Chapter 8

Delocalized
Electrons and Their
Effect on Stability,
pKa, and the
Products of a
Reaction
Paula Yurkanis Bruice
University of California,
Santa Barbara
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Localized Electrons

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Delocalized Electrons

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What is the Structure of Benzene?

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Degree of Unsaturation = 4

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Two Disubstituted Products

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Four Disubstituted Products

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Two are in Rapid Equilibrium

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It was Confirmed that Benzene

is Cyclic in 1901

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The Structure of Benzene

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Showing Delocalized Electrons

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Resonance Contributors
Resonance Hybrid

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Resonance Contributors
Resonance Hybrid

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Cyclooctatriene Does Not Have

Delocalized Electrons

Cyclooctatetraene is not planar.

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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.
2. Only electrons and lone-pair electrons move.

3. The total number of electrons in the molecule

does not change.
4. An sp3 carbon cannot accept electrons;
it already has an octet.
5. Do not break sigma bonds.
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Move Electrons to an
sp2 Carbon

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Cannot Move Electrons to an

sp3 Carbon

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Move Electrons to an sp2 Carbon

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Move Lone-Pair Electrons to

an sp2 Carbon

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Move Electrons to an sp Carbon

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How Delocalized Electrons Affect

Protein Structure

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A is More Stable Than B

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A and B are Equally Stable

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F is More Stable Than G;

G is More Stable Than E

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H is More Stable Than I

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K is More Stable Than J

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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.

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 Number of Relatively Stable Resonance

Contributors is What is Important
Little delocalization energy

Significant delocalization energy

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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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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 electrons.

(cyclic, planar, every ring atom must have a p orbital).
The cloud must have an odd number of pairs of electrons.

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Examples of Compounds
That are Not Aromatic

Cyclobutadiene has an even number of pairs of electrons.

Cyclooctatetraene has an even number of pairs of electrons and
it is not planar.

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Nonaromatic and Aromatic Compounds

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Resonance Contributors and the

Resonance Hybrid

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Aromatic Compounds

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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

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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Resonance Contributors of Furan

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More Aromatic
Heterocyclic Compounds

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Relative Stabilities

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Antiaromatic Compounds

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An MO Description of
Aromaticity and Antiaromaticity

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Conjugated and Isolated Dienes

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The Smaller the Heat of Hydrogenation,

the More Stable the Compound

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Conjugated Dienes Have

Delocalized Electrons

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An sp2sp2 Bond Is Stronger

Than an sp2sp3 Bond

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Carbon-Carbon Bond Length

Depends on Hybridization

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Cumulated Double Bonds

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Organic Compounds That

Conduct Electricity

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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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An MO Diagram for Ethene

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Resonance Contributors of
1,3-Butadiene

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An MO Diagram for 1,3-Butadiene

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Symmetric and Antisymmetric

Molecular Orbitals

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MO Diagrams for 1,4-Pentadiene and

1,3-Butadiene

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Delocalized Electrons Affect

pKa Values

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Proton Loss is Accompanied by

Greater Delocalization Energy

The negative charge is on one oxygen.

The negative charge is shared by two oxygens.

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Phenols versus Alcohols

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No Electron Delocalization

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Why Phenols are More Acidic

The base has greater delocalization energy than the conjugate acid.
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Protonated Anilines versus

Protonated Amines

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No Delocalized Electrons

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Why Protonated Anilines

are More Acidic

The base has greater delocalization energy than the conjugate acid.

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Important!!!

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Withdrawing Electrons by Resonance

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Donating Electrons by Resonance

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Only One Product is Formed Because

of Electron Delocalization

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Isolated and Conjugated Dienes

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Reactions of Isolated Dienes

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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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Which Carbon Gets 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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The 1,2-Product is Always

The Kinetic Product

DCl was used instead of HCl, so the 1,2- and 1,4-products would be different.

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The Proximity Effect

The proximity effect causes the 1,2-product to be 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 DielsAlder Reaction

Forms a Six-Membered Ring

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The Mechanism

a pericyclic reaction takes place by a cyclic shift of electrons

a [4+2] cycloaddition reaction
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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 DielsAlder Reaction

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Alkynes Can Also Be Dienophiles

The cyclic product has two double bonds.

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Another DielsAlder Reaction

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Both Reactants are Not Symmetric

Two products are possible.

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The Reactants Can Be

Aligned in Two Ways

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Which Alignment Gives

The Major Product?

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The Answer

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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

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Endo and Exo

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Bridged Bicyclic Rings and

Fused Bicyclic Rings

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If the DielsAlder Reaction Creates

an Asymmetric Center

A racemic mixture

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Cis Forms Cis

Trans Forms Trans

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How to Determine the Reactants

of a DielsAlder Reaction

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How to Determine the Reactants

of a DielsAlder Reaction

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Group I Compounds are Nucleophiles;

They React with Electrophiles

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