Adama Science and Technology University

School of Applied Natural Sciences

Department of Applied Chemistry

Chemistry of Aromatic Compounds

Endale Mulugeta (PhD)
Office Room No 26: Old Admin Building
Adama, Ethiopia
©2020
 Aromatic Compounds

 Aromatic compounds, originally named because of their fragrant

properties
 They are unsaturated hydrocarbon ring structures that exhibit
special properties, including unusual stability, due to their
aromaticity
 They are often represented as resonance structures containing
single and double bonds
 Structure of Aromatic Compounds

 The Kekulé structure:-The ring system had alternating double and

single bonds
 Two resonance forms of benzene, and, on the right, the common
representation of benzene showing all of the bonds are equal

 Spectroscopic analysis of the structure of benzene showed that it

had six equal carbon-carbon bond lengths of 1.39Å (this is
compared to a normal C-C of 1.47Å and C=C of 1.34Å).
 Aromaticity and Antiaromaticity

 „aromatic‟ was originated from the characteristic odor or „aroma‟

of benzene-like compounds

 Criteria for aromaticity

 The molecule must be cyclic

 Planar with uninterrupted cloud of π electrons above and below
the plane of the ring
 It should have 4n+2 π electrons
 Non aromatic compounds:- are not aromatic due to reasons
such as lack of planarity or disruption of delocalization. They
may contain 4n or 4n+2 π electrons
 Antiaromatic compounds are planar, cyclic, conjugated systems
with an even number of pairs of electrons (4n, n = 1, 2, 3 etc)

? ?
 Aromaticity in fused rings The criteria for aromaticity in mono
cyclic hydrocarbons can be applied for polycyclic hydrocarbons
as well
 Aromatic Heterocycles
 Huckel's rule also can be extended to heterocycles, ring systems
that incorporate non carbon atoms

 Physical Properties of Aromatic Compounds

 Aromatic compounds are generally nonpolar and immiscible with
water
 They are often unreactive, they are useful as solvents for other
nonpolar compounds
 Aromatic compounds are characterized by a sooty yellow flame
 Annulenes

 General name given to rings that contain alternating single and

double bonds
 Benzene is [6]annulene ; cyclooctatetraene is [8]annulene
 Naming Aromatic Compounds
 Monosubstituted Derivatives of Benzene
 Many simple monosubstituted derivatives of benzene are named
systematically by adding the name of the substituent to
“benzene” which is the parent:

 If the substituent is an alkyl chain with more carbon atoms than

benzene, then benzene can be treated as a substituent. The ring, in
this case, is called a phenyl group
 There are also monosubstituted benzene rings that have common
names
 Disubstituted Derivatives of Benzene

 For the other rings with common names, start numbering the ring
from the substituent that is part of the common ring such that the
other groups get the smallest possible position
 In general, to name an aromatic compound, you can follow these
steps:
1. Identify and name the parent. If it is not one of the common names,
then use benzene
2. Identify and name the substituents
3. Number the ring to give the substituents the smallest possible number
4. Put the substituents alphabetically followed by the parent name

 For example, in ortho-dibromobenzene, numbering from the top Br goes

clockwise to have a 1,2, instead of 1,6 order:
 If the numbering does not make a difference, then give a smaller
position to the alphabetical priority
Exercise 1. Give an acceptable IUPAC name for each molecule
according to the nomenclature of aromatic compounds. For some
compounds, there may be more than one acceptable name.
 Electrophilic Aromatic Substitution
 The Mechanism of Electrophilic Aromatic Substitution
 Halogenation of Benzene
 Benzene only reacts with bromine and chlorine in the presence of Lewis
acids as they coordinate to the halogens and generate strong electrophilic
species
 The Lewis acids are usually aluminum chloride (AlCl3) or iron chloride
(FeCl3) used for the chlorination, and iron bromide (FeBr3) for the
bromination of the aromatic ring
 Iodination of Benzene
 Iodine is unreactive under identical conditions and the iodination of
benzene is achieved in the presence of an oxidizing agent such
as nitric acid or a mixture of hydrogen peroxide and sulfuric acid
 They oxidize the I2 to I+ and after this, it follows the standard
mechanism of the electrophilic aromatic substitution
 Fluorination of Benzene
 Fluorination of benzene, on the other hand, is a violent reaction and
cannot be achieved directly. Plus, handling F2 is also difficult.
Instead, it is done by converting benzene into an arenediazonium
salt which is then replaced by fluorine by reacting it with
fluoroboric acid (HBF4) via the Schiemann named reaction
 Nitration of Benzene
 Electrophile in the nitration of benzene is the +NO2 (the nitronium
ion), which is formed by protonation of HNO3 by H2SO4
 Sulfonation of Benzene
 Benzene can be converted into benzenesulfonic by reacting it with fuming
sulfuric acid which is prepared by adding sulfur trioxide (SO3); electrophile in
this reaction is the sulfonium ion (+SO3H)
 One interesting feature and advantage of the sulfonation is that it is
a reversible reaction: If you need to remove the sulfonate group
then a dilute solution of H2SO4 should be used. This selective
placing of the SO3 group on the aromatic ring is used
as a protecting group, to temporarily block its position from other
electrophiles, or as a directing group
Exercise 2: Draw a mechanism for the following Electrophilic
Aromatic Substitution Reactions:
 Friedel-Crafts Alkylation

