Week 1-4 - OrgChemII - Combined - 2021

Organic Chemistry II, 2020
Chapter 8
Delocalized
Electrons and Their
Effect on Stability,
pKa, and the
Products of a
Reaction
Paula Yurkanis Bruice
University of California,
Santa Barbara
Lecturer: C. V. RAIDRON
© 2014 Pearson Education, Inc.
What you should know at the
end of this chapter:
• Determine the degree of unsaturation
• Explain the concept of delocalized and
localized electrons by giving examples
• Explain the concept of resonance
• Draw resonance contributors, and
include the curved arrows to indicate
how the electrons move
• Predict the stabilities of resonance
contributors
end of this chapter: cont.
• Memorize and apply the criteria for
aromaticity
• Explain Hückel’s rule (4n + 2 rule)
• Define a heterocyclic compound and
judge whether they are aromatic or not
• Define antiaromaticity
• Explain the stability of isolated and
conjugated dienes
• Explain the stability of allylic and
benzylic cations
• Explain the stability of allylic and
benzylic radicals
• Explain how delocalized electrons affect
pKa values
• Explain how delocalized electrons affect
the product of a reaction
• Draw the mechanism for isolated and
conjugated dienes
• Use thermodynamic vs. kinetic control to
determine whether the 1,2-addition
product or the 1,4-addition product will
be the major product of the reaction

• Draw the mechanism for the Diels-Alder
reaction
• Predict the products of a Diels-Alder
reaction by respecting the conformers
and stereochemistry

Degree of Unsaturation = 4
Remember, the degrees of unsaturation only gives the sum of
double bonds, triple bonds and/or rings. For instance, a degree
of unsaturation of 3 can contain 3 rings, 2 rings+1 double
bond, 1 ring+2 double bonds, 1 ring+1 triple bond, 1 double
bond+1 triple bond, or 3 double bonds.

Localized & Delocalized
Electrons

Two are in Rapid Equilibrium

The Structure of Benzene
Showing Delocalized Electrons

Resonance Contributors
Resonance Hybrid

Cyclooctatetraene Does Not Have
Delocalized Electrons
Electron delocalization is most effective if all the atoms

sharing the delocalized electrons lie in the same
plane, so that their p orbitals can overlap maximally.
Cyclooctatetraene is not planar. Bond angles
are 120°.
Resonance Contributors and the
Resonance Hybrid
If a lone pair can be used to form a π bond in
the ring of a resonance contributor of the
compound, then the lone-pair electrons are π
electrons.

Delocalized electrons result from the p

orbital of one atom
overlapping the p orbitals of two adjacent
atoms (which are in the same plane,
remember!! ).
Rules for Drawing Resonance
Contributors
1. Only electrons move.
2. Only π 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. sp2 carbons can
5. Do not break sigma bonds.
Cannot Move Electrons to an
sp3 Carbon

Move π Electrons to an sp2 Carbon

Move Lone-Pair Electrons to
an sp2 Carbon

Move π Electrons to an sp Carbon

Practice Problem 1
Which of the following have delocalized electrons?
Draw the resonance contributors for the compounds
that have delocalized electrons.

A is More Stable Than B
Energy is
required to
keep opposite
charges
separated
The greater the stability of a resonance contributor, the more it

contributes to the structure of the resonance hybrid.
The more the resonance contributor contributes to the structure

of the resonance hybrid, the more similar the contributor is to
the real molecule.
A and B are Equally Stable

F is More Stable Than G;
G is More Stable Than E
When electrons can be moved in more than one
direction, the most stable resonance contributor
is obtained by moving them toward the more
electronegative atom.

H is More Stable Than I
The only time you need to show a resonance

contributor that is obtained by moving electrons
away from the most electronegative atom, is when
that is the only way electrons can be moved.

K is More Stable Than J
Oxygen can better accommodate the negative
charge, because it is more electronegative than
carbon.
K is predicted to be more stable than J.

Practice Problem 2
Draw resonance contributors for each of the
following species and rank them in order of
decreasing contribution to the hybrid:

Practice Problem 3
Draw the resonance hybrid for each of the
species in Practice Problem 2.

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.

The Number of Relatively Stable Resonance
Contributors is What is Important
Little delocalization energy
Significant delocalization energy
Delocalization
energy?
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.
Criteria for a Compound to
Be Aromatic
• It must have an uninterrupted cloud of π electrons.

