UNIT – I BENZENE AND ITS DERIVATIVES

Aromaticity and Electrophilic Aromatic Substitution: Benzene, aromaticity, and other aromatic systems, Nomenclature of benzene
derivatives, Other aromatic systems Electron donating and withdrawing groups, Inductive vs. resonance effects; effects of sub stituents,
General mechanism of electrophilic aromatic substitution, Halogenation, Nitration, Sulfonation, Friedel-Crafts Alkylation and Acylation,
Directing and activating effects in electrophilic aromatic substitution, Use of electrophilic aromatic substitution in synthesis, Nucleophilic
substitution of aryl halides (benzyne and addition-elimination mechanisms).

 Structure of Benzene
The molecular formula of benzene has been found from analytical data, to be C6H6. Relatively higher proportion
of carbon and addition of chlorine to benzene molecule indicate it to be an unsaturated compound. Depending
on the various facts available to scientists from time to time, many structures for benzene had been proposed.
Some are described below.
 Open Chain Structure
- Based upon observable facts given above and the tetravalency of carbon, the following open chain
structures were proposed for benzene.

 Drawbacks of open chain structure: The open chain structure for benzene was rejected due to the
following reasons:
- Addition reactions usually given by alkenes and alkynes are not given by benzene.
- Benzene forms only one kind of mono-substituted product.
- An open chain structure however, can form more than one kind of monosubstituted product as shown
below:

- The open chain compounds do, not give reactions such as FriedelCraft reaction, nitration, sulphonation.
- On reduction with hydrogen in the presence of Ni at 200°C, actually a cyclic compound cyclohexane is
obtained.
 An orbital model for the benzene structure
 Building the orbital model
- Benzene is built from hydrogen atoms (1s1) and carbon atoms (1s22s22px12py1).
- Each carbon atom has to join to three other atoms (one hydrogen and two carbons) and doesn't have
enough unpaired electrons to form the required number of bonds, so it needs to promote one of the 2s2 pair
into the empty 2pz orbital.
 Promotion of an electron

- There is only a small energy gap between the 2s and 2p orbitals, and an electron is promoted from the 2s to
the empty 2p to give 4 unpaired electrons. The extra energy released when these electrons are used for
bonding more than compensates for the initial input. The carbon atom is now said to be in an excited state.
 Hybridisation
Because each carbon is only joining to three other atoms, when the carbon atoms hybridise their outer orbitals
before forming bonds, they only need to hybridise three of the orbitals rather than all four. They use the 2s
electron and two of the 2p electrons, but leave the other 2p electron unchanged.

Page | 1
- The new orbitals formed are called sp2 hybrids, because they are made by an s orbital and two p orbitals
reorganizing themselves.
- The three sp2 hybrid orbitals arrange themselves as far apart as possible which is at 120° to each other in a
plane. The remaining p orbital is at right angles to them.
- Each carbon atom now looks like the diagram on the right. This is all exactly the same as happens in ethene.
- The difference in benzene is that each carbon atom is joined to two other similar carbon atoms instead of
just one. Each carbon atom uses the sp2 hybrids to form sigma bonds with two other carbons and one
hydrogen atom.
- The next diagram shows the sigma bonds formed, but for the moment leaves the p orbitals alone.

Since sigma bond results from the overlap of above said planar orbital, all H and C atoms are in the same plane
and their generate a hexagonal ring of C atoms.

Each C atom in benzene also has an unhybrid 2pz orbital containing one electron. These 2pz orbital are
perpendicular to the plane of sigma bonds.

Actually these 2pz orbital produce a π (pi) molecular orbital containing six electrons. One half of this π (pi)
molecular orbital lies above the plane of hexagonal ring and remaining half below the ring like a sandwich.

The overlap of these 2pz orbital results in the formation of a fully delocalized π (pi) bond, which extends all over
the six C atoms of benzene nucleus. The molecular orbital approach clearly indicates that these six electrons could
be found anywhere in highly delocalized manner. As a result of delocalization, a stronger π (pi) bond and a more
Page | 2
stable benzene molecule is obtained which undergo substitution reactions more frequently than addition
reactions.
Bond Length Analysis in Benzene C-C
length in alkane = 1.54oA C=C length in
alkene = 1.34oA
But in benzene,
C-C length = 1.397oA
C=C length = 1.397oA
- This shows that in benzene single and double bonds have quite extraordinary character as they do not
resemble to alkane and alkene in bond lengths.
- That is why benzene shows a behavior of saturated as well as an unsaturated hydrocarbon simultaneously.
 Modern Representation of Benzene
- With the help of molecular orbital behavior we conclude that benzene has
 A regular hexagonal structure with an inscribed circle.
 A hexagon with alternate double and single bonds.