 Following an identical mechanism, two reactions, discovered by

Charles Friedel and James Crafts in 1877, allow for making a new
carbon–carbon bond with the aromatic ring
 The first step is a Lewis acid-base reaction where the activator AlCl3 takes a lone pair
from Cl and eventually breaks it off from the carbon. As a result, a 3o carbocation is
formed which is a strong electrophile and can be attacked by the aromatic ring:
 Rearrangements in Friedel–Crafts alkylation

 Carbocations can undergo rearrangements reactions by hydride or

methyl shift
 Rearrangement affect the Friedel–Crafts alkylation

Eg. 1

Eg. 2
 The reason for this is that the complex formed in the Lewis acid-
base reaction has a very electrophilic carbon connected to the Cl
and it still promotes a 1,2-hydride shift:
 Limitations of Friedel-Crafts Alkylation
 For a successful Friedel–Crafts alkylation, the halogen of the alkyl halide must be
connected to an sp3 hybridized carbon atom because carbocations with the positive
charge on an sp2 carbon are unstable and do not form readily. Therefore, vinyl halides
and aryl halides do not undergo a Friedel–Crafts alkylation
 Friedel-Crafts alkylations and acylations are the slowest in
electrophilic aromatic substitution reactions, so they do not work
when a strongly deactivating group is present:
 Intramolecular Friedel-Crafts Alkylation
 Aromatic compounds that contain a functional group that can be
converted into an electrophile, can undergo
an intramolecular Friedel-Crafts Alkylation:
Exercise 3. Draw the mechanism for each Friedel-Crafts
alkylation reaction
  In Friedel-Crafts acylation aromatic compounds are reacted with an acyl
halide to prepare an aryl ketone

 The electrophile in this reaction is the resonance stabilized acylium

ion which is formed when the Lewis acid AlCl3 ionizes the C-Cl
bond of the acyl chloride:
 The acylium ion is a good electrophile and can be attacked by the
aromatic ring according to the general
 Carboxylic acid anhydrides can also be used for Friedel-Crafts
acylations since the leaving group here is the acetate ion which is
a resonance-stablizied, good leaving group
 Advantage of the Friedel-Crafts acylation reactions is that they
do not undergo rearrangements like Friedel-Crafts alkylations do
 This allows to prepare primary alkyl substituted aromatic
compounds since the aryl ketones can be reduced by the Wolff-
Kishner or Clemenson reduction
 The Intramolecular Friedel-Crafts Acylation is possible for
aromatic compounds containing the acyl chloride functional group:
 The limitation of the Friedel-Crafts alkylation not working with
deactivated aromatic rings are still applied to the Friedel-Crafts
Acylation as well:

 Because of this, polyacylation cannot be achieved since the

carbonyl added in the first acylation is deactivating the ring
Exercise 4.Determine whether each of the following reactions will
proceed and predict the major product and draw the mechanism for the
following Friedel-Crafts Acylation reactions:
 Directing effect: ortho-, meta- and para- directors in electrophilic
aromatic substitution (EAS)

 Depending on the group (X) that is initially present on the benzene

ring, the second substituent goes either to ortho/para or the meta
position
 Activating group directs the electrophile to the ortho and para-positions
 Deactivating group directs the electrophile to the meta-position
 To explain this regioselectivity, we need to draw the complete
electrophilic substitution mechanism
 The aromatic ring is activated by the resonance effect.
 The para product is more favorable because of the steric strain
between the closer located ortho substituents; and the larger the
groups, the higher the strain, therefore the higher the regioselectivity
 Deactivating groups slow down electrophilic aromatic substitutions
and direct the substituents to the meta-position
 The only exceptions are the halogens that deactivate the aromatic
ring yet directing the electrophile to the ortho and para positions
 They are still electron-donators by resonance which does stabilize
the transition state by an additional resonance
 Meta Directors
Exercise 5. Show how each compound can be synthesized from
benzene and any other organic or inorganic reagents
 Arenediazonium salts in EAS
 Aryl diazonium salts can be used as an alternative to the standard
electrophilic aromatic substitution reactions for preparing aromatic
compound as well as for synthesizing compounds that cannot be
prepared directly from benzene
Q: What are aryl diazonium salts?
 Arenediazonium salts are very important and useful intermediates in
synthesis of aromatic compounds since they contain one of the best
leaving groups, N2 which can be replaced by a variety of other atoms or
functional groups
 Electrophilic aromatic substitution with two directing groups:
which group “Wins” ?

E.g.
 The -OCH3 is an ortho-,para- director, but since the para- position is already
substituted (with NO2), only the ortho- positions are available.
 The -NO2 is a meta- director, and the positions meta- to the NO2 happen to also
be the positions ortho- to the OCH3. As it turns out, both substituents direct to the
same position (C–2). This gives us the product 2-chloro-1-methoxy-4-
nitrobenzene, which indeed is the major product
 When two or more substituents are present on an aromatic ring, the
directing group will be the most activating substituent
 When attack at two or more electronically equivalent sites is
possible, the electrophile will favor the position flanked by the
fewest number of substituents