CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES

Introduction:
● Introduction to Haloalkanes
● Classification of Haloalkanes
● Nomenclature of Haloalkanes
● Nature of C–X Bond
● Methods of Preparation of Haloalkanes
● Physical Properties of Haloalkanes
● Chemical Properties of Haloalkanes
● Introduction to Haloarenes
● Classification of Haloarenes
● Nomenclature of Haloarenes
● Methods of Preparation of Haloarenes
● Physical Properties of Haloarenes
● Chemical Properties of Haloarenes
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Introduction:
● The organohalogen compounds in which the halogen atom (F, Cl,
Br or I) is present in an aliphatic chain are known as the
haloalkanes.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Haloalkanes:
● Haloalkanes are the halogen derivatives of alkanes.

R-X

R= Aliphatic hydrocarbon

X = Halogen atom

-H
R- H R- X
+X
Aliphatic Haloalkane
hydrocarbon
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:

Classification of Haloalkanes

On the basis of
On the basis of number hybridisation of carbon to
of halogen atoms which halogen is
attached
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:
● On the basis of number of halogen atoms -

Monohalogen Dihalogen Polyhalogen

Monohaloalkane Dihaloalkane Trihaloalkane

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:
● On the basis of hybridisation of carbon to which halogen is attached -

Compounds Compounds
containing containing sp2
sp3 C—X Bond C—X Bond
(X= F, Cl, Br, I) (X= F, Cl, Br, I)
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:
● Compounds Containing sp3 C—X Bond -

Alkyl Halides Allylic Halides Benzylic Halides

where, X= F, Cl, Br, I

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:
● Alkyl Halides or Haloalkanes (R—X) -

Primary (1°) Secondary (2°) Tertiary (3°)

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:
Allylic Halides-

● Halogen atom is bonded to a sp3 hybridised carbon next to C=C

bond, i.e., to an allylic carbon.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:
Benzylic Halides-

● Halogen atom is bonded to a sp3 hybridised carbon atom next to an

aromatic ring.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloalkanes:
● Compounds Containing sp2 C—X Bond -

Vinylic Halides Aryl Halides

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
Common System-

● In the common or trivial system, the monohalogen derivatives of

alkanes are named ‘alkyl halides’.

● Their names are derived by naming the alkyl group attached to

halogen and adding the name of the halide, like fluoride, chloride,
bromide or iodide.

Examples:

Ethyl Chloride

Isobutyl chloride
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
IUPAC System-

● According to the IUPAC system, the monohalogen derivatives of the

alkanes are named as haloalkanes.

● The secondary prefix ‘halo’ is added to the name of the alkane.

Examples:

Bromo + ethane 1-Bromoethane

CH3CH2Br

Common name- Ethyl bromide

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
Some other examples-

Common name IUPAC Name Structure

n-Propyl bromide 1- Bromopropane

Isopropyl bromide

Isobutyl chloride 1-Chloro 2-methylpropane

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
● Try to write the IUPAC name of the given alkyl halide.

2-Bromo-3-methylbutane
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
Dihalogen Compounds

Alkylidene Alkylene
Polymethylene
dihalides dihalides
dihalides
(gem-dihalides) (vic-dihalides)

Ethylidine dibromide Ethylene dibromide Trimethylene dibromide

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
Dihalogen Compounds-

● The alkyl halides having two halogen atoms attached to the

adjacent C-atom are also called the vicinal dihalides.

● The alkyl halides having two halogen atoms attached to the

same C-atom are also called the geminal dihalides or
gem-dihalides.

