2022-08-30

Chapter 8
had Mail

n
same 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

© 2017 Pearson Education, Ltd.

Preview for chapter 8

For Preview (Chapter 8)

1. Delocalization of electrons: https://www.youtube.com/watch?v=jP_6Ro-

XUnU

2. Structure of benzene: https://www.youtube.com/watch?v=sYJkqX14BYY

3. Resonance Contributors: https://www.youtube.com/watch?v=_zhU_r4Yv8g

4. Delocalization energy: https://www.youtube.com/watch?v=oNtnEi-

Fojw&t=355s
5. 1,2-Addition and 1,4-Addition:
https://www.youtube.com/watch?v=peF0tXZFCAA

6. Kinetic and Thermodynamic Products: https://www.youtube.com/watch?v=l-

l_8cSQdEw

7. The Diels–Alder Reaction: https://www.youtube.com/watch?v=9Ng6Zv9oLzk

© 2017 Pearson Education, Ltd.

1
i­
2022-08-30

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:

© 2017 Pearson Education, Ltd.

What is the Structure of Benzene?

Molecular Formula = C6H6 CnH2n+2 = C6H14 4.

i i.
+ 3
Therefore, benzene has a degree of unsaturation of 4. e,
- 2 2 2 + 2

3 t 1

C 6

2 hard

,,

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

TV 2t T 2

T1 3t ng 1.
ri
=
4
=
4.

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Benzene Forms Three Disubstituted Products

•
Compound I forms two disubstituted products.

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The Structure of Benzene

1,
3

a
Compound II forms four disubstituted products. T
o o
t
3

1 at
Equiibrium Very
↓

© 2017 Pearson Education, Ltd.

(

Kekule’s Proposal for

the Structure of Benzene
Benzene is a mixture of two compounds in rapid equilibrium.

and
Therefore, three disubstituted products are formed.

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Can't te See period

4
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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.

④
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Showing Delocalized Electrons

nrnn

C: 10t i
☆

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

Notstereois.net

☐
not real notre.ae

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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.

1
Cyclooctatetraene is not planar,
so it does not have delocalized electrons.

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P Over kp ✗

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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.

-2Eur

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

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

t.IO
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.

lnt
satratedunc.at
rated

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Move π Electrons to an sp2 Carbon

E I O
• •

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

→
para N
positive

5 ,

© 2017 Pearson Education, Ltd.

9
6
.it
①
C) U
②

③
tre ii.
< pattern >

① f) +1h
③
f) .fi
↓
"
C ?

◦
A

③
i. hxi
④
in
2022-08-30

⑦
Move Lone-Pair Electrons to an sp2 Carbon

Eat structure ,
€0
f)
resona ne Con

Hybrid X .

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Move π Electrons to an sp Carbon

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Delocalized Electrons Affect Protein Structure

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Better
which One is
Strong ( ?

A Has a Greater Predicted Stability Than B

Better(Major)

contibutortfneut.ae
.

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

""

<
chargese.peration
No
charge O

i N y ans
table
re a

F has an incomplete octet. (Minor

>

,
smanpa.im

© 2017 Pearson Education, Ltd.

12
?⃝
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G Has a Greater Predicted Stability Than H

No
charge Charge
de "

omoreelectronegatie.ms

matched.lt
H has a positive charge on an electronegative atom.

© 2017 Pearson Education, Ltd.

-
c
than
is Better

J Has a Greater Predicted Stability Than I

charge charge d.

J has a negative charge on oxygen,

whereas I has negative charge on carbon.

© 2017 Pearson Education, Ltd.

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Features That Decrease

The Predicted Stability

nnn~nvetunstable.z_tos-i.cn
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.

table .

4. Separated charges.
Nhnnn
< res onMe >

© 2017 Pearson Education, Ltd.

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.

SSE27
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

Major minor Major Major ,

d e . b a / i z a H o n e rg y i s1 2 rg e r
e)

The delocalization energy is greater for State

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

ddocalizati.in E

significant delocalization energy: three relatively stable resonance

contributors

significant delocalization energy: two equivalent resonance contributors

-

State
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pssibkres.name
stabilit.IT t 0 H E
4.

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

:
3(
i

✗
© 2017 Pearson Education, Ltd.

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The Smaller the Heat of Hydrogenation,

the More Stable the Compound

E
.fi?Stableswhy? ramnes
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

"
"

State

i
Shorten
layer

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

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Conducting polymers are used in LED displays.

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Allyl and Benzyl

O
Allylic and Benzylic

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Resonance Contributors for an Allylic Cation

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Resonance Contributors for a Benzylic Cation

reahyst.be

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Relative Stabilities of Carbocations

State ,

) 7 10
°

3 2

i
i
be
i
~

10

•
© 2017 Pearson Education, Ltd.
.

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Relative Stabilities of Carbocations

• • •

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The MO Diagram for Ethene

←
S .

Full?
-

←
5th
© 2017 Pearson Education, Ltd.

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Resonance Contributors of 1,3-Butadiene

minor
Major minor

Four π electrons are delocalized over four carbons.

© 2017 Pearson Education, Ltd.

The MO Diagram for 1,3-Butadiene

de SP "

( H2

※
(H2 =
(H -
CH =

t.se
↓
i.
-
E

© 2017 Pearson Education, Ltd.

