HPFP 1217 ORGANIC CHEMISTRY II

MODULE 2: AROMATIC COMPOUNDS

Mr. Libbohole Adwell

Texila American University,
Zambia
MODULE 2: AROMATIC COMPOUNDS
LEARNING OBJECTIVES

At the end of the Module, students will be able to:

• Understand what characteristics make this class of organic compounds
so unique?
• Learn the preparations of aromatic compounds.

• Understand the stability and Physical properties of aromatic compounds.

• Learn the nomenclature of Aromatic compounds.

• Understand concept of aromaticity and anti-aromaticity.

• Naming the di-substituted aromatic compounds and orientation effects.

2.0 INTRODUCTION
Chemists and scientist started naming certain carbon-compounds having a
distinct odour as an aromatic hydrocarbon. One of the major reasons for
such a nomenclature method was because the compounds such as benzene
and toluene were able to emit a sweet smell. This made the scientists name
the compounds as aromatic hydrocarbons (the Greek word for
pleasant smelling compounds).

Therefore, aromatic hydrocarbon consists primarily of carbon and hydrogen.

They are stable and unsaturated cyclic organic compounds.
Aromatic hydrocarbons or arenes have a special smell to the compound,
hence the name aromatic compounds. Mostly the compounds will contain as
well as retain one or more benzene ring, even after undergoing different
reactions.

However, there is another class of aromatic hydrocarbon which do not

contain benzene ring but they have a highly unsaturated ring. Aromatic
compounds with benzene ring refer to as benzenoids and the compounds
which do not contain benzene ring refer to as non-benzenoids.
Definition of Aromatic Hydrocarbons
Aromatic Hydrocarbons are compounds having sigma bonds as well as
delocalized pi electrons in between the carbon atoms present in the ring
form. Refer to see the different examples of aromatic compounds containing
a benzene ring. A hydrocarbon can be an aromatic compound if it follows
the Huckel Rule. According to this rule, a compound can be aromatic if it
contains the following distinct properties:

• Planarity
• Cyclic
• Delocalization of the pi-electrons in the carbon ring entirely
• A compound having (4n + 2) π electrons in its structure, where n is an
integer.
2.1 Preparation of Aromatic Hydrocarbons
One of the important commercial preparation methods of benzene is by
isolation of coal tar. However, the laboratory techniques for preparation of
aromatic hydrocarbons are different.
1. Cyclic Polymerization of Alkynes:
Alkynes undergo polymerization reaction similar to alkenes. It can undergo
two types of polymerization reaction- linear and cyclic. However, only cyclic
polymerization can yield ethyne.
Cyclic polymerization of ethyne results in the formation of aromatic
hydrocarbons. It is one of the important chemical reactions in alkynes.
Ethyne undergoes reaction by passing it from the red-hot iron tube at a very
high temperature of 873K to form benzene. This reaction is cyclic
polymerization of ethyne. Refer to the example below
 Cont...
2. Aromatic Hydrocarbons by Decarboxylation of Aromatic Acids
The sodium salt of benzoic acid and soda lime react under heating
conditions to produce benzene.

3. Aromatic Hydrocarbon by Reduction of Phenol

Phenol vapours undergo reduction reaction by passing extremely heated
zinc dust. This reaction results in the formation of benzene.
 2.2 Properties of Aromatic Compounds
• Benzene was first isolated in 1825 by Michael Faraday, who
deduced that its empirical formula was CH.

• In 1834, the German chemist Eilhard Mitscherlich determined that

benzene’s Mr was 78, and its formula was C6H6. However, it was not
until 1931 that benzene’s structure was fully resolved.

• Benzene’s molecular formula suggests it is a highly unsaturated

compound. But unlike alkenes, it does not readily undergo addition
reactions. This suggests that i ts structure and bonding i
s fundamentally different.
STRUCTURAL PROPERTIES OF BENZENE
Background
• Benzene (C6H6) is the simplest aromatic hydrocarbon (or arene).
• Benzene has four degrees of unsaturation, making it a highly unsaturated
hydrocarbon.
• Whereas unsaturated hydrocarbons such as alkenes, alkynes and dienes
readily undergo addition reactions, benzene does not.
 Cont...

• Benzene does react with bromine, but only in the presence of FeBr3 (a
Lewis acid), and the reaction is a substitution, not an addition.