(cyclic, planar (flat), every ring atom must have a p
orbital or conjugated all around the ring).
• The π cloud must have an odd number of pairs of
π electrons. (Hückel’s rule: 4n + 2 rule)
Huckel’s Rule Applied
The rule states that for a planar, cyclic compound to
be aromatic, its uninterrupted π electrons must have
2 (n = 0), 6 (n = 1), 10 (n = 2), 14 (n = 3), 18 (n = 4),
and so on π electrons.
Because there are two electrons in a pair, Hückel’s

rule requires that an aromatic compound have, 1, 3,
5, 7, 9 and so on pairs of π electrons.
Thus Hückel’s rule is a mathematical way of saying

that an aromatic compound must have an odd
number of pairs of electrons.
Practice Problem 4
1. What is the value of n in Hückel’s rule
when a compound has nine pairs of π
electrons?
2. Is such a compound aromatic?

Practice Problem 4 solved
1. In the case of 9 pairs of π electrons, there
are 18 electrons. Therefore, 4n + 2 = 18
where n = 4.
2. Because it has an odd number of π

electrons, it will be aromatic if its is cyclic
and planar, and if every atom in the ring has
a p orbital.

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.
Nonaromatic and Aromatic
Compounds
Cyclopentadiene –
• no uninterrupted ring of p-orbitals (one of carbon atoms is
sp3 hybridized.
• only sp2 and sp carbons have p orbitals.
Cyclopentadienyl cation –
• although it has an uninterrupted ring of p orbitals, its π
cloud has an even number (two pairs) of π electrons.
Aromatic Compounds
The same criteria to determine whether a

monocyclic hydrocarbon is aromatic can also be
used to determine whether a polycyclic
hydrocarbon is aromatic.

Heterocyclic Aromatic Compounds
A heterocyclic compound is a cyclic compound in

which one or more of the ring atoms is an atom other
than carbon.

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.

Resonance Contributors of Furan

More Aromatic
Heterocyclic Compounds

Antiaromatic Compounds
A compound is classified as being antiaromatic if it
fulfills the first criterion for aromaticity, but does
not fulfill the second.
• Planar (flat), cyclic & uninterrupted ring of atoms
with p-orbital,
• Contain an even number of π electrons

Relative Stabilities
Aromaticity is characterized by stability,

whereas antiaromaticity is characterized by
instability.

Nonaromatic compounds
These are compounds that fail any
one of the criteria for aromaticity.
e.g. cyclooctatetraene.

Conjugated and Isolated Dienes
Stability of Dienes
More examples that show how delocalized electrons
increase stability:

The Smaller the Heat of Hydrogenation,
the More Stable the Compound
The most stable alkene has the smallest heat of hydrogenation; it gives
off the least heat when it is hydrogenated because it has less energy to
begin with.
A conjugated diene, therefore, is more stable than

an isolated diene.
Conjugated Dienes Have
Why is a conjugated diene more stable than an isolated
diene?
Electron delocalization stabilizes a compound.

An sp2–sp2 Bond Is Stronger
Than an sp2–sp3 Bond
The hybridization of the orbitals forming the C—C single bonds also
causes a conjugated diene to be more stable than an isolated diene.
sp2 ̶ sp2 overlap is shorter and stronger than sp3 ̶ sp2 overlap
Resonance Contributors for
an Allylic Cation
REMEMBER:
An allylic cation: a carbocation with a +’ve charge on an allylic carbon
An allylic carbon is a carbon adjacent to an sp2 carbon of an alkene
an allylic carbon
The positive charge is not localized but shared by

two carbons of two resonance contributors.
Resonance Contributors for
a Benzylic Cation
REMEMBER:
An benzylic cation: a carbocation with a +’ve charge on a benzylic
carbon
An benzylic carbon is a carbon adjacent to an sp2 carbon of a benzene
ring
a benzylic carbon
It has five resonance contributors, and the positive charge is

shared by four carbons.
Relative Stabilities of Carbocations
Because allyl and benzyl cations have delocalized electrons,

they are more stable than other carbocations

Relative Stabilities of Carbocations

Delocalized Electrons Affect
pKa Values
A carboxylic acid is a stronger acid than alcohol-
• because the carboxylate ion (conjugate base of carboxylic acid) is a
more stable (weaker) base than the alkoxide ion (conjugate base of
alcohol).
The more stable the base, the

stronger its conjugate acid.

Delocalized Electrons Affect
pKa Values cont.
The greater stability of the carboxylate ion is attributable to two
factors:
• Electron delocalization
• Inductive electron withdrawal
• i.e. the C═O stabilizes the carboxylate ion by decreasing
the electron density of the negatively charged oxygen by
inductive electron withdrawal and by an increase in
delocalization energy.

