CHM 203

Basic Organic Chemistry

– Benzene & Aromaticity –

Dr. A. A. Abayomi & Dr. A. Asekunowo
 CHM 213

BENZENE AND
AROMATICITY
➢ Introduction
➢ Aromaticity
➢ Nomenclature
➢ Sources
➢ Reactions of Benzene
➢ Substituent Group Effects
➢ Addition Reaction
 CHM 213

Introduction

▪ Benzene is the simplest member of a group

of cyclic compounds known as aromatic
hydrocarbons
▪ The word “aromatic” is derived from the
Greek word “aroma” meaning "pleasant smell“
▪ Not all pleasant-smelling compounds are
aromatic
Benzene & Aromaticity

Introduction

▪ The molecular formula of benzene is C6H6

▪ A comparison of this formula with that of
corresponding six-membered alkane, alkene
and alkyne suggests that benzene is an
unsaturated compound
▪ Benzene does not undergo the usual addition
reactions which other unsaturated
hydrocarbons – alkenes and alkynes readily do
Benzene & Aromaticity

Introduction

▪ Benzene does not decolourize KMnO4

▪ It does not react with halogens except in the
presence of a catalyst
▪ Benzene undergoes substitution reactions
but not addition reactions
▪ Benzene does not have any isomers
▪ All the carbon atoms are equivalent
▪ Benzene has a special, unusual type of
unsaturation – different to alkenes
Benzene & Aromaticity

Introduction

▪ August Kekule proposed the cyclic structure

of benzene
▪ The benzene structure could be referred to as
a cyclic triene – cyclohexatriene
▪ Benzene is a resonance hybrid of the two
canonical (Kekule's) structures
Benzene & Aromaticity

Introduction

▪ The non-existence of real double bonds in

benzene explains why the compound fails to
undergo the usual addition reactions expected
for an unsaturated hydrocarbon
▪ The alternating single and double bonds
explain the equivalence of all the six carbon
and hydrogen atoms, and the existence of only
one 1,2-disubstituted isomer
Benzene & Aromaticity

Introduction

▪ The carbon–carbon bond lengths in the

Kekule structures are equal and between that
of a pure single and double bond
▪ The resonance hybrid structure is more
stable than any of the contributing limiting
(canonical) structures
Benzene & Aromaticity

Introduction

▪ The stability of benzene and the non-

existence of real double bonds in the benzene
molecule explains its tendency to undergo
substitution reactions rather than addition
reactions
▪ Benzene resists any reaction that would
destroy its aromatic nature
Benzene & Aromaticity

Introduction

▪ Benzene has peculiar characteristics – these

characteristics are termed aromatic behaviour
and this means:
(i) Resistance to oxidation
(ii) Resistance to addition reactions and ease
of substitution reactions
(iii) Unusual stability as evidenced by its low
heat of hydrogenation/combustion
Benzene & Aromaticity

Introduction

▪ Let us take a very brief look at the modern

molecular orbital picture of benzene
(i) The carbon and hydrogen atoms are planar
(i.e., they all lie on the same plane)
(ii) The bonds are sp2-hybridized orbitals
Benzene & Aromaticity

Introduction

▪ In sp2-hybridized orbitals
- Each bond angle is close to 120o
- The carbon atoms are arranged in the form of
a regular hexagon
- Each carbon atom has 3 sp2 hybrid orbitals
and forms 2 sigma bonds (sp2–sp2) with 2
other carbon atoms on either side and 1 sigma
bond (sp2–s) by overlapping with the 1s
orbital of hydrogen
Benzene & Aromaticity

Introduction

▪ At each sp2 hybridized carbon there is an

unhybridized p orbital lying perpendicular to
the plane of the three hybrid orbitals
Benzene & Aromaticity

Introduction

▪ These p orbitals overlap laterally with each

other (on either side) to form two Kekule
structures
Benzene & Aromaticity

Introduction

▪ All the p orbitals overlap to produce a

continuously overlapping array of p orbitals
▪ π-electron clouds are formed above and
below the plane of the six-carbon-atom
hexagon