● The alkyl halides having two halogen atoms attached to the

terminal C-atom are called the polymethylene dihalides.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
Nomenclature of Dihalogen Compounds-

Common name IUPAC Name Structure

Ethylene dibromide 1,2-Dibromoethane

Ethylidene dibromide 1,1-Dibromoethane

Trimethylene dibromide 1,3-Dibromopropane

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
Some Other Examples of Dihalogen Compounds-

Common name IUPAC Name Structure

Isopropylidene dichloride 2,2-Dichloropropane

Propylene dichloride 1,2-Dichloropropane

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloalkanes:
Some Other Examples of Dihalogen Compounds-

Common name IUPAC Name Structure

sec-Butyl chloride 2-Chlorobutane

Neopentyl bromide 1-Bromo-2,2-dimethylpropane

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nature of C - X Bond:
C–X Bond lengths, Bond Enthalpies and Dipole Moments-
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Methods of Preparation:
Methods

From From Halogen

From Alcohols
Hydrocarbons exchange
1. By action of HX 1. By free radical 1. By Finkelstein
2. By reaction with halogenation reaction
the phosphorus 2. From alkenes 2. By Swarts
halides reaction
3. By reaction with
SOCl2
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Alcohols:
● The hydroxyl group of an alcohol is replaced by a halogen atom.

+X
R- OH R- X
-OH

● To replace the hydroxyl group, alcohols are treated with the conc.
halogen acids, phosphorus halide or thionyl chloride.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Alcohols:
1. By the action of halogen acids (Grove’s process)-

ZnCl2
R- OH + HX R- X + H2O

Alcohol Alkyl halide

● Reactions of 1° and 2° alcohols with HX are carried out in the

presence of anhydrous ZnCl2. The purpose of anhydrous ZnCl2 is to
help in the cleavage of C–O bond.
● With 3° alcohols, the reaction is conducted by shaking them with
the conc. HCl at room temperature.
● Constant boiling with HBr (48%) is used for preparing alkyl bromide.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Alcohols:
● Alkyl bromides can also be prepared by the action of conc.
H2SO4 and NaBr on alcohols.

R- OH + NaBr + H2SO4 R- Br + NaHSO4 + H2O

● Good yields of R–I may be obtained by heating alcohols with
NaI or KI in 95% phosphoric acid.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Alcohols:
● Order of reactivity of halogen acids with alcohols

H–I > H–Br > H–Cl > H–F

● Order of reactivity of alcohols

Tertiary > Secondary > Primary

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Alcohols:
2. By the action of phosphorus halides-

PX3 or PX5
R- OH R- X
● Preparation of alkyl halides

R- OH + PCl5 R- Cl + POCl3 + HCl

Alcohol Alkyl chloride

3R- OH + PCl3 3R-Cl + H3PO3

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Alkyl Bromide and Alkyl Iodide:
● PBr3 and PI3 are not very stable compounds. They are prepared in
situ (produced in the reaction mixture) by the reaction of red
phosphorus with bromine and iodine, respectively.

Red P/X2
R- OH R- X
X2 = Br2, I2
Alcohol Alkyl halide
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Alkyl Bromide and Alkyl Iodide:
3. By reaction with thionyl chloride

Pyridine
R- OH + SOCl2 R- Cl + SO2↑ + HCl↑

Alcohol Thionyl Alkyl chloride

chloride

Since, thionyl chloride method gives almost pure alkyl chloride, so it is

preferred over the other methods for the preparation of the alkyl
chlorides.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Hydrocarbons:
1. By free radical halogenation-

Cl2/UV/Light/Heat
CH3CH2CH2CH3 CH3CH2CH2CH2Cl

Butane 1- Chlorobutane

CH3CH2CH2CH2Cl
2- Chlorobutane

A mixture of isomeric mono- and poly haloalkanes is formed, which is

difficult to separate as pure compounds.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Hydrocarbons:
2. From alkenes-

By addition of halogen halide (HX)

● Alkenes react with halogen acids to form haloalkanes.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes from Hydrocarbons:
● Predict the product of the following reaction-
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Markovnikov’s Rule:
● “The addition of the unsymmetrical reagents such as HX to the
unsymmetrical alkenes occurs in such a way that the negative part
of the adding molecule gets attached to the carbon atom of the
double bond, which has the lesser number of the hydrogen atoms”.