QUESTION: WRITE A NOTE ON THE STABILITY OF BENZENE RING.

ANSWER:
- In benzene ring π (pi) molecular orbital is in a state of vibration due to this vibration resonance is
produced. The stability of benzene ring is due to resonance energy of the system. The resonance energy is
the difference in energy content of benzene compared with that of a formal written structure. The Kekule’s
structure requires localization of 2p-electrons as specific π (pi) bonds alternately between particular C
atoms.
- The actual resonance hybrid structure has these electrons delocalized spread over the whole ring. Hence, π
(pi) electrons of benzene are not readily available at particular positions as in alkenes, and so do not assist
the attack of a weak electrophile in the same way as in alkenes. On the other hand the reactivity of benzene
ring is also affected by the presence of annular π (pi) electronic cloud which acts as a repelling shield to
any nucleophilic attack. Thus electrophilic substitution is more common in benzene but for a powerful
electrophile reagent.

Page | 3
 Resonance hybrid structure of benzene
 The currently accepted structure was developed by the application of the theory of resonance proposed
in 1933. This theory states that benzene is a resonance hybrid of the following canonical forms.

 Since, the forms I and II are the most contributing, hence benzene is represented as a hybrid structure
of these two structures, i.e.,

Page | 4
SIR ERICH ARMAND ARTHUR JOSEPH HUCKEL (August 9, 1896, Berlin – February 16, 1980, Marburg) was a
German physicist and physical chemist. He is known for two major contributions:
i. The Debye–Huckel theory of electrolytic solutions
ii. The Huckel method of approximate molecular orbital (MO) calculations on π electron systems.

Page | 5
  HUCKEL'S RULE
- In 1931, Sir Erich Huckel proposed a rule to determine if a planar ring molecule would have aromatic
properties. This rule states that if a cyclic, planar molecule has 4n+2 π-electrons, it is aromatic. This rule
would come to be known as Huckel's Rule.
- Four Criteria for Aromaticity
i. The molecule is cyclic (a ring of atoms)
ii. The molecule is planar (all atoms in the molecule lie in the same plane)
iii. The molecule is fully conjugated (p orbitals at every atom in the ring)
iv. The molecule has 4n+2 π-electrons (n=0 or any positive integer)
- Why 4n+2 π-Electrons?
 According to Hückel's Molecular Orbital Theory, a compound is particularly stable if all of its bonding
molecular orbitals are filled with paired electrons.
 This is true of aromatic compounds, meaning they are quite stable.
 With aromatic compounds, 2 electrons fill the lowest energy molecular orbital, and 4 electrons fill each
subsequent energy level (the number of subsequent energy levels is denoted by π), leaving all bonding
orbitals filled and no anti-bonding orbitals occupied.
 This gives a total of 4n+2 π-electrons.
 The molecular orbital diagram for the aromatic compound, benzene, below.

Molecular Orbitals levels of Benzene

Benzene has 6π- electrons. Its first 2π-electrons fill the lowest energy orbital, and it has 4π-electrons
remaining. These 4 fill in the orbitals of the succeeding energy level. Notice how all of its bonding
orbitals are filled, but none of the anti-bonding orbitals have any electrons.
- Which Electrons are π -Electrons
 Huckel's Rule is figuring out which electrons in the compound are actually π-electrons.
 The rule is quite straight forward; π-electrons lie in p orbitals.
 Sp2 hybridized atoms have 1 p orbital each.
 So if every molecule in the cyclic compound is sp2 hybridized, this means the molecule is fully
conjugated (has 1 p orbital at each atom), and the electrons in these p orbitals are the π-electrons.
 A simple way to know if an atom is sp2 hybridized is to see if it has 3 attached atoms and no lone pairs
of electrons.
 In a cyclic hydrocarbon compound with alternating single and double bonds, each carbon is attached to
1 hydrogen and 2 other carbons. Therefore, each carbon is sp2 hybridized and has a p orbital.
 As for example, benzene:

