Chapter 5

Delocalized Electrons and

Their Effect on Stability, pKa,
and the Products of a
Reaction
Concepts and drawing
resonance structures
Aromatic Chemistry
Electrophilic Aromatic
Substitution (4 reactions),
reduction. and side chain
oxidation

Curved arrows denote electron

flow

Both positive and negative charge may be delocalized

Delocalized Electrons Affect

pKa Values

Delocalization in acids

Phenols versus Alcohols

Why Phenols are More Acidic

Allylic and Benzylic

Resonance Contributors for

an Allylic Cation

Allylic not a primary carbocation

Resonance Contributors for

a Benzylic Cation

Resonance Contributors for

a Benzylic Cation

Delocalization Energy

he delocalization energy is the extra stability a compound ha

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.

Benzene extreme delocalization

Heats of hydrogenation

The delocalization energy of benzene is 36 kcal/mol.

Benzene an aromatic molecule

riteria for a Compound to Be Aromat

Must be cyclic
All atoms must be sp2 hybridized flat
Must have 2, 6, 10... electrons (Huckel number)

Polycyclic Aromatic Hydrocarbons

e
2
6
10
14
18
etc.

10 e

14 e

 e
2
6
10
14
18
etc.

Examples of Compounds
That are Not Aromatic

Cyclobutadiene doesnt have a Huckel number of electrons.

Cyclooctatetraene is not planar.

Aromatic ions
e
2
6
10
14
18
etc.

cyclopentadiene

cyclopentadienyl anion

Anion is aromatic

Heterocyclic Aromatic Compounds

e
2
6
10
14
18
etc.

pyrimidine

purine

caffeine

nicotine

LSD

Orbital Structure of Pyridine

Orbital Structure of Pyrrole and

Furan

Pyrrole similar to cyclpentadienyl anion in structure

Protonated Anilines versus

Protonated Amines

Nitrogen Containing
Heteroaromatics

Nitrogen Containing
Heteroaromatics

Nitrogen Containing
Heteroaromatics

e
2
6
10
14
18
etc.

Combining Concepts:
Withdrawing Electrons by
Resonance

Withdrawing Electrons by
Resonance

Combining concepts
hydrohalogenation and resonance
delocalization

Why the Difference in Rate?

Localized vs. delocalized

Reactions of
Electrophilic
Aromatic Substitution
Benzene
(EAS)
1. Halogenation
2. Nitration
3. Acylation
4. Alkylation
Redox reactions of substituted
benzenes
6. Side chain oxidation
7. Reduction of nitrobenzene

The Nomenclature of
Substituted Benzenes

some monosubstituted benzenes are named

just by adding the name of the substituent to
benzene

The Nomenclature of
Substituted Benzenes

Most aromatic compounds are commonly

named.

Electrophilic Aromatic
Substitution

Aromatic compounds such as benzene undergo

electrophilic aromatic substitution reactions (EAS).
Of the four EAS reactions that will be discussed, all
proceed with the mechanism shown above only
differing in the identity of the electrophile

Nobel Prize in Chemistry 2016

Jean-Pierre Sauvage

J. Fraser Stoddart

Bernard L. Feringa

Nobel Prize in Chemistry 2016

Jean-Pierre Sauvage

J. Fraser Stoddart

Bernard L. Feringa

Substitution not addition

The electrons are nucleophilic (like electrophilic addition)

Aromaticity is restored in the product from electrophilic
substitution.

Common EAS mechanism

1. Halogenation of Benzene

Bromination or chlorination of benzene requires a Lewis acid

catalyst because benzenes aromaticity causes it to be less
reactive than an alkene.
Iron (III) or aluminium chlorides or bromides are the typical Lewis acid
catalysts.

EAS mechanism - halogenation

M = metal = aluminum or iron (III)

Br+ or Cl+ is the electrophile
(e.g., FeCl3 or FeBr3)

2. Nitration of Benzene

EAS mechanism - nitration

Sulfuric acid protonates nitric acid.

Protonated nitric acid loses water
to form the electrophile (the nitronium
ion).

3. EAS Acylation

An acid (acyl) chloride is the source of the acyl group

Acid chlorides are easy to make with thionyl chloride

EAS mechanism - acylation

The acylium ion is the electrophile.

EAS acylation - intramolecular

Cyclic compounds are formed from intramolecular reactions.

Formation of five- and six-membered rings are favored.

4. EAS Alkylation

An alky halide is the source of the alkyl

group.
A Lewis acid (AlCl3) is
required.

EAS mechanism - alkylation

A carbocation is the electrophile.

This reaction is limited to alkyl halides that can form carbocations

5. Side chain oxidation - no

mechanism
functional group transformation = alkyl benzene to benzoic
acid
Alkyl benzene must have at least one benzylic hydrogen
Multiple side chains can be oxidized

or KMnO4

or KMnO4

6. Nitrobenzene reduction no
mechanism
Nitrobenzene reduction functional group transformation
Nitrobenzene to aniline

Nomenclature of Disubstituted
Benzenes

The relative positions of two substituents can be indicated

by numbers or by the prefixes ortho (1,2), meta (1,3) or para
(1,4)

The Effect of Substituents on

Reactivity

EAS requires the electrons in ring to attack electrophile

Electron Donating Groups (EDG) donate electron density to the

benzene ring increasing benzenes nucleophilicity and stabilizing the
carbocation intermediate.

Electron Withdrawing Groups (EWG) withdraw electron density to the

benzene ring decreasing benzenes nucleophilicity and destabilizing
the carbocation intermediate.

Electron Donating Groups (EDG)

The methoxy group is electron donating.

Same argument as to why phenol is a stronger acid than cyclohexanol

--electron delocalization

Electron Withdrawing Groups

(EWG)

The nitro group is electron withdrawing

An atom directly attached to the ring that is doubly or triply

bonded to an electronegative atom withdraws electrons by
resonance.

Compared with benzene

Electron donating groups

EDG donate electron density to the benzene ring increasing

benzenes nucleophilicity and

activating towards EAS.

Electron withdrawing groups

EWG withdraw electron density to the benzene ring

decreasing benzenes nucleophilicity and
towards EAS

deactivating

Electronic effects
EWG: Substituents that withdraw electron density have a full
or partial positive charge next to the aromatic ring

EDG: Substituents that donate electron density have a alkyl

group or a heteroatom (lone pair) next to the aromatic ring and
activate the compound towards additional EAS

Remember that alkyl groups can donate electron density

this was used to explain the order of carbocation stability

Synthesis of di-substituted
aromatics directing effect
All activating substituents are orthopara directors.

Activation means that toluene will be brominated

compared with benzene

faster

Meta Directors
All deactivating substituents are meta directors.

Deactivation means that nitrobenzene will be brominated

slower compared with benzene

Halogens are unique

Halogens withdraw electron density (more electronegative than carbon)
but have lone pair electrons so they are deactivating but ortho/para
directors. This is the only exception

Nitration of phenol

ortho

para

Bromination of nitrobenzene
Br

meta

Br

Positive charge (+) always is ortho

and para to sp3 carbon of
intermediate

Positive charge (+) always is ortho

and para to sp3 carbon of
intermediate

The Order of the Reactions is

Important

The Order of the Reactions is

Important

Recognize EWG and EDG and

extend to other systems

Explain the trend of pKa values