Proton Loss is Accompanied by
Greater Delocalization Energy
The negative charge is on one

oxygen.
The negative charge is

shared by two oxygens.

Phenols versus Alcohols
• sp2 carbon is more electronegative than the sp3 carbon.
• Greater inductive electron withdrawal by more electronegative

sp2 carbon stabilizes the conjugate base by decreasing the
electron density of its negatively charged oxygen.
No Electron Delocalization

Cyclohexanolate ion
Why Phenols are More Acidic
Notice the separated charges and the +’ve charge

on Oxygen on three of the resonance structures
of phenol – stability??
The base has greater delocalization energy than

the conjugate acid.
Protonated Anilines versus
Protonated Amines
Do you notice that in aniline, the Do you notice that in cyclohexylamine,

nitrogen is attached to an sp2 carbon? the nitrogen is attached to an sp3
More electronegative carbon? Less electronegative

No Delocalized Electrons

Why Protonated Anilines
are More Acidic
The base has greater delocalization energy than

the conjugate acid.
Determining Relative Acidities
Which is a stronger acid?
CH3CH2OH or CH2═CHOH
ethanol vinyl alcohol
Problem –solving strategy:

• The strength of an acid depend on the stability of its
conjugate base.
• Bases are stabilized by electron-withdrawing
substituents and by electron delocalization.
• Compare the stabilities of the two conjugate bases:
the more stable base will have the more acidic
conjugate acid.
cont.
Which is a stronger acid?
CH3CH2OH or CH2═CHOH
ethanol vinyl alcohol

Draw the conjugate bases of each and compare their
stability.

cont.
• All the electrons in ethanol’s conjugate base are

localized.
• Vinyl alcohol’s conjugate base is stabilized by
electron delocalization.
• Its oxygen is attached to an sp2 carbon which is
more electronegative than the sp3 carbon to
which the oxygen in ethanol is attached.
• Vinyl alcohol is a stronger acid than ethanol.
Use the strategy you have just learned to solve the next
problems.
Practice Problem 4
1. Which member of each pair is the stronger acid?

Practice Problem 4 cont.
2. Which member of each pair is the strongest base?
a. ethylamine or aniline
b. phenolate ion or ethoxide ion
c. ethylamine or ethoxide ion
3. Rank the following compounds in order from

strongest acid to weakest acid:

Withdrawing Electrons by Resonance
Which of the following is the strongest acid?
Solution:
The nitro–substituted compound is the strongest acid,
• The nitro-substituent withdraws electrons both
inductively (through the σ bonds) and by resonance
(through the π bonds).
• Withdrawal of electrons through π bonds is called
resonance electron withdrawal.
• Electron withdrawing substituents increase the acidity
of a compound by stabilizing its conjugate base
Withdrawing Electrons by Resonance

Donating Electrons by Resonance
A methoxy substituent attached to a
benzene ring withdraws electrons
inductively (through the σ bond). Why?
The group also donates electrons
through π bonds (resonance electron
donation).

Only One Product is Formed Because
of Electron Delocalization
Very Important: Revise electrophilic addition reactions
• Some carbocations are stabilized by electron

delocalization.
• Inspect the relative stabilities of the individual
carbocations to predict the major product of the
reaction.
Practice Problem 5
What is the major product obtained from the
addition of HBr to the following compound?
Tip: if a more stable carbocation can be

formed as a result of carbocation
rearrangement, rearrangement will occur.
Reactions of Isolated Dienes
The electrophile adds to the sp2 carbon bonded to the

most hydrogens, as predicted from our knowledge of the
mechanism for the reaction of alkenes with electrophilic
reagents.
Mechanism

Double Bonds Can Have
Different Reactivities
If there is only enough electrophilic reagent
to add to one of the double bonds, it will
add preferentially to the more reactive
one.

Reactions of Conjugated Dienes
• An isolated diene undergoes 1,2-addition.

• A conjugated diene undergoes both 1,2- and
1,4-addition.
1,2-Addition and 1,4-Addition
• 1,2-addition is called direct addition.

• 1,4-addition is called conjugate addition.
Mechanism for the Reaction of
a Conjugated Diene

Which Carbon Gets the Proton?
Protonate the end that forms the more stable

carbocation: (in asymmetric conjugated dienes)
3°allylic and 1°allylic 2°allylic and 1°allylic

carbocation carbocation
Kinetic and Thermodynamic Products
Two factors:
1. Structure of reactant
2. Temperature of the reaction
For the reaction of 1,3-butadiene
Kinetic product: the more rapidly formed product.