● The major product of the reaction of propene with HBr will be

2-bromopropane.

Propene 2- Bromopropane
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Anti- Markovnikov’s Rule:
● The addition of HBr to propene in the presence of the organic
peroxide takes place, contrary to Markovnikov’s rule i.e., anti
Markovnikov addition of HBr.

1- Bromopropane

● The effect is known as ‘Peroxide effect’ or the ‘Kharasch effect’.

● It follows free radical mechanism.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Anti- Markovnikov’s Rule:
● In case of HCl, the H–Cl bond is stronger (430.5 kJ mol-1) than the
H–Br bond (363.7 kJ mol-1) and is not cleaved by the homolytic
fission to form the free radical.

● In case of HI, the H–I bond is weaker (296.8 kJ mol-1) and the iodine
free radicals combine to form iodine molecules instead of adding
across the double bond.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes by Halogen Exchange:
1. Finkelstein reaction-

● Alkyl iodides are prepared by treating the solution of sodium iodide

in acetone with the alkyl bromides or alkyl chlorides.

Dry acetone
R- X + NaI R- I + NaX

X = Cl, Br

● The by-product sodium bromide or sodium chloride are less soluble

and gets precipitated.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloalkanes by Halogen Exchange:
2. Swarts reaction-

● Alkyl fluorides are prepared by heating alkyl chlorides or alkyl

bromides with the metallic fluorides such as AgF, Hg2F2,
CoF2 or SbF3.

R- X + AgF R- F + AgX

Alkyl halide Alkyl fluoride

X = Cl, Br
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloalkanes:
1. Physical state, colour, odour:

● CH3Cl, CH3Br and C2H5Cl are gases at room temperature. Higher

members are either liquids or solids.

● Alkyl halides are colourless in pure state.

● However, alkyl bromides and alkyl iodides develop colour

when exposed to light.

● Many volatile halogen compounds have sweet smell.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloalkanes:
2. Melting and Boiling Point:

● Haloalkanes have higher boiling points as compared to these of

corresponding alkanes. This is due to their polar nature &
strong dipole – dipole interactions between their molecules.

● The boiling points of haloalkanes are in the order – (RCl < RBr <
RI). It is because with the increase in size & mass of halogen
atom the magnitude of Van der Waal’s force of attraction
increases.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloalkanes:
● Among isomeric alkyl halides, the boiling point decreases with
increases in branching in the alkyl group. This is due to the reason
that with increases in branching, the molecules attains a spherical
shape with less surface area.

● As a result, inter-particles forces becomes weaker resulting in lower

boiling point.

● For example, among isomeric butyl chlorides, the straight chain

isomers, n-butyl chloride has highest boiling point whereas
tert-butyl chloride has the lowest boiling point.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloalkanes:
3. Density:

● Bromo, iodo & polychloro derivatives of hydrocarbon are heavier

than water. The density increases with increase in no. of C- atoms,
halogen atoms & atomic mass of the halogen atom.

4. Solubility:

● Haloalkane & haloarenes are practically insoluble in water because

they are not able to form the intermolecular H-bonds with water
molecules. Now, however they are soluble in organic solvents.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloalkanes:
5. Stability:

Strongest bond Weakest bond

C–F > C–Cl > C–Br > C–I

(Bond strength decreases with an increase in the bond length)

Now, the order of stability of the alkyl halides is:

R–F > R–Cl > R–Br > R–I

Alkyl iodides decompose slowly in the presence of light to give

iodine and become purple or brown coloured.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloalkanes:
6. Inflammability:

Haloalkanes are less flammable than the corresponding

hydrocarbons.

The combustibility, however, decreases with an increase in the

halogen content. For example:

CH4 > CH2Cl2 > CHCl3 > CCl4

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Chemical Properties of Haloalkanes:

Reactions of Haloalkanes

Nucleophilic
Elimination Reaction with
Substitution
Reaction Metals
Reaction
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
● The substitution reactions taking place by the attack of a
nucleophile are termed as nucleophilic substitution reactions.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
● Substitution reactions involve the substitution of an atom or the
group of atoms by some other atom or group of atoms.