▪ This is called the delocalization of π-electrons

Benzene & Aromaticity

Aromaticity

▪ Aromatic compounds are cyclic

▪ They are flat (or nearly flat) molecules
▪ To be an aromatic compound, the molecule
must have a cloud of delocalized π-electrons
above and below its plane
▪ The compound must contain a total of
(4n + 2) π-electrons where n = no. of rings
– the Huckel rule
Benzene & Aromaticity

Aromaticity

▪ In other words, delocalization alone is not

enough for aromaticity
▪ The requirements of the Huckel’s rule must
be fulfilled
▪ The compound must contain a total of
(4n + 2) π-electrons where n is number of
rings in a molecule
Benzene & Aromaticity

Aromaticity

▪ Benzene has 6 π-electrons

(n = 1)

▪ Napthalene has 10 π-electrons

(n = 2)

▪ Anthracene has 14 π-electrons

(n = 3)
Benzene & Aromaticity

Aromatic or NOT Aromatic?

I II

III

IV V
Benzene & Aromaticity

Aromaticity

▪ Properties that all aromatic compounds have

in common include:
(a) Resistance to oxidation (e.g., with KMnO4)
(b) Substitution reactions rather than addition
reactions
(c) Thermal stability – heat of hydrogenation
and combustion usually less than expected
(d) Obedience of the Huckel’s 4n+2 rule
Benzene & Aromaticity

Nomenclature of Benzene Derivatives

▪ A derivative of benzene is a molecule in

which one or more of the hydrogen atoms
have been replaced by a group or atom
▪ Monosubstituted derivative (e.g., C6H5Br –
Bromobenzene): when only one hydrogen
atom has been replaced
▪ Phenyl (C6H5): when one of the hydrogen
atoms is removed from benzene (C6H6)
Benzene & Aromaticity

Nomenclature of Benzene Derivatives

▪ A disubstituted derivative is obtained by

replacing two hydrogen atoms (e.g., C6H4AB)
▪ There are three possible isomers of a
disubstituted benzene
A A A

B
1,2-disubstituted derivative 1,3-disubstituted derivative 1,4-disubstituted derivative
ortho- meta- p ara-
Benzene & Aromaticity

Nomenclature of Benzene Derivatives

▪ Trisubstituted derivatives are obtained by

replacing three hydrogen atoms (e.g., C6H3XYZ)
▪ There are also three possible isomers of a
trisubstituted benzene
X A X

Y Y

Z Z Y

Z
1,2,3-trisubstituted 1,3,5-trisubstituted 1,2,4-trisubstituted
derivative derivative derivative
Benzene & Aromaticity

Nomenclature of Benzene Derivatives

▪ In naming benzene derivatives, the positions

substituted are indicated by numbering the
carbon atoms in the ring, in such a manner as to
obtain the lowest possible combination of
numbers NO 2 NO2 NO 2

O2N NO2

NO2

NO 2 NO2 NO 2

1,4,6-trinitrobenzene 1,2,4-trinitrobenzene 1,3,4-trinitrobenzene

Benzene & Aromaticity

Nomenclature of Benzene Derivatives

▪ Substituted phenyl groups (e.g., C6H5, C6H4X,

C6H3XY, C6H2XYZ) are also called aryl groups
▪ The atoms or groups which may replace
hydrogen atoms in the benzene molecule are
varied and each gives rise to different
functionalities in the benzene family
Benzene & Aromaticity

Functionalities in the Benzene Family

Benzene & Aromaticity

Sources of Benzene and other Aromatics

▪ Coal and Petroleum are the two major

sources of aromatic hydrocarbons
▪ Carbonization of coal (also referred to as
destructive distillation of coal) yields
a mixture of gases and coal tar as the residue
▪ Distillation of coal tar yields major fractions
consisting of aromatic compounds – phenols,
hydrocarbons, anthracene, phenanthrene, etc.
Benzene & Aromaticity CHM 203

Sources of Benzene and other Aromatics

▪ Petroleum is also an important source

of benzene and aromatic hydrocarbons
▪ Catalytic reforming is applied to
the aliphatic and alicyclic hydrocarbons –
mainly hexanes and cyclohexanes to increase
the yield of benzene obtainable from petroleum
▪ It is not usual to prepare benzene in the
laboratory – it is available in sufficient
quantities from the petroleum industry
Benzene & Aromaticity CHM 203