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Symmetric and Antisymmetric

Molecular Orbitals

2 node

o
Il o o o

odd number → S4MM e.ven number

a MM t
→

e.

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Localized Electrons versus

Delocalized Electrons

'

4.

© 2017 Pearson Education, Ltd.

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Delocalized Electrons Affect pKa Values

iii.
ii.
iii.
More
s
i
•
o

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

Review
ph

deh.cat
(
www.d-moreswsk
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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.

© 2017 Pearson Education, Ltd.

Electronic Effects
⊖
Erich "

o
- base ←
(B
( es
est

th
.

d.
acidi
Electron donation decreases acidity.
More
y
Electron withdrawal increases acidity.
© 2017 Pearson Education, Ltd.

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Inductive Electron Withdrawal

reduee-density.NO
-

dire.CHy .

05
.

inductive electron withdrawal =

withdrawal of electrons through sigma bonds

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Donating Electrons by Resonance

M e .
M

e.
minor contract
?
for What
→ Reso name Hybrid .

© 2017 Pearson Education, Ltd.

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Withdrawing Electrons by Resonance

C.

ooe-Yi.in
contribntrweakerBaseimorestable.fCBles table.my?Nosvb
© 2017 Pearson Education, Ltd.

Electronic Effects and pKa Values

CI 6
.

'

in - i
stmgatw.it (

withdrawinggwup.cl
○
.

- "

(B : loss State

© 2017 Pearson Education, Ltd.

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= + Hn → A.

Electron Delocalization Can Affect

the Product of a Reaction

⊕ ⑦

2° 20 .

More
222ⁿᵈ State
A secondary benzylic carbocation is more stable
- ,
than a secondary alkyl carbocation.

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Isolated and Conjugated Dienes

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OF
Reactions of Isolated Dienes

i
Et t

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The Mechanism

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The Double Bonds Have Different Reactivities

⊕
,

•o i.
↑

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i
○
Reactions of Conjugated Dienes

②
-

© 2017 Pearson Education, Ltd.

34
?⃝
2022-08-30

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

resonanel.TStructure
,T

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

Protonate the end that forms the more stable carbocation.

30 100 20 10

-
30 .

i
© 2017 Pearson Education, Ltd.
CH Ed ( H-
3

Br

Kinetic and Thermodynamic Products

For the reaction of 1,3-butadiene:

End at sI ?
'
© 2017 Pearson Education, Ltd.
↑ ↑
disuhstitudesukt.me
M0m

36
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If the Reaction is Irreversible,

the Kinetic Product Predominates

↓ (Slow)
lowerteIE.at

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If the Reaction is Reversible,

the Thermodynamic Product Predominates

○
.

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Why?

f)
snjf.ie
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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

CNO addi.li on reaction

.

At C.

cyclohe.ee
.

A dienophile “loves” a diene.

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( 1 )
Concertet reaction

The Mechanism
.
Concert reaction

3 bond Breaking
Formation
3 bond

5Mg 5 -D
.

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

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

4. (on jugatedbie.ve C .

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2.
dienoph.tl ( .

The Diels–Alder Reaction is

a 1,4-Addition Reaction

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w w.HhdrawiygwpiO.NO2-taster.unstablenset ctn densi

An Electron Withdrawing Group
Increases the Reactivity of the Electrophile

ty 4

0 O
© 2017 Pearson Education, Ltd.

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?

and

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9
ion in teration

s-Cis and s-Trans Conformations

Q
a
unstabk
!!
© 2017 Pearson Education, Ltd.
( is

!!!

46
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The Diene Must Be in an s-Cis Conformation

↓
( is
-7 No Reaction

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Locked in an s-Cis Conformation

O
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

[email protected]

1i03 ( 4.3 ,

BICyclonc.name

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Endo and Exo Products

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

a⑤
π electrons.

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Stereochemistry of
the Diels–Alder Reaction

→
li 1 enantiomo
If the reaction creates a new asymmetric center,
a racemic mixture is formed.

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KX
+
cilcEn
If the Reaction Creates
Two New Asymmetric Centers
&
cis forms cis

a
trans forms trans

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How to Determine the Reactants

of a Diels–Alder Reaction

ildum …

COct

+ K
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How to Determine the Reactants

of a Diels–Alder Reaction

© 2017 Pearson Education, Ltd.

.
:

! ! ."
!
.
1 1
50
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Delocalized Electrons Make

a Compound More Stable

imaginayre.ae

☐
The delocalization energy of benzene is 36 kcal/mol.

G 0
© 2017 Pearson Education, Ltd.

① Should he
number
TV Electron
② (
④
③ Plan

Criteria for a Compound to Be Aromatic ☐

TS6

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

4M0

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.
© 2017 Pearson Education, Ltd.

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

c
aromatic
Anti
awm

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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.

© 2017 Pearson Education, Ltd.

Aromatic Compounds

"
M
"
1

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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

C0
"

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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.
O Nvitoger
The aromatic ring of pyrrole is more electron-dense
than benzene because
the nitrogen donates electrons into the ring.

© 2017 Pearson Education, Ltd.

[x
More Examples of
Aromatic Heterocyclic Compounds
0
[32 <
m

KK
[ ]): CK
.
© 2017 Pearson Education, Ltd.

[3
[
:D 57
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How Benzene Reacts Br

= + HBr → rd
H

→
A

Sbs
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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61