• Proposed structures of benzene must account for its high degree of

unsaturation and its lack of reactivity towards electrophilic addition.
• August Kekulé proposed that benzene was a rapidly equilibrating mixture
of two compounds, each containing a six-membered ring with three
alternating  bonds.
• In the Kekulé description, the bond between any two carbon atoms is
sometimes a single bond and sometimes a double bond.
 Cont...
• These structures are known as Kekulé structures.

• Although benzene is still drawn as a six-membered ring with alternating 

bonds, in reality there is no equilibrium between the two different kinds of
benzene molecules.
• Current descriptions of benzene are based on resonance and electron
delocalization due to orbital overlap.
• In the nineteenth century, many other compounds having properties
similar to those of benzene were isolated from natural sources. Since these
compounds possessed strong and characteristic odors, they were called
aromatic compounds. It should be noted however, that it is their chemical
properties, and not their odor, that make them special.
 Cont...

The Structure of Benzene

Any structure for benzene must account for the following facts:
1. It contains a six-membered ring and three additional degrees of
unsaturation.
2. It is planar.
3. All C—C bond lengths are equal.

The Kekulé structures satisfy the first two criteria but not the third, because
having three alternating  bonds means that benzene should have three
short double bonds alternating with three longer single bonds.
 Cont...
The Structure of Benzene
• The resonance description of benzene consists of two equivalent Lewis
structures, each with three double bonds that alternate with three single
bonds.
• The true structure of benzene is a resonance hybrid of the two Lewis
structures, with the dashed lines of the hybrid indicating the position of
the  bonds.
• We will use one of the two Lewis structures and not the hybrid in drawing
benzene. This will make it easier to keep track of the electron pairs in the
 bonds (the  electrons).
 Cont...

The Structure of Benzene

• Because each  bond has two electrons, benzene has six  electrons.
 Cont...

The Structure of Benzene

• In benzene, the actual bond length (1.39 Å) is intermediate between the

carbon—carbon single bond (1.53 Å) and the carbon—carbon double bond
(1.34 Å).
Resonance Structure Cont...

Each sp2 hybridized C in the ring has an unhybridized p orbital

perpendicular to the ring which overlaps around the ring.
Reaction properties
Unusual Reactions
• A l k e n e + K M 4  d i o l ( a d d i t i o n )
Benzene
n O + KMnO4  no reaction.

• Alkene Br2/CCl4  dibromide (additio

Benzene
+ ) 4  no reaction.
+ Br2n/CCl

• With Fe Cl 3 catalyst, Br 2 reacts with benzene to form

b r o m o b e n z e n e + H B r
(substitution!). Double bonds remain.

16
Unusual Stability Cont...

Hydrogenation of j u s to n e double bond i

n b e n z e n e i s endothermic!

17
Electronic Properties

• The Six Electrons in the pi

Bonds are L o o se l y Held
Compared to the
Electrons in the sigma
Bonds
• Those Six E l e c t ro n s are
Delocalized
• This causes a cloud of
electrons above a
n d below the plane of
the benzene molecule.
2.3 Physical Properties of Aromatic Compounds

• Aromatic compounds are less dense than water, although they are
usually more dense than other hydrocarbons.
• Halogenated benzene compounds are denser than water.

• Aromatic hydrocarbons are insoluble in water and are used as

solvents for other organic compounds.
• Only aromatic compounds containing strongly polar functional
groups such as — OH or — COOH will be somewhat soluble in water.
• Benzene and other aromatic compounds are resistant to reactions
that break up the aromatic system, although they are flammable.
Isomerism of Aromatic Hydrocarbons
If we consider any “disubstituted benzene”, there is a possibility of the
formation of three different position isomers on the basis of substituent’s
position in relation to the other. Thus, we use ortho-position to indicate the
position of two substituents (1,2-).
Similarly, meta-position will represent the relative position (1,3-) and para-
position will represent the relative position (1,4-). Let’s take the example
of xylene. Refer to the diagram below to observe the different isomers
of xylene (dimethylbenzene) depending on the position.
2.4 Nomenclature of Aromatic Hydrocarbons
IUPAC System
Rule 1: As per IUPAC nomenclature system, it is important to place the
substituent’s name before the name of the compound as a prefix in any
substituted aromatic hydrocarbon. For example, nitrobenzene where the
benzene ring is present along with a nitro group.