Each double bond (π bond) always

contributes 2 π electrons. Benzene
has 3 double bonds, so it has 6 π
electrons.
Page | 6
- Aromatic Ions
 Hückel's Rule also applies to ions. As long as a compound has 4n+2 π electrons, it does not matter if the
molecule is neutral or has a charge.
 For example, cyclopentadienyl anion is an aromatic ion: Carbons 2-5 are sp2 hybridized because
they have 3 attached atoms and have no lone electron pairs. Whereas about carbon-1 another simple
rule to determine if an atom is sp2 hybridized is if an atom has 1 or more lone pairs and is attached to
an sp2 hybridized atom, then that atom is sp2 hybridized also. Therefore, carbon 1 has a p orbital.
Cyclopentadienyl anion has 6 π electrons and fulfills the 4n+2 rule.

- Heterocyclic Aromatic Compounds

 Compounds with elements other than carbon in the ring can also be aromatic, as long as they fulfill the
criteria for aromaticity. These molecules are called heterocyclic compounds because they contain 1 or
more different atoms other than carbon in the ring.
 A common example in furan: This contains an oxygen atom. All carbons in furan are sp2 hybridized.
The oxygen has at least 1 lone electron pair and is attached to an sp2 hybridized atom, so it is sp2
hybridized as well. Notice how oxygen has 2 lone pairs of electrons. An sp2 hybridized atom only has
1 p orbital, which can only hold 2 electrons, while the other pair is in an sp2 orbital. So, only 1 of
oxygen's 2 lone electron pairs are π electrons. Furan has 6 π electrons and fulfills the 4n+2 rule.

Page | 7
QUESTION: Using the criteria for aromaticity, determine if the following molecules are aromatic.

ANSWER:
1. Aromatic - only 1 of S's lone pairs counts as π electrons, so there are 6 π electrons, n=1
2. Not aromatic - not fully conjugated, top C is sp3 hybridized
3. Not aromatic - top C is sp2 hybridized, but there are 4 π electrons, n=1/2
4. Aromatic - N is using its 1 p orbital for the electrons in the double bond, so its lone pair of electrons are
not π electrons, there are 6 π electrons, n=1
5. Aromatic - there are 6 π electrons, n=1
6. Not aromatic - all atoms are sp2 hybridized, but only 1 of S's lone pairs counts as π electrons, so there 8 π
electrons, n=1.5
7. Not aromatic - there are 4 π electrons, n=1/2
8. Aromatic - only 1 of N's lone pairs counts as π electrons, so there are 6 π electrons, n=1
9. Not aromatic - not fully conjugated, top C is sp3 hybridized
10. Aromatic - O is using its 1 p orbital for the elections in the double bond, so its lone pair of electrons are not
π electrons, there are 6 π electrons, n=1

Page | 8
  THE ELECTROPHILIC SUBSTITUTION REACTION BETWEEN BENZENE
 Mechanism of Electrophilic Aromatic Substitution (Ar-SE)
- Electrophilic aromatic substitution is a multistep process.
- In the first step, the addition of an electrophile yields a high-energy carbocation in which the aromatic
π system has been broken. Subsequently, the aromatic system is recovered by splitting off a proton.
Therefore, the mechanism of an electrophilic aromatic substitution (Ar-SE) may be classified as an
addition-elimination mechanism.

- Initially, the approaching electrophile interacts with the nucleophilic, aromatic π electron cloud. The so-
called π complex.
- The π complex that is initially generated by the aromatic π system's nucleophilic attack on the electrophile
is then rapidly converted into a cyclohexadienyl cation known as either the Wheland complex or
the σ complex, or the arenium ion. In the σ complex, the electrophile is connected to one of the aromatic
ring carbons by a σ bond.
- In the second step, a proton is eliminated from the σ complex and then accepted by a base. The base is
frequently the counterion of the electrophile; occasionally, the solvent acts as the base. The first step of
Ar-SE reaction, that is, the formation of the σ complex, requires a particularly high amount of energy, as the
aromatic π system is broken. In the second step, that is, in the deprotonation, the aromatic π system is
recovered.
- In some cases, it is not a proton but another cation that is eliminated from the σ complex. As a result, the
aromatic compound is defunctionalized - it loses a functional group. Such a reaction is called an Ipso Attack.
- In the cyclohexadienyl cation (σ complex), the positive charge is delocalized - that is, it is shared by
several carbon atoms.