● The carbon atom of the C–X bond in haloalkanes possesses a partial

positive charge due to the higher electronegativity of the halogen
atom.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
● In the given reaction, a nucleophile (OH- ion) substitutes the chloride
ion of chloromethane.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
1. Reaction with aqueous alkali:
Δ
RX + KOH (aq) ROH + KX

Δ
CH3CH2Br + NaOH (aq) CH3CH2OH + NaBr

Ethyl bromide Ethanol

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN1 Reaction:

S N1
Substitution
Nucleophilic Unimolecular
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN1 Reaction Mechanism:
● The alkaline hydrolysis of tertiary butyl bromide with aqueous KOH
proceeds via SN1 mechanism.

● This reaction occurs in two steps.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN1 Reaction Facts:
● It is a two-step reaction, which proceeds via the carbocation
intermediate.

● In the slow rate determining step, only one molecule of the

substrate (alkyl halide) is involved.

Rate ∝ [Substrate]

● It is a unimolecular reaction.

● This reaction is usually carried out in the polar protic solvent.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN1 Reaction Mechanism:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Factors Affecting SN1 Mechanism:
1. Ease with which the leaving group dissociates from the carbon.

2. The reactivity of the nucleophile has no effect on the rate of SN1

reaction.

3. Polar protic solvent having the high dielectric constant increases the
rate of SN1 reaction.

4. Stability of the carbocation:

The order of reactivity of the alkyl halide towards SN1 reaction is

decided on the basis of the stability of the carbocation formed.

More the substitution on carbocation, more will be its stability.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Factors Affecting SN1 Mechanism:
● Since, the tertiary carbocation has the highest number of the alkyl
groups, it has the highest stability.

Methyl
Primary (1°) Secondary (2°) Tertiary (3°)
carbocation
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Factors Affecting SN1 Mechanism:
● Higher the stability of carbocation, easier will be the formation of
the alkyl halide and faster will be the reaction rate.

● Now, the order of reactivity of the alkyl halides towards SN1 reaction
is as follows:

Tertiary halide, secondary halide, primary halide, CH3X

For SN1 reaction

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Factors Affecting SN1 Mechanism:
● Allylic and benzylic halides show high reactivity towards the SN1
reaction than the other simple primary halides (R–CH2–X).

● This is due to greater stabilisation of the allyl and benzyl carbocation

intermediates by resonance.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN2 Reaction:

S N2
Substitution
Bimolecular
Nucleophilic
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN2 Reaction Mechanism:
● The reaction of methyl bromide with the aqueous KOH proceeds via
SN2 mechanism.

● This reaction proceeds in a single step.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN2 Reaction Mechanism:
●
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN2 Reaction Facts:
● It is a single step reaction and it proceeds via the transition
state.

● The transition state shows that the breaking of the C–X bond
and the formation of the C–OH bond takes place
simultaneously.

● Transition state is a unstable state and cannot be isolated.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN2 Reaction Facts:
● SN2 reaction follows second order kinetics.

Rate ∝ [Substrate] [Nucleophile]

● SN2 reaction is a bimolecular reaction.

● SN2 reaction is carried out in an aprotic solvent.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Factors Affecting SN2 Mechanism:
1. Steric Effect:

● The presence of the bulky substituent hinders the approach of

a nucleophile.

● It means lesser the substitution on the carbon atom on which

the nucleophile attacks, easier will be the formation of the
transition state.

● The order of reactivity of the alkyl halide towards the SN1

reaction is:

CH3X > Primary halide > Secondary halide > Tertiary halide
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Factors Affecting SN2 Mechanism:
2. Concentration of nucleophile:

An increase in the concentration of a nucleophile increases the

rate of reaction since the reaction follows the first order
kinetics for nucleophile.

