Formula = C6H6 CnH2n+2 = C6H14

Therefore, benzene has a degree of unsaturation of 4.

Benzene forms only one monosubstituted compound.

Therefore, all of its hydrogens are identical.
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 Possible Structures
structures with six carbons,
identical hydrogens,
and a degree of unsaturation of 4

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 Benzene Forms Three Disubstituted Products

Compound I forms two disubstituted products.

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 The Structure of Benzene

Compound II forms four disubstituted products.

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 Kekule’s Proposal for
the Structure of Benzene
Benzene is a mixture of two compounds in rapid equilibrium.

Therefore, three disubstituted products are formed.

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 Conformation (in 1910) That
Benzene is a Cyclic Compound

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 Benzene Has Delocalized Electrons

All the carbon–carbon bonds in benzene were found to have

the same length:

They are longer than a double bond but shorter than a single bond.

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 Showing Delocalized Electrons

These structures show that the π electrons are delocalized.

But they do not show the number of π electrons.

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 Resonance Contributors and
the Resonance Hybrid

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 Resonance Contributors and
the Resonance Hybrid

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 Cyclooctatetraene
For maximal p orbital overlap,
the atoms that share the delocalized electrons
must lie in the same plane.

Cyclooctatetraene is not planar,

so it does not have delocalized electrons.

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 Delocalized Electrons

Delocalized electrons result from the p orbital of one atom

overlapping the p orbitals of two adjacent atoms.

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 Rules for Drawing Resonance Contributors

1. Only electrons move. Atoms never move.

2. Only π electrons (electrons in π bonds) and lone-pair

electrons can move. (Sigma (σ) electrons never move.

3. The total number of electrons in the molecule does not

change.

4. Electrons always move to an sp2 or sp atom; sp3 atoms

cannot accept electrons.

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 Move π Electrons to an sp2 Carbon

Electrons cannot move to an sp3 carbon,

because an sp3 carbon has a complete octet.

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 Move π Electrons to an sp2 Carbon

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 Move Lone-Pair Electrons to an sp2 Carbon

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 Move π Electrons to an sp Carbon

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Delocalized Electrons Affect Protein Structure

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 A Has a Greater Predicted Stability Than B

B has separated charges.

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 C and D Have an Equal Predicted Stability

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 E Has a Greater Predicted Stability Than F

F has an incomplete octet.

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 G Has a Greater Predicted Stability Than H

H has a positive charge on an electronegative atom.

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 J Has a Greater Predicted Stability Than I

J has a negative charge on oxygen,

whereas I has negative charge on carbon.

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 Features That Decrease
The Predicted Stability

1. An atom with an incomplete octet.

2. A negative charge that is not on the most

electronegative atom.

3. A positive charge that is on an electronegative atom.

4. Separated charges.

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 Delocalization Energy

The delocalization energy is the extra stability a compound

has as a result of having delocalized electrons.

Electron delocalization is also called resonance.

Therefore,
delocalization energy is also called resonance energy.

The resonance hybrid is more stable than any of its

resonance contributors is predicted to be.

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 The Greater the Number of Relatively Stable Resonance
Contributors, the Greater the Delocalization Energy

The delocalization energy is greater for

the carboxylate ion than for the carboxylic acid.

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 The Greater the Number of Relatively Stable Resonance
Contributors and the More Nearly Equivalent Their
Structures, the Greater the Resonance Energy

little delocalization energy: one relatively stable resonance contributor

significant delocalization energy: three relatively stable resonance

contributors

significant delocalization energy: two equivalent resonance contributors

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 Summary

• The greater the predicted stability of a resonance

contributor, the more it contributes to the resonance
hybrid.

• The greater the number of relatively stable resonance

contributors, the greater the delocalization energy.

• The more nearly equivalent the resonance

contributors, the greater the delocalization energy.

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 Isolated and Conjugated Dienes

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 The Smaller the Heat of Hydrogenation,
the More Stable the Compound

Therefore, a conjugated diene is more stable

than an isolated diene.

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 Conjugated Dienes Have
Delocalized Electrons

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 An sp2–sp2 Bond is Stronger and Shorter
Than an sp2–sp3 Bond

Stronger bonds cause a compound to be more stable.

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 Carbon–Carbon Bond Length and Strength
Depend on Hybridization

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 Allenes
Compounds with Cumulated Double Bonds

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 Organic Compounds That
Conduct Electricity

Conducting polymers are used in LED displays.

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 Allyl and Benzyl
Allylic and Benzylic

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 Resonance Contributors for an Allylic Cation

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Resonance Contributors for a Benzylic Cation

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 Relative Stabilities of Carbocations

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 Relative Stabilities of Carbocations

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 The MO Diagram for Ethene

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 Resonance Contributors of 1,3-Butadiene

Four π electrons are delocalized over four carbons.

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 The MO Diagram for 1,3-Butadiene

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 Symmetric and Antisymmetric
Molecular Orbitals

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 Localized Electrons versus
Delocalized Electrons

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 Delocalized Electrons Affect pKa Values

A carboxylic acid is a stronger acid than an alcohol because

of inductive electron withdrawal and electron delocalization.
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 Proton Loss Is Accompanied by
an Increase in Delocalization Energy

The negative charge is

shared by two oxygens.

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 Phenol versus Cyclohexanol

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 No Electron Delocalization

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 Why Phenol is More Acidic

The conjugate base has greater delocalization energy

than the acid.
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 Protonated Aniline versus
Protonated Cyclohexylamine

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 No Delocalized Electrons

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 Why Protonated Aniline is More Acidic

The conjugate base has greater delocalization energy

than the acid.