Rule 2: You have to attach Greek numerical prefixes such as di, tri, and
tetra to indicate similar substituents group in case of compounds with more
than one substituent group present in the benzene ring. For instance, a
benzene ring with two bromo groups present on the adjacent carbon atoms
of the benzene ring refers to as 1,2-di-bromobenzene.
Click To Edit Master Title Style Cont...

Rule 3: If different substituent groups are present in the aromatic

compounds, it is important to assign number one position to the substituent
of the base. Furthermore, the numbering direction for the rest of the
compound is chosen in such a manner that the next substituent will have
the lowest numbering position. Moreover, we have to use alphabetical order
for the naming of the substituent. For example, if a benzene consists of
chloro group as well as a nitro group, then we start with the chloro group
and then the nitro groups on the basis of the alphabetical order.
Click To Edit Master Title Style Cont...
Rule 4: In case of aromatic compounds with more than one substituents, it is
necessary to use terms such as ortho, meta, and para as prefixes to represent
the relative positions like 1,2-; 1,3-; 1,4-. For instance, we can rewrite 1,2 di-
bromo-benzene as o-di-bromo-benzene.
Rule 5: If an organic compound consists of an alkane with a functional group
and aromatic compound, then the aromatic compound will act as a
substituent instead of the parent group. For instance, when there is a benzene
ring joined with an alkane and a functional group, then the aromatic group is
known as phenyl (Ph-).

Diagrams representing Nomenclature of Aromatic Hydrocarbons

 Cont...

Monosubstituted benzenes

Monosubstituted benzenes, like hydrocarbons, are systematically named

with –benzene as the parent name
Cont...
 Cont...

• “Phenyl” refers to C6H5

– It is used when a benzene ring is a substituent

– “Ph” or “f” can also be in place of “C6H5”

• “Benzyl” refers to “C6H5CH2”

Cont...
Cont...
 Cont...

When two substituents are present their position may be indicated by

the prefixes ortho, meta, and para (o, m and p) or by the corresponding
numerical positions.

 If the two groups on the benzene ring are different, alphabetize the
names of the substituents preceding the word benzene.
 If one substituent is part of a common root, name the molecule as
a derivative of that monosubstituted benzene.
 Cont...

Multisubstituted benzenes

 For three or more substituents on a benzene ring:

 Number to give the lowest possible numbers around the ring.

 Alphabetize the substituent names.

 When substituents are part of common roots, name the molecule

as a derivative of that monosubstituted benzene. The
substituent that comprises the common root is located at C1.

30
 Cont...

• Multisubstituted benzenes (more than two substituents) are named as

follows:
– Choose the sequence when the substituents have the lowest possible
number
– List substituents alphabetically with hyphenated numbers

– Use common names, such as “toluene”, as parent name (as in TNT)

 Practice Problem

Practice Problem: Tell whether the following compounds are ortho-, meta-,
or para-disubstituted

(a) Meta (b) Par (c) Ortho

 Cont...

(a) m-Bromochlorobenzene (b) (3-Methylbutyl)benzene

(c) p-Bromoaniline (d) 2,5-Dichlorotoluene
(e) 1-Ethyl-2,4-dinitrobenzene (f) 1,2,3,5-Tetramethylbenzene

a) p-Bromochlorobenzene
b) p-Bromotoluene
c) m-Chloroaniline
d) 1-Chloro-3,5-dimethylbenzene
 Cont...

m-fluoronitrobenzene

o-bromochlorobenzene

34
Cont...

35
Polynuclear Aromatic Hydrocarbons:

36
 2.5 AROMATICITY AND ANTIAROMATICITY
The Criteria for Aromaticity

Four structural criteria must be satisfied for a compound to be aromatic.

[1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with p orbitals on adjacent

atoms.
 Cont.....

[2] A molecule must be planar.

All adjacent p orbitals must be aligned so that the  electron density can be
delocalized.

Since cyclooctatetraene is non-planar, it is not aromatic, and it undergoes

addition reactions just like those of other alkenes.
 Cont.....

[3] A molecule must be completely conjugated.

Aromatic compounds must have a p orbital on every atom.

 Cont.....
[4] A molecule must satisfy Hückel’s rule, and contain a
particular number of  electrons.

Hückel's rule:

Benzene is aromatic and especially stable because it contains 6  electrons.

Cyclobutadiene is antiaromatic and especially unstable because it
contains 4  electrons.
 Cont.....