Thermodynamic product: the more stable product.
If the Reaction is Irreversible,
the Kinetic Product Predominates
If the reaction conditions are mild, i.e. at low
temperatures, the major product will be the
faster-formed product. i.e. the kinetic product.
Remember:
Alkene stability is determined by the number of alkyl groups bonded to
its sp2 carbons – the greater the number of alkyl groups, the greater its
stability.
If the Reaction is Reversible, the
Thermodynamic Product Predominates
If the reaction conditions are vigourous, i.e. at
higher temperatures, the major product will be the
more stable product. i.e. the thermodynamic
product.

Why?

Kinetic Control

Thermodynamic Control

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.

The Proximity Effect
The proximity effect causes the 1,2-product

to be formed faster.
Although the 1,2-product is always the

kinetic product, do not assume that the
1,4-product is always the thermodynamic
product.
• The 1,2- and 1,4- addition products obtained have the same
stability, because both have the same number of alkyl groups
bonded to their sp2 carbons.
• Neither is the thermodynamic product.
• Approximately equal amounts of both products will be formed
under conditions that cause the addition reaction to e
reversible.
• The 1,2-addition product is the kinetic product.
Practice Problem 6
a.When HBr adds to a conjugated diene, what
is the rate-determining step?
b.When HBr adds to a conjugated diene, what

is the product-determining step?

Solution - Practice Problem 6
a. The rate-determining step is the formation
of the carbocation.
b.The product-determining step is the reaction

of the carbocation with the nucleophile.

Practice Problem 7
What are the major 1,2- and 1,4-addition products
of the following reactions? For each reaction,
indicate the kinetic and the thermodynamic
products.

The Diels–Alder Reaction
- 1,4-addition reaction
Reactions that create new carbon-carbon bonds are very
important to synthetic organic chemists.
 Small carbon skeletons can be converted to larger ones
 In a Diels-Alder reaction:
 two new carbon-carbon bonds are created,
 a cyclic compound is formed. -(product often called an adduct)
adduct
The Diels–Alder Reaction
Forms a Six-Membered Ring
• A pericyclic reaction is one that takes place by a cyclic shift of

electrons.
• A cycloaddition reaction is one in which two reactants form a
cyclic product.
• a [4+2] cycloaddition reaction
• 4 of the six π electrons come from the conjugated diene
• 2 of the 6 π electrons come from the dienophile
The Mechanism
It is a 1,4-addition of
• an electrophile and a nucleophile to a conjugated
diene in a single step.

Mechanism
Always this pattern:

• break 3 C—C pi bonds
• form 2 C—C single bonds and 1 C—C pi bond
• a double bond is always formed between C2 and C3 of
the product formed
Faster if There is an Electron
Withdrawing Group on the Dienophile
• The reactivity of the dienophile is increased if an electron-
withdrawing group is attached to its sp2 carbons:
• e.g. a carbonyl group (C═O) or cyano group (C≡N),

• withdraws electrons from dienophile’s double bond
• puts a partial +’ve on the sp2 carbon
• makes the dienophile a better electrophile

The Electron Withdrawing Group Makes
the Electrophile a Better Electrophile

Another Diels–Alder Reaction
A wide variety of cyclic compounds can be obtained by varying the
structures of the conjugated diene and the dienophile.
Electron withdrawing groups:

C═O (carbonyl group) or C≡N (cyano group)
Alkynes Can Also Be Dienophiles
The cyclic product has two isolated double bonds.

Another Diels–Alder Reaction
If the dienophile has two C ═ C, two successive Diels-Alder
reactions can occur if excess diene is available.

Both Reactants are Not Symmetric
Two products are possible – because the

reactants can align in two different ways.
–constitutional isomers
The Reactants Can Be
Aligned in Two Ways
Don’t change the position of one of the
reactants and turn the other upside down.

Which Alignment Gives
The Major Product?
Need to draw the resonance contributors of the
reactants.

