Organic Chemistry

4th Edition
Paula Yurkanis Bruice

Chapter 16
Reactions
of
Substituted
Benzenes

Irene Lee
Case Western Reserve University
Cleveland, OH
2004, Prentice Hall

Examples of Substituted Benzenes

The relative positions of the two substituents are

indicated by numbers or by prefixes

The two substituents are listed in alphabetical order

If one of the substituents can be incorporated into a

name, that name is used and the incorporated
substituent is given the 1-position
NH2
Cl

OH
CH2CH3

CH3
NO2

2-chlorotoluene
ortho-chlorotoluene

4-nitroaniline
para-nitroaniline

2-ethylphenol
ortho-ethylphenol

Some disubstituted benzenes have names that

incorporate both substituents

Naming Polysubstituted Benzenes

The incorporated substituent is given the 1-position; the

ring is numbered in the direction that yields the lowest
possible number

Reaction of Alkyl Substituents

The halogen in the benzylic position can be replaced by

a nucleophile

A halo-substituted alkyl group can undergo elimination

Reduction of Unsaturated Substituents

Oxidation of the Alkyl Substituent

The same reagent that oxidizes the alkyl substituent will

oxidize the alcohol

Therefore, a milder oxidizing reagent is used:

Reduction of a Nitro Substituent

It is possible to selectively reduce just one nitro group

Donation of electrons through a bond is called inductive

electron donation
An alkyl group is more electron donating than hydrogen
because of hyperconjugation

Withdrawal of electrons through a bond is called

inductive electron withdrawal
The NH3 group is more electronegative than a hydrogen

A substituent can also donate electrons into the ring by

delocalizing its lone-pair electrons

Electron withdrawing by resonance occurs when the

electrons from the ring are delocalized onto the
substituent

Substituents such as CO, CN, and NO2 withdraw

electrons by resonance

The strongly activating substituents make the benzene

ring more reactive toward electrophilic substitution

All the strongly activating substituents donate electrons

by resonance and withdraw electrons inductively

The moderately activating substituents can donate

electrons into the ring and away from the ring

Overall, they donate electrons by resonance more

strongly than they withdraw electrons inductively

These substituents are slightly more electron donating

than they are electron withdrawing

These substituents donate into the ring by resonance and

withdraw electrons from the ring inductively

They withdraw electrons inductively more strongly than

they donate electrons by resonance

These substituents withdraw electrons both inductively

and by resonance

These substituents are powerful electron-withdrawing

groups

These substituents withdraw electrons both inductively

and by resonance

The substituent already attached to the benzene ring

determines the location of the new substituent

All activating substituents and the weakly deactivating

halogens are orthopara directors
All substituents that are more deactivating than halogens
are meta directors

The relative stabilities of the carbocations formed from

the electrophilic substitution of the substituted benzene
determine the preferred reaction pathway

Any substituent that donates electrons inductively is an

orthopara director

All substituents that donate electrons by resonance are

orthopara directors

Electron withdrawal decreases reactivity toward

electrophilic substitution and increases acidity

Electron donation increases reactivity toward electrophilic

substitution and decreases acidity

The orthopara product ratio decreases with an increase

in the size of the substituents

Methoxy and hydroxy substituents are so strongly

activating that halogenation is carried out without Lewis

Aniline and N-substituted anilines do not undergo

FriedelCrafts reaction

Aniline cannot be nitrated but tertiary aromatic amines

can be nitrated

In designing a disubstituted benzene, the order in which

the substituents are to be placed on the ring must be
considered

Synthesis of Trisubstituted Benzenes

Steric hindrance makes the position between the

substituents less accessible

A strongly activating substituent will win out over a

weakly activating substituent or a deactivating substituent

If the two substituents have similar activating properties,

neither will dominate

Synthesis of Substituted Benzenes

Using Arenediazonium Salts

Preparation of the Diazonium Salt

Consider the synthesis of para-chloroethylbenzene

Fluorination of Benzene

The Arenediazonium Ion as an

Electrophile

Only highly activated benzene rings can undergo this

reaction
Substitution takes place preferentially at the para position

However, if the para position is blocked

Reaction of Amines with Nitrous Acid

Nucleophilic Aromatic Substitution

Reactions

The electron-withdrawing substituents must be ortho or

para to the site of nucleophile attack

The electrons of the attacking nucleophile can be

delocalized

Formation of Benzyne

Benzyne Is an Extremely Reactive

Species

Polycyclic Benzoid Hydrocarbons

Electrophilic substitution reactions of naphthalene and

substituted naphthalenes

1-substituted naphthalenes are easier to form

2-substituted naphthalenes are more stable

In substituted naphthalenes, the nature of the

substituent determines which ring will undergo
electrophilic substitution