3. Increasing nucleophilic strength favours SN2 mechanism:

OH- > H2O > NH2- >NH3 > CH3O- > CH3OH
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
SN1 Vs SN2:
Order of reactivity of alkyl halides for SN2 Reaction

Tertiary halide, Secondary halide, Primary halide, CH3X

Order of reactivity of alkyl halides for SN1 Reaction

● For a given alkyl group, the reactivity of the alkyl halide (R–X)
follows the same order in both SN1 and SN2 mechanisms.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Comparison between SN1 Vs SN2:

Feature SN1 SN2

Number of Steps Two- step mechanism One- step mechanism

Rate= k[Halide][Nu] ; second

Reaction rate and order Rate= k[Halide]; first order
order

Molecularity Unimolecular Bimolecular

Stereochemistry Racemisation Inversion of configuration

Nature of Solvent Polar protic solvent Non- polar solvent

Order of reactivity of halides 3° > 2° > 1° > Methyl halide Methyl halide > 1° > 2° > 3°
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
1. Reaction with alkali metal iodide:

On reaction with the alkali metal iodide solution, haloalkanes form

alkyl iodide.

C2H5Br + KI (aq) C 2H 5I + KBr

Ethyl bromide Ethyl iodide

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
2. Reaction with Ammonia or Hofmann Ammonolysis:

● When an alkyl halide is treated with an ethanolic solution of

ammonia, a mixture of amines is produced.

● 1° amine is obtained as a major product when ammonia is in excess.

C2H5OH
R- X + NH3 RNH2 + HX

Alkyl halide 1° amine

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
● If the alkyl halide is in excess, then the quaternary ammonium salt is
a major product.

RX RX RX
RNH2 R2NH R 3N R4N+X-

1° 2° 3° Quaternary Amm. Salt

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
3. Reaction with sodium acetylide:

This reaction is used for the conversion of lower alkyne into higher
alkyne.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
4. Reaction with metal cyanides:

RX + KCN RCN + KX

Pot. cyanide Alkyl cyanide

5. Reaction with silver cyanide:

C2H5OH/ H2O
RX + AgCN RNC + AgX

Alkyl isocyanide
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
6. Reaction with silver oxide:

2RX + Ag2O R-O-R + 2AgX

Ether

7. Reaction with alcoholic silver nitrate:

RX + AgNO3 + C2H5OH ROC2H5 + AgX + HNO3

Ether
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
8. Reaction with alkali metal nitrite:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Examples of the Nucleophilic Substitution Reactions.
9. Reaction with silver nitrite:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Ambident Nucleophile:
● It can attack from two or more sites (due to the presence of the
unshared pair of electrons present on different donor atoms)
resulting in two or more products.

● It possesses two or more nucleophilic centres.

● Reagents with the ability to do this are known as the ambident

nucleophiles.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Ambident Nucleophile:
Nitrite as ambident nucleophile:

● Nitrite ion is an ambident nucleophile with two different points of

linkage.

● The linkage through the oxygen results in the alkyl nitrites while
through the nitrogen atom leads to nitroalkanes.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Ambident Nucleophile:
Cyanide as amidentate nucleophile:

● Cyanide group can act as a nucleophile in two different ways.

● Linking through the carbon atom results in the formation of the alkyl
cyanides and through the nitrogen atom leads to the formation of
the isocyanides.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Ambident Nucleophile:
Thiocyanate as ambidentate nucleophile:

● Thiocyanate ion (SCN-) may attack through either S or N.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Elimination Reactions:
● The chemical reactions that involve the elimination of two or more
atoms or groups from the same or the adjacent atoms are called the
elimination reactions.

● Elimination leads to the formation of multiple bond.

● Since, in this reaction, the hydrogen atom is lost from the -carbon,
this reaction is classified as the -elimination reaction.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Elimination Reactions:

● Since, in this reaction, the hydrogen atom is lost from the -carbon,
this reaction is classified as the -elimination reaction.