Physical Properties

▪ Benzene is a colourless liquid; it boils at 80 oC

and melts at 5.5 oC
▪ It has a characteristic aromatic odour
▪ It does not mix with water and has a lower
density than water
▪ Benzene is an important solvent in the
laboratory and chemical industry
▪ It burns with a smoky flame – due to its
highly unsaturated nature
Benzene & Aromaticity

Physical Properties

▪ Unsaturation is often detected in the

laboratory by the “flame test”
▪ Any compound that burns with a sooty
flame is likely to be unsaturated
Benzene & Aromaticity

Reactions of Benzene

▪ In benzene, the hexagonal arrangement of

the six carbon atoms is sandwiched between
an upper and lower cloud of π electrons
▪ The benzene molecule is a very rich source
of electrons, and it is attacked by electron-
deficient reagents or species
▪ The most common type of reactions
undergone by benzene is electrophilic in
nature
Benzene & Aromaticity

Reactions of Benzene

▪ Benzene undergoes electrophilic substitution

rather than electrophilic addition
▪ Benzene has a special kind of stability due to
resonance energy
▪ Addition reactions would destroy the
aromatic sextet of electrons of benzene, and
the molecule formed would be less stable than
the (resonance-stabilized) benzene molecule
Benzene & Aromaticity

Reactions of Benzene

▪ Due to its stability, benzene requires more

forcing conditions, such as heat or use of
catalyst, to react with reagents like halogens
▪ Under severe conditions, benzene can be
hydrogenated
Benzene & Aromaticity

Reactions of Benzene

▪ Benzene does not react with bromine (in

CCl4), hydrogen halides and hot or cold KMnO4
– alkenes and alkynes readily do
Benzene & Aromaticity

Reactions of Benzene

▪ Electrophilic Aromatic Substitution

(General Mechanism)
▪ Nitration of Benzene
▪ Sulphonation of Benzene
▪ Halogenation of Benzene
▪ Friedel–Crafts Alkylation of Benzene
▪ Friedel–Crafts Acylation
Benzene & Aromaticity

General Mechanism of
Electrophilic Aromatic Substitution

▪ Electrophilic aromatic substitution occurs in

two steps:
Step 1:

Attack of the electrophilic reagent E+ on the π

electrons of the benzene ring
Benzene & Aromaticity

General Mechanism of Electrophilic Aromatic

Substitution

▪ Benzonium ion
(Resonance-stabilised
Intermediate)

Structures I, II & III

are canonical forms
IV is the resonance hybrid
Benzene & Aromaticity

General Mechanism of
Electrophilic Aromatic Substitution

▪ Step 2: Re-aromatisation

A proton H+ is lost from the intermediate ion

and accepted by a nucleophile
Benzene & Aromaticity

Nitration of Benzene

▪ Step 1:

▪ Step 2:

▪ Step 3:
Benzene & Aromaticity

Sulphonation of Benzene

▪ The sulphonation reaction is reversible

▪ lt is favoured in strong acids whereas
desulphonation is favoured in dilute acids
▪ The reactive electrophile is either HSO3+ or
SO3
Benzene & Aromaticity

Halogenation of Benzene

▪ Halogenation is the introduction of a halogen

▪ The reagents for bromination are bromine and
iron (III) bromide
▪ The reactive electrophile is Br+
Benzene & Aromaticity

Friedel–Crafts Alkylation of Benzene

▪ Alkylation is the introduction of the alkyl

group R into a benzene nucleus
▪ The reagents are an alkyl chloride and
aluminium chloride (Lewis acid catalyst)
▪ The reactive electrophile is a carbonium ion R+
Benzene & Aromaticity

Friedel–Crafts Alkylation – Limitations

- Aryl halides and vinylic halides cannot be used

as the halide component because they do not
form carbocations readily
- Gives poor yields when powerful electron-
withdrawing groups are present on the
aromatic ring e.g., NO2 and NH2
Benzene & Aromaticity