The Criteria for Aromaticity—Hückel’s Rule

Note that Hückel’s rule refers to the number of  electrons, not the number
of atoms in a particular ring.
 Cont.....

Considering aromaticity, a compound can be classified in one of three ways:

1. Aromatic—A cyclic, planar, completely conjugated compound with

4n + 2 electrons.
2. Antiaromatic—A cyclic, planar, completely conjugated compound
with 4n electrons.
3. Not aromatic (nonaromatic)—A compound that lacks one (or
more) of the following requirements for aromaticity: being cyclic,
planar, and completely conjugated.
 Cont.....

Note the relationship between each compound type and a similar open-
chained molecule having the same number of  electrons.
AROMATICITY OF BENZENOID COMPOUNDS
• Completely conjugated rings larger than benzene are also aromatic if
they are planar and have 4n + 2  electrons.
• Hydrocarbons containing a single ring with alternating double and single
bonds are called annulenes.
• To name an annulene, indicate the number of atoms in the ring in
brackets and add the word annulene.
 Cont.....

• [10]-Annulene has 10  electrons, which satisfies Hückel's rule, but a

planar molecule would place the two H atoms inside the ring too close to
each other. Thus, the ring puckers to relieve this strain.

• Since [10]-annulene is not planar, the 10  electrons can’t delocalize over

the entire ring and it is not aromatic.
 Cont.....
• Two or more six-membered rings with alternating double and single
bonds can be fused together to form polycyclic aromatic hydrocarbons
(PAHs).
• There are two different ways to join three rings together, forming
anthracene and phenanthrene.

• As the number of fused rings increases, the number of resonance

structures increases. Naphthalene is a hybrid of three resonance
structures whereas benzene is a hybrid of two.
 Cont.....

• Why does the number of  electrons determine whether a compound is

aromatic?
• The basis of aromaticity can be better understood by considering orbitals
and bonding.
 Cont.....
Frost Circles: relative energies of the molecular orbitals of cyclic, conjugated
systems

Inscribe the cyclic, conjugated molecule into a circle so that a vertex is at the
bottom. The relative energies of the MO’s are where the ring atoms intersect
the circle benzene:

The bonding MO's will be filled for aromatic compounds, such as benzene.

48
 Cont.....
Cyclobutadiene:

Foranti-aromaticcompounds,suchascyclobutadien
e a n d cyclooctatetraene, there will be unpaired electrons in
bonding, non- bonding or antibonding MO's.
Cyclooctatetraene:

49
 AROMATICITY OF CHARGED IONS
Both negatively and positively charged ions can be aromatic if they possess
all the necessary elements.
 Cont.....

pi-electrons sp2 hybridized carbons

p atomic orbitals

2 pi-electrons

. :

0 pi-electrons 1 pi-electron 2 pi-electrons

 Cont.....

• Having the “right” number of electrons is necessary for a species to be

unusually stable by virtue of aromaticity.
• Thus, although five resonance structures can also be drawn for the
cyclopentadienyl cation and radical, only the cyclopentadienyl anion has
6
 electrons, a number that satisfies Hückel’s rule.
 Cont.....
Cyclopropenyl cation
4n+2=2
n=0
aromatic

Cyclopentadienyl cation

4n=4
n=1
anti-aromatic

Cycloheptatrienyl cation
Y6 Y7
H H
Y4 Y5
H H 4n+2=6
Y2 Y3 n=1
H H
H
1 aromatic
cycloheptatrienyl cation
6 p-electrons

53
 Cont.....

Cyclopropenyl anion

4n=4
n=1
anti-aromatic

Cyclopentadienyl anion

4n+2=6
n=1
aromatic

54
AROMATICITY OF AROMATIC
HETEROCYCLIC COMPOUNDS
Heterocyclic Aromatic Compounds (please read) Heterocycle: any cyclic
compound that contains ring atom(s) other than carbon (N, O, S, P). Cyclic
compounds that contain only carbon are called carbocycles.
N
N N
N
N N O S O
H S H
pyridine imidazole furan thiazole oxazole
pyrr
Heterocyclic Aromatic
ole thiophene and Hückel's Rule Pyridine: -electron
Compounds
structure resembles benzene (6 -electrons) The nitrogen lone pair electrons
are not part of the aromatic system.

pyridine

55
 Cont.....

• Heterocycles containing oxygen, nitrogen or sulfur, can also be aromatic.