● The halogen atom is eliminated along with the hydrogen atom from
-carbon atom to form C=C bond.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Elimination Reactions:
● In case of dehydrohalogenation of an alkyl halide, if halogen is
present on the terminal carbon atom of the chain, elimination will
occur only in one direction to give the terminal alkene only.

Example:

1-Bromobutene on dehydrohalogenation gives but-1-ene.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Elimination Reactions:
● If halogen is present on any carbon atom within the chain, the alkyl
halide will undergo dehydrogenation in two or more different
directions.

● The alkyl halide can undergo dehydrogenation in two or more

different directions.
● In such cases, the major elimination product is decided on the basis
of Saytzeff’s rule.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Saytzeff Rule:
● The formation of a product during the dehydration and
dehydrohalogenation reaction is governed by Saytzeff rule.

● It says that hydrogen is preferably eliminated from the carbon atom that
has less number of hydrogen atoms.
Less number of
hydrogen atoms
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Reaction with Metals:
● Active metals like Na, Mg, Cd, Li, etc., readily combine with alkyl
chlorides, bromides and iodides to give corresponding compounds
containing carbon-metal bonds. Such compounds are called
organometallic compounds.

Alkyl halide + Active Metal Organometallic compounds

● An important class of organometallic compounds is alkyl magnesium

halides (RMgX).

● In 1900, Victor Grignard discovered the alkyl magnesium halides. These

are now called the Grignard reagents.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Reaction with Metals:
● Grignard reagents are prepared by the reaction of the haloalkane with
the magnesium turning in dry ether.

Dry Ether
R- X + Mg RMgX
Grignard reagent
Dry Ether
C2H5Br + Mg C2H5MgBr
Ethyl magnesium bromide
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Reaction with Metals:

In Grignard reagent:

● the carbon–magnesium bond is covalent but highly polar (because

carbon pulls electrons from the electropositive magnesium atom).

● the magnesium–halogen bond is ionic.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Reaction with Metals:
● Grignard reagents are highly reactive and react with any source of proton
to give hydrocarbons.

RMgX + H2O R-H + Mg(OH)X

Grignard Reagent Alkane

● Since, the Grignard reagents react with water, therefore, it is necessary to

avoid even the traces of moisture.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Reaction with Metals:
2. Reaction with sodium (Wurtz reaction):
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Introduction to Haloarenes:
● They are responsible for spreading diseases like malaria and
dengue.

● DDT is a well known insecticide, used for killing mosquitoes.

● It is an organic halogen compound known as chlorobenzene.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Introduction to Haloarenes:
● In chlorobenzene, the halogen atom is attached to the
carbon atom of an aromatic ring.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Introduction to Haloarenes:
● The organohalogen compounds in which the halogen atom
(F, Cl, Br or I) is directly attached to an aromatic ring are
called the haloarenes.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Haloarenes:
● Haloarenes are obtained by the replacement of one or more
hydrogen atoms of an aromatic hydrocarbon by an equal
number of halogen atoms.

-H
Ar- H Ar- X
+X
Aromatic Haloarene
hydrocarbon

● Haloarenes are called aryl halides.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Haloarenes:
● In haloarene (aryl halide), the carbon atom attached to the
C–Cl bond is sp2 hybridised.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Classification of Haloarenes:
● On the basis of number of halogen atoms-

Monohalogen Dihalogen Polyhalogen

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloarenes:
● In case of monohalogen compounds prefix halo is added
before the name of the aromatic hydrocarbon.

● Monohalogen compounds have same names in common

system as well as in IUPAC system.

● For example:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloarenes:
● Examples:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloarenes:
● For the dihalogen derivative, the prefixes o-, m-, and p- are
used before the name of the haloarenes in the common
system.