- If the three resonance structures of the σ complex are simply superposed, the positive charge in each ortho
and para position would amount to +0.33. In an improved model, the meta position also carries a small
positive charge (+0.10).

Page | 9
- Atom’s electric charges of several σ complexes

QUESTION: WHAT ARE IPSO, MESO, AND PERI SUBSTITUTIONS IN ORGANIC CHEMISTRY?

ANSWER:
- Ipso Substitution: The ipso- prefix is used when two substituents share the same ring position in an
intermediate compound. This could occur in an electrophilic aromatic ring substitution.
- Meso Substitution: The meso- prefix is used when substituents occupy a benzylic position, when the first
carbon covalently bonds adjacent to benzene or other aromatic ring. It is seen in acridines and calixarenes.
- Peri Substitution: The peri- prefix is used to describe substituents at the 1 and 8 positions. It is seen
specifically in naphthalenes.

Page | 10
SUBSTITUTION REACTIONS OF BENZENE DERIVATIVES


- According to the considerations above, substituents may be classified into two main groups:
i. ACTIVATING SUBSTITUENTS: Those are capable of stabilizing the positive charge of the σ complex.
Compared to benzene, such substituents result in a higher reaction rate of (a second) electrophilic
aromatic substitution.
Examples of activating groups in the relative order from the most activating group to the least activating:

[R as alkyl groups (CnH2n+1)]

ii. DEACTIVATING SUBSTITUENTS: Those additionally destabilize the positive charge of the σ complex.
Compared to benzene, such substituents characteristically result in a lower reaction rate of (a second)
electrophilic aromatic substitution.
Examples of deactivating groups in the relative order from the most deactivating to the least deactivating:

[R as alkyl groups (CnH2n+1)]

The order of reactivity among Halogens from the more reactive (least deactivating substituent) to the
least reactive (most deactivating substituent) halogen is:

- Halogen substituents are a little unusual in that they are deactivating but still direct ortho/ para. The
reason is that they are both inductive electron withdrawing (electronegativity) and resonance donating
(lone pair donation). The inductive effect lowers the reactivity but the resonance effect controls the
regiochemistry due to the stability of the intermediates.

- The stabilization as well as the destabilization of the σ complex may be the outcome of two different effects.
i. Inductive increase or decrease, respectively, in the aromatic system's electron density through polarization
of the σ bond between the substituent and the aromatic ring. This quality of substituents is known as the
electron-donating inductive effect (+I effect) or electron-withdrawing inductive effect(-
I effect), respectively.

Alkyl groups and the negatively charged The atom of a substituent with a -I effect that is directly bound to
oxygen of a phenolate anion are examples the aromatic ring carbon carries a partially positive charge. R3N+-
of substituents with a +I effect and SO3H- are examples of substituents with a -I effect

Page | 11
An increase or decrease of the aromatic system's electron density through resonance (mesomerism). That is, the
substituent participates in the aromatic π electron system either by donating π electron density (lone electron
pair) or by accepting π electron density. These qualities of a substituent are called electron-donating
mesomeric effect (+M effect) or electron-withdrawing mesomeric effect (-M effect),respectively. In Lewis
formulas, the mesomeric effect of a substituent is illustrated by several possible resonance structures of the σ
complex. Mesomeric effects are usually much stronger than inductive effects.

Substituents such as the amino group (NH2-) of aminobenzene (aniline) or the methoxy group
(OCH3-) of methoxybenzene (anisole) show a considerable +M effect.

The nitro group and carboxyl groups are examples of substituents with a -M effect.

- The activating group directs the reaction to the ortho or para position, which means the electrophile
substitute the hydrogen that is on carbon 2 or carbon 4.
- The deactivating group directs the reaction to the meta position, which means the electrophile substitute
the hydrogen that is on carbon 3 with the exception of the halogens that is a deactivating group but directs
the ortho or para substitution.