• With heteroatoms, we must determine whether the lone pair is localized
on the heteroatom or part of the delocalized  system.
• An example of an aromatic heterocycle is pyridine.
 Cont.....
• Pyrrole is another example of an aromatic heterocycle. It contains a five-
membered ring with two  bonds and one nitrogen atom.
• Pyrrole has a p orbital on every adjacent atom, so it is completely
conjugated.
• Pyrrole has six  electrons—four from the  bonds and two from the lone
pair.

• Pyrrole is cyclic, planar, completely conjugated, and has 4n + 2 

electrons, so it is aromatic.
2.6 Disubstituted Benzenes: Orientation

Product ratio conclusion:

40% ortho, 40% meta,
20% para

58
 Cont.....

• Monosubstituted benzenes undergo electrophilic aromatic

substitution.
• Substituents influence reactivity.

• Substituents determine position of second electrophilic substitution.

• Substituents that increase electron density increase reactivity.

• Substituents that decrease electron density decrease reactivity.

 Substituent Effects
D W

   

 

CH3 O O
O N

Both types of substituents, electron Donating and electron Withdrawing, act

on the same positions, namely ortho and para, however, in opposite
directions.
 Cont.....

• A group which makes the ring more reactive than that of

benzene is called an activating group.

• A group which makes the ring less reactive than benzene is

called a deactivating group.

• A group which leads to the predominant formation of ortho

and para isomers is called an “ortho - para directing
group.”
• A group which leads to the predominant formation of the meta
isomer is called a “meta directing group.”
Electron-donating Substituents
H3 C
O CH3 H3C O O

O CH3 O CH3

Resonance contributors increase electron density in ortho and para

positions. Overall electron density is bigger.
GENERAL REACTIONS
Activating-Deactivating (Resonance)

 Any resonance effect, such as that of -NH 2 , -OH, and -OR,

that delocalizes the positive charge on the cation has an activating
effect toward further EAS.
 Any resonance effect, such as that of -NO2, -CN, -C=O, and -SO3H, that
decreases electron density on the ring deactivates the ring toward
further EAS.
Activating-Deactivating (Inductive Effects)

 Any inductive effect, such as that of -CH 3 or other alkyl group, that
releases electron density toward the ring activates the ring toward
further EAS.

 Any inductive effect, such as that of halogen, -NR3+, -CCl3, or -CF3,

that decreases electron density on the ring deactivates the ring toward
further EAS.
Activating-Deactivating (halogens)
• For the halogens, the inductive and resonance effects run counter to
each other, but the former is somewhat stronger.
• The net effect is that halogens are deactivating but ortho-para
directing.

H + H
: :
: :

+ + :C + :Cl
:Cl E
E E

:
l
CLASSIFICATION OF SUBSTITUENTS

Chapter 15 67
Examples:

68
Examples:

69
Reference textbooks

1. Brown, William H., Introduction to Organic Chemistry, 1st

edition, Saunders College Publishing.
2. 2. Carey, Francis A., Organic Chemistry, 5th edition, 2003,
McGraw Hill, NewYork, USA.
3. 3. Vogel’s Textbook of Practical Organic Chemistry 5 th
edition
SAMPLE QUESTIONS (MCQs)
1. With respect to the electrophilic aromatic substitution of benzene which of the following is
not true?

a) A non-aromatic intermediate is formed

b) Benzene acts as an electrophile

c) A proton is lost in the final step

d) Resonance forms are important

2. Which of the following statements is incorrect: aromatic compounds...

a) Are planar

b) Have 4n π-electrons

c) Are cyclic

d) Are generally less reactive than similarly substituted alkenes

SAMPLE QUESTIONS (MCQs)

3. When considering electrophilic aromatic substitution reactions electron withdrawing

substituents (e.g. nitro) are described as...
a) Ortho/para directing and activating
b) Ortho/para directing and deactivating
c) Meta directing and activating
d) Meta directing and deactivating

4. The Friedel-Crafts alkylation...

a) Works very well for primary chlorides
b) Works very well for tertiary chlorides
c) Works very well for acyl chlorides
d) Works very well without a catalyst

5.When considering electrophilic aromatic substitution reactions the halides are described as...
a) Ortho/para directing and activating
b) Ortho/para directing and deactivating
c) Meta directing and activating
d) Meta directing and deactivating