● Examples:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloarenes:
● In the IUPAC system, the position of the substituents is
defined by numbering the carbon atoms of the ring such that
the substituents are located at the lowest possible numbers.

● Examples:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nomenclature of Haloarenes:

Common name p-Chlorotoluene o-Chlorotoluene sym-Tribromobenzene

IUPAC Name 4-Chlorotoluene 2-Chlorotoluene 1,3,5-Tribromobenzene

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Methods of Preparation of Haloarenes:

From Diazonium Salt By Electrophilic Substitution

Reactions of Benzene
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes from Diazonium Salt:
Sandmeyer’s reaction:
● In this reaction diazonium salt is warmed with Cu2Cl2 in HCl or Cu2Br2 in HBr to
form corresponding halide.

Cu2Cl2 or Cu2Br2
Diazonium salt + HCl or HBr Chloro or Bromo derivative

● Diazonium salt is prepared by treating aniline with NaNO2 and HCl at 0 – 5°C.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes from Diazonium Salt:
Sandmeyer reaction:

● Examples-

Aniline Benzenediazonium chloride

Benzenediazonium chloride Bromobenzene

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes from Diazonium Salt:
Gattermann reaction:

● In this reaction, diazonium salt is warmed with Cu powder and HCl or

HBr to form corresponding chloro- or bromoarene.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes from Diazonium Salt:
Replacement of Diazonium Group by Iodine:

● When benzenediazonium chloride is treated with the excess of KI,

iodobenzene is formed.

Benzenediazonium chloride Iodobenzene

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes from Diazonium Salt:
Replacement of Diazonium Group by Fluorine:

● For the preparation of fluorobenzene, benzenediazonium chloride is

treated with fluoroboric acid (HBF4).

NaNO2 HBF4
+
HCl, 278 K △

Benzene diazonium chloride Fluorobenzene

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes:
By Electrophilic Substitution Reaction:

● Chlorobenzene as well as bromobenzene can be prepared by the

electrophilic substitution reaction of benzene.

● This reaction is carried out at low temperature, in the absence of

sunlight and in the presence of Lewis catalyst such as FeCl3 and
anhydrous AlCl3.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes by Electrophilic Substitution Reaction:
● Examples:

Anhyd AlCl3

Benzene
Chlorobenzene

Anhyd AlCl3

Benzene Bromobenzene

● Fluoro compounds are not prepared by this method because of the high reactivity of
fluorine.
● The reaction of fluorine with benzene is very violent and cannot be easily controlled.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes by Electrophilic Substitution Reaction:
● Electrophilic substitution reaction of benzene with I2 is reversible
in nature.

Benzene
Iodobenzene

● Hence, the presence of an oxidising agent (HNO3,HIO4) is required

to oxidise the HI formed during iodination.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Preparation of Haloarenes by Electrophilic Substitution Reaction:
● When toluene is taken as a starting material, the substituted
halobenzene can be prepared.

Toluene o- Chlorotoluene
p- Chlorotoluene

● Ortho and para isomers can be easily separated by the fractional

distillation due to a large difference in their melting points.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloarenes:
1. Melting and Boiling Points:

Most of the haloarenes are liquids at room temperature.

For the same aryl group, the melting and boiling point increases as
the size of the halogen atom increases.

Order of Melting and Boiling Point

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloarenes:
● The boiling points of ortho, para and meta isomers are nearly the
same.

o- Dichlorobenzene p- Dichlorobenzene m-Dichlorobenzene

B.p. 453 K B.p. 448 K B.p. 446 K
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloarenes:
● The melting point of the p-isomer of dihalobenzene is always
higher than that of o- and m- isomer.

Name o- Dichlorobenzene m- Dichlorobenzene p- Dichlorobenzene

m.p. 256 K 249 K 323 K

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloarenes:
● The p-dichlorobenzene is highly symmetrical as compared to the
ortho- and meta-isomers and therefore, its molecules are closely
packed in crystal lattice.