Page | 12
 1. ACTIVATING GROUPS (ortho or para directors)
- When the substituents like OH have an unshared pair of electrons, the resonance effect is stronger than the
inductive effects which make these substituents stronger activators, since this resonance effect direct the
electron toward the ring. In cases where the subtituents is esters or amides, they are less activating because
they form resonance structure that pull the electron density away from the ring.
OR
- Electron Donating Groups (EDG) with lone pairs (e.g. :O:Me, :NH2) on the atoms adjacent to the π system
activate the aromatic ring by increasing the electron density on the ring through a resonance donating
effect. The resonance only allows electron density to be positioned at the ortho and para positions. Hence
these sites are more nucleophilic, and the system tends to react with electrophiles at these ortho and para
sites.

2. DEACTIVATING GROUP (meta directors)

- The deactivating groups deactivate the ring by the inductive effect in the presence of an electronegative
atom that withdraws the electrons away from the ring.
- Electron Withdrawing Groups (EWG) with π bonds to electronegative atoms (e.g. C=O, NO 2) adjacent to
the π system deactivate the aromatic ring by decreasing the electron density on the ring through a
resonance withdrawing effect. The resonance only decreases the electron density at the ortho and para
positions. Hence these sites are less nucleophilic, and so the system tends to react with electrophiles at the
Meta sites.

 There are two main electronic effects that substituents can exert: 
- RESONANCE effects are those that occur through the π system and can be represented by resonance
structures. These can be either electron donating (e.g. OMe) where π electrons are pushed toward the arene
or electron withdrawing (e.g. C=O) where π electrons are drawn away from the arene.
- INDUCTIVE effects are those that occur through the π system due to electronegativity type effects. These
too can be either electron donating (e.g. Me) where π electrons are pushed toward the arene or electron
withdrawing (e.g. CF3, +NR3) where π electrons are drawn away from the arene.

NOTE BY:
WHAT ARE ARENES?
Arenes are aromatic hydrocarbons. The term "aromatic" originally referred to their pleasant smells,
but now implies a particular sort of delocalised bonding.
The arenes are likely to meet at this level are based on benzene rings. The simplest of them is
benzene itself, C6H6. The next simplest is methylbenzene (old name: toluene) which has one of the| 13
Page
hydrogen atoms attached to the ring replaced by a methyl group - C6H5CH3.
EDG / activating groups direct
ortho / para
EWG / deactivating
groups direct meta
except halogens (X)
which are deactivating but
direct ortho / para
EDG add electron density to
the p system making it more
nucleophilic
EWG remove electron density
from the p system making it
less nucleophilic

EWG = Electron Withdrawing

Group
EDG = Electron Donating Group
The H atom is the standard and
is regarded as having no effect.

Page | 14
 1. NITRATION OF BENZENE
- Benzene reacts with concentrated nitric acid at 500 – 600 C in the presence of concentrated sulphuric acid to
form nitrobenzene. This reaction is known as nitration of benzene.
- Reaction type: Electrophilic Aromatic Substitution
- General Reaction

Benzene Nitrobenzene

- Reaction Mechanism

Step 1: Nitric acid accepts a proton from sulphuric acid and then dissociates to form nitronium ion.

Step 2: The nitronium ion acts as an electrophile in the process which further reacts with benzene to form
arenium ion.

Step 3: The arenium ion then loses its proton to Lewis base forming nitrobenzene.

Page | 15
 2. SULFONATION OF BENZENE
- Sulfonation of benzene is a process of heating benzene with fuming sulphuric acid (H2SO4 +SO3) to produce
benzenesulfonic acid. The reaction is reversible in nature.
- Sulphonation of benzene requires “fuming sulphuric acid”, which is sulphuric acid with extra SO3 added.
The sulphuric acid produces even more SO3, which is the electrophile in this reaction.
- Reaction type: Electrophilic Aromatic Substitution
- General Reaction

Benzene Sulphuric Acid Benzenesulfonic Acid

- Reaction Mechanism

Step I: Formation of Electrophilic species, SO3 which can be formed by the loss of water from the sulfuric acid

Step 2:
The π electrons of the aromatic C=C act as a nucleophile,
attacking the electrophilic S, pushing charge out onto an
electronegative O atom. This destroys the aromaticity giving the
cyclohexadienyl cation intermediate.

Step 3:
Loss of the proton from the sp3 C bearing the sulfonyl-
group reforms the C=C and the aromatic system.