Friedel–Crafts Alkylation – Limitations

- Skeletal rearrangements of the alkyl groups

particularly when 1o alkyl halides are used e.g.,

- Polyalkylation often occurs in Friedel-Crafts

alkylation since the product (alkylbenzene) is
more reactive than the starting material
Benzene & Aromaticity

Friedel–Crafts Acylation of Benzene

▪ Acylation is the introduction of the acyl group

–COR into a benzene nucleus
▪ The reagents are an acyl chloride and
aluminium chloride (Lewis acid catalyst)
▪ The reactive electrophile is an acylium ion R+
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

▪ Methylbenzene (toluene) reacts faster than

benzene because the methyl group is slightly
electron-donating and has the effect of
activating the ring
▪ Subsequent substituents are directed to the
ortho and para positions
▪ Toluene undergoes nitration ca. 20 x faster
than benzene under comparable conditions
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

▪ Using a mixture of concentrated nitric and

sulphuric acid at 20 oC, nitration gives a mixture
of the ortho- and para- substituted products
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

▪ Conversely, nitrobenzene reacts slower than

benzene because the nitro group (an electron-
withdrawing group) deactivates the ring and is
meta-directing
▪ The functional groups already attached to the
ring are the activating and deactivating groups
▪ Electron-donating groups are activating while
electron-withdrawing groups are deactivating
to electrophilic reagents
 Benzene & Aromaticity

Effects of Substituent Groups on Benzene

▪ Activating (ortho-/para- directing)

(a) Strongly activating: NH2, NHR, NR2, OH
(b) Moderately activating: OCH3, OC2H5, NHCOCH3
(c) Weakly activating: CH3, C2H5, C6H5

▪ Deactivating (meta- directing)

NO2, +N(CH3)3, CN, COOH, COOR, SO3H, CHO, COR

▪ Deactivating (ortho-/para- directing)

F, Cl, Br, I
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

▪ Relies on the balance of inductive and

resonance effects
(a)The group attached increases or decreases
the electron density of the ring

increase
decrease
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

(b) The group attached interacts with the

electronic structure of the ring in such a way
that the ortho and para positions acquire a
partial negative or positive charge

This can be understood most easily in terms

of the resonance theory
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

- Groups in which the atom attached to the ring

carries one or more lone pairs of electrons act
as electron donors (e.g., aniline)

- The resonance hybrid structure carries a small

negative charge at the ortho/para positions thereby
promoting electrophilic attack at these sites
 Benzene & Aromaticity

Effects of Substituent Groups on Benzene

- Groups with a double bond between the atom joined

to the ring and another atom can show a similar but
opposite effect (e.g., nitrobenzene)

- The resonance hybrid structure carries a small positive

charge at the ortho/para positions thereby inhibiting
electrophilic attack at these sites but it occurs slowly at
the meta position
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

- The halogens (electron-withdrawing group but

with three pairs of lone electrons) are ortho-
and para- directing

- Halogens have a strong

electron-withdrawing
inductive effect but a
weak electron-donating
resonance effect
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

- Hydroxyl and amino groups have weak

electron-withdrawing inductive effects but
strong electron-donating resonance effect and
are therefore activators
- In general, any substituent that has a lone
pair of electrons on the atom attached to the
aromatic ring has an electron-donating
resonance effect and is ortho-/para- directing
- Halogens, hydroxyl and amino groups are
therefore ortho-/para- directors
Benzene & Aromaticity

Effects of Substituent Groups on Benzene

Benzene & Aromaticity

Addition Reactions of Benzene

▪ Addition of Hydrogen
▪ Addition of Halogens
▪ Reaction with Ozone
Benzene & Aromaticity

Addition of Hydrogen

▪ Benzene can be converted into the saturated

compound cyclohexane by passing hydrogen
gas over a platinum catalyst at 200 oC and 10
atm.
Benzene & Aromaticity

Addition of Halogens

▪ Addition reactions occur when halogens react

with benzene in the presence of UV light
▪ The reaction takes place by a free radical
mechanism and the product is a saturated
halogenocyclohexane
Benzene & Aromaticity

Reaction with Ozone

▪ Like the alkenes, benzene reacts with ozone to

give an unstable ozonide, which on hydrolysis
gives ethanedial (glyoxal)