The Answer
• The partially +’vely charged carbon on dienophile will

preferentially bond to the partially –’vely charged carbon of
diene.
• The major product: 2-methoxy-3-cyclohexene carbaldehyde.
s-Cis and s-Trans Conformations
Conformations results from rotation about single bonds
A conjugated diene is most stable in a planar
conformation:
• s-cis conformation (cis about a single (s) bond)
• s-trans conformation (trans about a single (s) bond)

The Diene Must Be in
an s-Cis Conformation

Locked in an s-Cis Conformation
When the diene is a cyclic compound, the Diels-Alder
reaction product is a bridged bicyclic compound.
endo configuration or exo configuration

Endo and Exo

Bridged Bicyclic Rings and
Fused Bicyclic Rings

Practice Problem 9
What are the products of the following reactions?

If the Diels–Alder Reaction Creates
an Asymmetric Center
the product will be a racemic mixture. Do you remember what
this means? Please revise stereochemistry from Organic
Chemistry 1.
A racemic mixture

The Stereochemistry of a
Diels-Alder Reaction
• It is a syn addition reaction.
• One face of the diene adds to one face of the
dienophile.
• i.e. if the substituents of the dienophile are cis,
then they will be cis in the product.
• If the substituents in dienophile are trans, then
they will trans in the product.
• Because each of the following reactions forms a
product with two new asymmetric centers, a pair of
enantiomers is formed.
Cis Forms Cis
Trans Forms Trans

How to Determine the Reactants
of a Diels–Alder Reaction
Retrosynthesis

How to Determine the Reactants
of a Diels–Alder Reaction
Retrosynthesis

Practice Problem 10
What diene and what dienophile should be used
to synthesize the following?

Group I Compounds are Nucleophiles;
They React with Electrophiles

Group I Compounds are Nucleophiles;
They React with Electrophiles
• Alkenes have one π bond undergoes one electrophilic addition
reaction.
• Alkynes have two π bonds undergo two electrophilic addition
reactions.
• if first addition reaction forms an enol, it rearranges to a ketone
(or aldehyde) and a second addition reaction can occur.
• if double bonds of a diene are isolated, they react just like alkenes
• if double bonds are conjugated, they undergo both 1,2- and 1,4-
addition reaction because the carbocation has delocalized
electrons
The Annulenes
 Annulenes are hydrocarbons with alternating

single and double bonds
 Hückel’s rule predicts that annulenes will be
aromatic if their molecules have (4n + 2) p
electrons and have a planar carbon skeleton
 Benzene is a six-membered annulene – i.e.
[6]-annulene
 Cyclobutane is a [4]-annulene
 Cyclooctatetraene is an [8]-annulene
© 2014 by John Wiley & Sons, Inc. All rights reserved.
 All these (4n + 2) p, planar
annulenes are aromatic
(4n + 2) p Benzene [14]Annulene

planar annulenes: [6]Annulene (aromatic)
[18]Annulene
(aromatic)

 Non-planar (4n + 2) p annulenes are
non-aromatic

 (4n) p non-planar annulenes are
antiaromatic
Do you agree with this?
Cyclobutadiene [8]Annulene [16]Annulene

[4]Annulene
 Fullerenes:
 Five- and six-membered rings
arranged to form a “soccer ball”
structure
 Consist of 20 hexagonal and 12
pentagonal rings
 Each carbon atom is bonded to three
others and is sp2 hybridized
 C60: buckministerfullerene

Figure: Friedrich Sauer – Science
Library
Figure: L. Cadars

Photo: from Chemistry world
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Organic Chemistry II, 2020

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

Showing Delocalized Electrons

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

Electron delocalization is most effective if all the atoms

© 2014 Pearson Education, Inc.

Delocalized electrons result from the p

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The greater the stability of a resonance contributor, the more it

The more the resonance contributor contributes to the structure

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The only time you need to show a resonance

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The delocalization energy is greater for the

© 2014 Pearson Education, Inc.

Significant delocalization energy

• The greater the number of relatively stable

• It must have an uninterrupted cloud of π electrons.

Because there are two electrons in a pair, Hückel’s

Thus Hückel’s rule is a mathematical way of saying

© 2014 Pearson Education, Inc.

2. Because it has an odd number of π

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Cyclobutadiene has an even number of pairs

Cyclooctatetraene has an even number of

The same criteria to determine whether a

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A heterocyclic compound is a cyclic compound in

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The aromatic ring of pyridine is less electron dense than benzene

The aromatic ring of pyrrole is more electron dense than benzene

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

Aromaticity is characterized by stability,

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

A conjugated diene, therefore, is more stable than

Electron delocalization stabilizes a compound.

The positive charge is not localized but shared by

It has five resonance contributors, and the positive charge is

Because allyl and benzyl cations have delocalized electrons,

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The more stable the base, the

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The negative charge is on one