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 Important!

Two new terms have been added to the Table 2.1 in Chapter 2.

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 Electronic Effects

Electron donation decreases acidity.

Electron withdrawal increases acidity.

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 Inductive Electron Withdrawal

inductive electron withdrawal =

withdrawal of electrons through sigma bonds

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 Donating Electrons by Resonance

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 Withdrawing Electrons by Resonance

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 Electronic Effects and pKa Values

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 Electron Delocalization Can Affect
the Product of a Reaction

A secondary benzylic carbocation is more stable

than a secondary alkyl carbocation.

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 Isolated and Conjugated Dienes

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 Reactions of Isolated Dienes

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 The Mechanism

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 The Double Bonds Have Different Reactivities

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 Reactions of Conjugated Dienes

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 1,2-Addition and 1,4-Addition

1,2-addition and 1,4-addition to the conjugated system

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 Mechanism for the
Reaction of a Conjugated Diene

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 Does C-1 or C-4 Get the Proton?

Protonate the end that forms the more stable carbocation.

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 Kinetic and Thermodynamic Products

For the reaction of 1,3-butadiene:

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 If the Reaction is Irreversible,
the Kinetic Product Predominates

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 If the Reaction is Reversible,
the Thermodynamic Product Predominates

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 Why?

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 Kinetic Control

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 Thermodynamic Control

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 In the Reaction Below, Why is the
1,4-Addition Product the Thermodynamic Product?

The more stable alkene has

the greater number of alkyl groups bonded to the sp2 carbons.

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 Why is the 1,2-Addition Product
the Kinetic Product?

The reason found to be wrong:

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 The 1,2-Addition Product is Always
the Kinetic Product

the correct reason—the proximity effect

The proximity effect causes

the 1,2-product to be formed faster.

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 Proof of the Proximity Effect

Both products have a resonance contributor with

the partial positive charge on a secondary carbon,
but the 1,2-addition product is formed faster.

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 Kinetic and Thermodynamic Products

Although the 1,2-product is always the kinetic product,

do not assume that the 1,4-product is always the thermodynamic product.

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 Kinetic and Thermodynamic Products

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 The Diels–Alder Reaction
Forms a Six-Membered Ring

A dienophile “loves” a diene.

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 The Mechanism

A pericyclic reaction takes place by a cyclic shift of electrons.

More precisely, it is a [4+2] cycloaddition reaction.

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 The Diels–Alder Reaction is
a 1,4-Addition Reaction

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 An Electron Withdrawing Group
Increases the Reactivity of the Electrophile

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 Examples of Diels–Alder Reactions

An alkyne can be a dienophile, forming a product with two double bonds.

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 The Molecular Orbital Description
of the Diels–Alder Reaction

must consider the HOMO of one reactant and the LUMO of the other

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 Both Reactants are Not Symmetric

Two products are possible because

the reactants can be aligned in two different ways.

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 Which Alignment Gives the Major Product?

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 s-Cis and s-Trans Conformations

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 The Diene Must Be in an s-Cis Conformation

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 Locked in an s-Cis Conformation

1,3-Cyclopentadiene is a highly reactive diene

because it is locked in an s-cis conformation.

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 Bridged Bicyclic Rings and
Fused Bicyclic Rings

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 Endo and Exo Products

The endo product is formed faster when the substituent (R) has
π electrons.

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 Stereochemistry of
the Diels–Alder Reaction

If the reaction creates a new asymmetric center,

a racemic mixture is formed.

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 If the Reaction Creates
Two New Asymmetric Centers
cis forms cis

trans forms trans

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 How to Determine the Reactants
of a Diels–Alder Reaction

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 How to Determine the Reactants
of a Diels–Alder Reaction

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 Delocalized Electrons Make
a Compound More Stable

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, and 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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 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

not aromatic because

it has an sp3 carbon

not aromatic because

it has an even number
of pairs of π electrons

aromatic

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 How Do We Know That Cyclopentadiene’s
Lone-Pair Electrons Are π Electrons?

If a lone pair can be used to form a π bond in a resonance contributor,

the lone-pair electrons are π electrons.

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 Aromatic Compounds

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 A Molecular Orbital Description
of Aromaticity

A compound with an odd number of pairs of π electrons

has completely filled bonding molecular orbitals.

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 Antiaromatic Compounds

An antiaromatic compound fulfills the first criterion for aromaticity

but has an even number of π electrons.

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 Heterocyclic Aromatic Compounds

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 Orbital Structure of Pyridine

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 Orbital Structure of Pyrrole and Furan

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 Resonance Contributors of Pyrrole and Furan

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 Benzene, Pyridine, and Pyrrole

The aromatic ring of pyridine is less electron-dense

than benzene because
the nitrogen withdraws electrons from the ring.

The aromatic ring of pyrrole is more electron-dense

than benzene because
the nitrogen donates electrons into the ring.

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 More Examples of
Aromatic Heterocyclic Compounds

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 How Benzene Reacts

Aromatic compounds such as benzene undergo

electrophilic aromatic substitution reactions.

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 The First Step of an
Electrophilic Aromatic Substitution Reaction
Adding an electrophile to benzene is the same as
adding an electrophile to an alkene.

benzene

alkene

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 The Second Step is Different

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 The Substitution Product is More Stable
Than the Addition Product

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 Addition of Br2 to an Alkene versus
Addition of Br2 to Benzene

alkene

benzene

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 Mechanism for an
Electrophilic Aromatic Substitution Reaction

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 Group I Compounds are Nucleophiles
They React with Electrophiles

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