Step 3:
Protonation of the conjugate base of the sulfonic acid by
sulfuric acid produces the sulfonic acid.

Page | 16
 3. REVERSE SULFONATION
- Sulfonation of benzene is a reversible reaction. Sulfur trioxide readily reacts with water to produce sulfuric
acid and heat. Therefore, by adding heat to benzenesulfonic acid in diluted aqueous sulfuric acid the reaction
is reversed.

 Applications of Nitration and Sulfonation

- Nitration is used to add nitrogen to a benzene ring, which can be used further in substitution reactions. The
nitro group acts as a ring deactivator. Having nitrogen present in a ring is very useful because it can be used
as a directing group as well as a masked amino group. The products of aromatic nitrations are very
important intermediates in industrial chemistry.

- Because sulfonation is a reversible reaction, it can also be used in further substitution reactions in the
form of a directing blocking group because it can be easily removed. The sulfonic group blocks the carbon
from being attacked by other substituents and after the reaction is completed it can be removed by reverse
sulfonation. Benzenesulfonic acids are also used in the synthesis of detergents, dyes, and sulfa drugs.
Bezenesulfonyl Chloride is a precursor to sulfonamides, which are used in chemotherapy.

Page | 17
 4. HALOGENATION OF BENZENE
- Reaction type: Electrophilic Aromatic Substitution
- An electrophilic aromatic halogenation is a type of electrophilic aromatic substitution. This organic reaction
is typical of aromatic compounds and a very useful method for adding substituents to an aromatic system.
- A few types of aromatic compounds, such as phenol, will react without a catalyst, but for typical benzene
derivatives with less reactive substrates, a Lewis acid catalyst is required. Typical Lewis acid catalysts
include AlCl3, FeCl3, FeBr3, and ZnCl2. These work by forming a highly electrophilic complex which is
attacked by the benzene ring.
- Electrophilic species: the halonium ion (i.e. X+; X = Cl2 and Br2) formed by the removal of a halide ion by
the Lewis acid catalyst
- Restricted for I- or F- are usually introduced using alternative methods
- General Reaction:

A. Chlorination of Benzene
- General Reaction:

- Mechanism of Chlorination of Benzene

Step 1: formation of a chloronium ion.

Step 2: attack of the chloronium ion on the ring

Step 3: proton transfer regenerates the aromatic character of the ring.

Page | 18
 B. Bromination of benzene

- General Reaction:

- Mechanism of Bromination of benzene

Page | 19
QUESTION: WHY IODINATION AND FLUORINATION OF BENZENE DIFFICULT?

ANSWER:
- When Benzene or the halogen in the starting material has to be slightly more reactive than the
other.
- For satisfying this condition, electron donating groups attached to the phenyl ring making it more
nucleophilic are preferred over unsubstituted Benzene. Also, the electrophilicity of the halogen is
increased by using a Lewis acid catalyst thereby making it more reactive.
- These changes in turn help to achieve transition state faster and stabilize it better.
- Electrophilic aromatic substitution reaction
X
X
Lewis acid catalyst First
H
+ X2 Step
Slow Step +

Transition State

Used lewis Acid to protonate it Faster reaction by Increasing

the stability of carbocation
(electron donating groups
& resonance stabilization )
Increase Nucleophilicity
by electron donating groups

- In case of the halogens, the electronegativity and electrophilicity decrease from F to I in the periodic table.
Fluorine is most electrophilic, and Iodine is least. Therefore, Fluorination is highly reactive, and
Iodination is highly unreactive for electrophilic aromatic substitution reactions.
- The exothermic rates of aromatic halogenation also decrease from Fluorine to Iodine. Fluorination reaction
being highly exothermic and explosive, the reaction cannot be controlled resulting in polyfluorinated
products. For Iodination, the reaction is endothermic with 12kJ/mol of energy absorbed. Therefore, it
cannot be done using the conventional method using Lewis acid catalyst and requires strong oxidizing
agents.
Atom Electronegativity Electrophilicity First Ionization Energy ( kJ/mol)
Fluorine 4.0 3.86 1681
Chlorine 3.0 3.67 1251
Bromine 2.8 3.40 1140
Iodine 2.5 3.09 1008

- Controlled fluorination of benzene is difficult, but it can be accomplished by a two-step THALLATION

PROCEDURE. Benzene reacts with thallium tris [trifluoroacetate, Tl(OCOCF3)3] to give an
organothallium intermediate. Further reaction with potassium fluoride and boron trifluoride gives the
aryl fluoride.

