CHAPTER SEVEN

AROMATIC
COMPOUNDS

Copyright 2014 McGraw-Hill Education. All rights reserved.

Hybrid of the two equivalent resonance forms

Delocalized p-orbitals of the three pi-bonds

 7.2 Prove of Resonance Stabilization = Aromaticity
The special stability of benzene and its derivatives due to delocalization energy or
resonance energy is the modern definition of the term aromaticity
1. Benzene is considered parent (Note: Many Substituted benzenes have common
name which can also be the parent e.g toluene, xylene, phenol, benzaldehyde)
2. List susbstituents in the alphabetical order
3. Number the ring in the direction that gives the lowest locant at first point
of difference (para, meta and ortho are not used for IUPAC)
Toluene

o-Xylene
 Nomenclature using different parent

The word 'phenyl' is used when the C6H5 A benzyl group is

group is attached as a substituent C6H5CH2

2-Phenylethanol Benzyl bromide

 - a collection of benzene rings fused together

Benzo[a]pyrene metabolized to the epoxide carcinogen

Benzylic carbocation stabilized by resonance
Control of Regioselectivity of the benzylic carbocation

Resonace stablized carbocation

 Selective Reaction of Side Chains in Benzene
Selective Oxidation

Selective Hydrogenation
The high electron density of the benzene ring makes it a nucleophile for
reaction with electrophiles, similar to alkenes
HOWEVER the initial disruption to the resonance stable benzene ring
compare to alkene make it less reactive with usual electrophilic species.

Reactive Less reactive = Reactions (HSAB theory)

No Reaction

Less Reactive Less reactive = No Reactions (HSAB theory)

Resonance stable benzene ring requires more reactive
electrophiles (by activation) than those which react with
alkenes

-requires the activation of electrophiles

e.g. Less reactive Reactive

No Reactions Reactions

Less Reactive
Step 1: Attack on the electrophile

Step 2: Loss of a proton gives the substitution product

WHY ELECTROPHILIC SUBSTITUTION FOR BENZENE
-electrophilic addition to the benzene ring first upset the delocalised
electron system, thus requires highly active electrophiles
-subsequent addition of nucleophile to the carbocation disrupt the
ring delocalised electron system permanently , which is not favored
-the elimination of a protons regenerate the stable benzene ring
 Some Substitution Reactions of Benzene
Cl
FeCl3
Halogenation + Cl2

CH3
AlCl3
Friedel-Crafts + CH3Cl
Alkylation O
O AlCl3 C R
Friedel-Crafts + C
Acylation R Cl
O
N O
+ O H2SO4 + -
Nitration + HO N
O O
-
O S OH
Sulfonation SO3
O
+ HO S OH
O
-Activation of electrophilic species in nitration

Nitronium ion
Lewis acid catalysed activation
Acyl cation can be represented by the two resonance forms:
1. What is the effect of a substituent on the rate of electrophilic
aromatic substitution?
- electrons donation to the ring increase reactivity

>

-electron withdrawing of the electrons from the ring decrease reactivity

<
Reactivity of the substituted -benzene compared with benzene

Inductive effect

I- - substituents with greater electronegativity that form sigma-bonds to the

aromatic ring exert an inductive electron withdrawal, which deactivates the
ring or conjugative interaction facilitates withdrawal of electron

I+ - conjugative interaction facilitates electron pair donation

 Increased Reactivity of the Benzene Ring - ACTIVATING

I- > I+
Dipole

Decreased Reactivity of the Benzene Ring - DEACTIVATING

I+ > I-
Dipole
ACTIVATING Group Ortho and para electrophilic substitution

DEACTIVATING Group - meta electrophilic substitution

WHY Alkyl group direct Ortho and para electrophilic substitution?
ortho

Most stable carbocation

Hyperconjugation = 4

meta

para
Most stable carbocation
Hyperconjugation = 4
 Alkoxyl and amino groups are strong electron-donating resonance effect
Favored the ortho and para positions

Ortho =4 x resonance

Most stable

meta =3 x resonance

para =4 x resonance

Most stable
Meta favored with no
destabilization of
carbocation

Deactivating
Groups
 Exception : Deactivating but ortho and para directors.

Reaction Rate:
Deactivating

Reagioselectivity:
Lone pair of electrons
from Halogen direct
ortho and para
The order of reaction sequence is important and can give different product(s)

Acylation followed
by bromination
Meta product

Bromination
Followed by
Acylation-Para
product
Reaction site determine by the reactivity induced by the substituents
-OH >> -CH3
The reaction site is too hindered
-Among planar, monocyclic, fully conjugated polyenes, only those
possessing (4n + 2) electrons will be especially stable ( or termed as
aromatic)
- have a closed loop of 4n+2 pi electrons in the cyclic
arrangement of p cyclic arrangement of p orbitals
 Pyrrole has six
electrons with the
lone pair = aromatic

Furan has six electrons plus an unshared pair in an

oxygen sp 2 orbital, which is perpendicular to the
system and does not interact with it (aromatic)
Pyridine has six pi- electrons plus an unshared pair in
a nitrogen sp2 orbital (aromatic)
The positively charged Pyrrole
has uses the lone pair and now
only has four pi- electrons-Not
aromatic

The positively charged Pyridine

although uses the lone pair ,
but still has six pi electrons-
Aromatic