Page | 20
 Exothermic

Most F
Fluorine

Chlorine Decreasing Electrophilicity Decreasing

and electronegativity Exothermic rates
Bromine Cl aromatic halogination

Iodine

Least
Br

Endothermic

- This is because, when Iodine adds to the Benzene reversibly generating HI. HI being a strong reducing
agent regenerates “I” from aryl iodide giving back the aromatic hydrocarbon. However, in the presence of
oxidizing agents such as HIO3, HI is converted back to Iodine thereby increasing the concentration of
Iodine in the reaction mixture. According to Le-Chatelier’s principle, if the concentration of one of the
reagents is increased then the equilibrium shifts in the forward direction to give aryl iodide as the desired
product.
I

+ I2 + HI

a) Oxidizing agents (HIO3, HNO3) reconverts HI to I2

- Another way to obtain aryl iodide is to remove HI as soon as it is formed in the reaction mixture, by forming
salts. For example, when the Mercuric oxide is used, it converts Hydrogen Iodide to Mercuric Iodide that is
then discarded.

b) Salt formation (alkali hydroxide, carbonate or hydrogen carbonate, borax, HgO, Hg-acetate or
aliphatic amine or Ammonia)

Page | 21
- The reaction mechanism of Iodination of benzene
 Oxidizing agents, when used, Iodine (I2) get oxidize to iodonium ion (I+) by using HNO3 or H2SO4 in
the presence of Acetic acid and this reaction was called Tronov-Novikov reaction.
 Iodine can be easily oxidized by using nitric acid (HNO3) in the presence of an Acetic acid and Iodine
generates Iodine cation that reacts with Benzene giving Iodobenzene, Nitrogen dioxide, and water.
 Here HNO3 is consumed in the reaction; hence it is a reagent and not a catalyst.
 Reaction mechanism:

H I
Acetic acid
+ + NO2 + H2O
+ 1/2I2 HNO3

Benzene
Iodobenzene

Generate of iodonium ion (I+)

H+ + HNO3 + 1/2I2 I+ + NO2 + H2O

Iodine cation

I2 + HNO3 + Acetic acid (H+) Tronov-Novikov Method

 A similar mechanism is seen for Cupric Chloride and Hydrogen peroxide for generation of Iodine
cation.
H I

CuCl2 + HI
+ I2
H2O2
Benzene Iodobenzene

 The best reagent for Iodination is Iodine monochloride (ICl) an interhalogen compound. Chlorine is
more electronegative and pulls the electron cloud towards itself giving Iodine a (delta) positive charge.
The Benzene ring can pick up this quickly than Iodine from the non-polar I bond thereby giving aryl
iodide as the desired product.
H I

AlCl3 + HCl
+ ICl

Benzene Iodobenzene

Page | 22
 5. FRIEDEL-CRAFTS ALKYLATION OF BENZENE
- Alkylation means substituting an alkyl group into something - in this case into a benzene ring. A hydrogen on
the ring is replaced by a group like methyl or ethyl and so on. Benzene is treated with a chloroalkane (for
example, chloromethane or chloroethane) in the presence of aluminium chloride as a catalyst.
- Reaction type: Electrophilic Aromatic Substitution
- General Reaction:

- Named after Friedel and Crafts who discovered the reaction in 1877.
- Reagent: normally the alkyl halide (e.g. R-Br or R-Cl) with aluminum trichloride, AlCl3, a Lewis acid catalyst
- The AlCl3 enhances the electrophilicity of the alkyl halide by complexing with the halide
- Electrophilic species: the carbocation (R+) formed by the "removal" of the halide by the Lewis acid catalyst
- The reactive electrophile, the carbocation is prone to rearrangement to a more stable carbocation which will
then undergo the alkylation reaction.

- Mechanism for the Friedel-Crafts Alkylation of Benzene

Step 1:
The alkyl halide reacts with the Lewis acid to form a more
electrophilic a carbocation

Step 2:
The p electrons of the aromatic C=C act as a nucleophile,
attacking the electrophilic C+. This step destroys the
aromaticity giving the cyclohexadienyl cation intermediate.

Step 3:
Removal of the proton from the sp3 C bearing the alkyl-
group reforms the C=C and the aromatic system, generating
HCl and regenerating the active catalyst.

Page | 23
 THE FRIEDEL-CRAFTS ALKYLATION AND ITS LIMITATIONS
- The Friedel-Crafts reaction is a convenient way to introduce alkyl groups in the benzene ring. It is a typical
electrophilic substitution process, in which the electrophile is (in most cases) a carbocation.
- There are three ways to generate the carbocationic species:
i. Via preliminary reaction of an alkyl chloride with AlCl3.
ii. Via preliminary reaction of an alcohol with a Lewis acid (such as BF3) or a Bronsted acid (usually H3PO4).
iii. Via preliminary reaction of an alkene with a Bronsted acid, whose anion is a weak nucleophile (HF)
- Four strict limitations for Friedel-Crafts Alkylation:
i. The reaction works only with benzene or ACTIVATED benzene derivatives. It will not occur if the benzene
ring is DEACTIVATED.
ii. The reaction works only with ALKYL halides (i.e. chlorides, bromides or iodides), but it does not work with
VINYL or ARYL halides.
iii. Because of the intermediate formation of carbocations, product mixtures might be obtained, due to
rearrangements of the carbocations.

iv. The Friedel-Crafts reaction often leads to the introduction of more than one alkyl group in the molecule.
The reason for such undesired polyalkylation

Page | 24
Note By:
VINYL HALIDE: In organic chemistry, a vinyl An ALLYLIC HALIDE is an alkyl halide in which there is
halide is any alkene with at least one halide one or more halogen atoms on an allylic carbon. Allylic
substituent bonded directly on one of the carbons are carbons bonded to carbon atoms that are
alkene carbons. doubly bonded to other carbon atoms

Page | 25
6. FRIEDEL-CRAFTS ACYLATION OF BENZENE
- Friedel-Crafts Acylation allows to synthesis of monoacylated products from the reaction between arenes
and acyl chlorides or anhydrides. The products are deactivated, and do not undergo a second substitution.
- General Reaction:

- Reaction type: Electrophilic Aromatic Substitution.

- Reagent: normally the acyl halide (RCOCl) with aluminum trichloride (AlCl3) which acts as a Lewis acid
catalyst.
- Alternatively, the acid anhydride [(RCO)2O] can be used instead of the acyl halide.
- The AlCl3 enhances the electrophilicity of the acyl halide by complexing with the halide.
- Electrophilic species: the acyl cation or acylium ion (RCO+) formed by the "removal" of the halide by the
Lewis acid catalyst
- The acylium ion is stabilized by resonance as shown below. This extra stability prevents the problems
associated with the rearrangement of simple carbocations:

acylium ion

- Mechanism for the Friedel-Crafts Acylation of Benzene

Step 1:
The acyl halide reacts with the Lewis acid to form a complex.

Step 2:
Loss of the halide to the Lewis acid forms the electrophilic
acylium ion.

Step 3:
The p electrons of the aromatic C=C act as a nucleophile,
attacking the electrophilic C+. This step destroys the
aromaticity giving the cyclohexadienyl cation intermediate.

Step 4:
Removal of the proton from the sp3 C bearing the acyl- group
reforms the C=C and the aromatic system, generating HCl and
regenerating the active catalyst.

Page | 26
SIR CHARLES FRIEDEL SIR JAMES CRAFTS

Page | 27
Uses:

1. It is an effective insecticide, particularly for mosquito, flies.

2. Responsible for the almost complete eradication of malaria-carrying mosquito.

3. DDT is still being widely used in poor country due to non-availability of other cheaper insecticides.

Uses:

1. It is generally used as artificial sweetner.

2. It is used in different vitamin supplement.

Page | 28
 3. Saccharin is used to sweeten products such as drinks, candies, cookies, and medicines.

4. Saccharin can be used to prepare exclusively disubstituted amines from alkyl halides also.

Uses:

1. Benzene hexachloride is used as an insecticide on crops, in forestry, for seed treatment.

2. It is used in the treatment of head and body lice.
3. It is used in pharmaceuticals.
4. It is used to treat scabies.
5. It is used in shampoo.

Uses:

1. It is used as a disinfectant.

Page | 29