● Hence, the para-isomer has stronger intermolecular force of

attraction and high melting point as compared to ortho- and
meta-isomers.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloarenes:
2. The density of haloarenes follows the order:

Iodobenzene Bromobenzene Chlorobenzene Fluorobenzene

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Physical Properties of Haloarenes:
3. Solubility:

Although the C–X bond is polar, the haloarenes are insoluble in

water because of the greater effect of the non-polar nature of the
aromatic ring.

These are however soluble in non-polar solvents.

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Chemical Properties of Haloarenes:

Reactions of Haloarenes

Nucleophilic Electrophilic
Reaction with
Substitution Substitution
Metals
Reaction Reaction
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
● Haloarenes are comparatively unreactive towards nucleophillic
reagents under ordinary laboratory conditions.

● Reasons for low reactivity of haloarenes are:

i. Resonance effect

ii. Difference in hybridisation of carbon atom in C–X bond

iii. Instability of phenyl cation

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
Resonance effect:

● In haloarenes, the lone pair of electron on the halogen atom is in

conjugation with the -electron of the ring.

● Thus, the lone pair of electron is delocalised over the benzene ring
due to resonance.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
Resonance effect:

● Due to resonance, the C–Cl bond acquires a partial double bond

character.

● As a result, the bond cleavage in haloarenes is difficult. Therefore,

they are less reactive towards the nucleophilic substitution
reaction.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
Difference in hybridisation of C-atom in C–X bond:

sp2 hybridised
sp3 hybridised
carbon
carbon

sp2 hybridised carbon

● As a result, the breaking of the C–X bond in the haloarenes is

difficult as compared to the alkyl halides

● In other words, the carbon atom attached to halogen atom in

haloarenes has lesser tendency to release the electrons.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
● sp2 hybridised carbon is more electronegative as compared to the
sp3 hybridised carbon atom. Hence, the sp2 hybridised carbon atom
holds the shared pair of electrons more tightly as compared to the
sp3 hybridised carbon atom.

● This tendency shortens the bond length of C–X bond in the aryl
halides.

● Since, the shorter bond length is difficult to break as compared to

the longer bond length, the aryl halides are less reactive than the
alkyl halides.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
Polarity of C- CI Bond:

● The low polarity of the C–Cl bond in chlorobenzene is also

responsible for its lesser reactivity as compared to the
chloroalkanes.
● This is again due to the difference in the hybridisation state of the
carbon atom of the C–Cl bond.

sp2 hybridised sp3 hybridised

carbon carbon

Chlorobenzene Chloromethane
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Nucleophilic Substitution Reaction:
Instability of Phenyl Cation:

● Phenyl cation formed as a result of the self-ionisation is not

stabilized by resonance. Therefore, SN1 mechanism is ruled out.

Aryl halide Phenyl cation

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Example of Nucleophilic Substitution Reaction of Haloarenes:
Replacement by Hydroxyl Group:

● Chlorobenzene, when heated with an aqueous solution of NaOH,

gives sodium phenoxide.

● Sodium phenoxide upon acidification, gives phenol.

dil HCl

Chlorobenzene Sodium
Phenol
phenoxide
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Replacement by Hydroxyl Group:

● Nucleophilic substitution reaction of the aryl halide takes place in

two steps.

First Step:

Nucleophile Chlorobenzene Carbanion

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Replacement by Hydroxyl Group:

● Carbanion formed is resonance stabilised.

● Here, we see that the negative charge gets dispersed over the
benzene ring.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Replacement by Hydroxyl Group:

Second Step:

Carbanion Phenol
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Effect of presence of electron withdrawing group:

● The presence of an electron withdrawing group at the ortho and

para positions increases the reactivity of the haloarenes towards
the nucleophilic substitution reaction.

Example:

In the presence of an electron withdrawing group, the replacement

of the halogen by the hydroxyl group takes place at the lower
temperature.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Effect of presence of electron withdrawing group:

● The electrophilic substitution reaction of chlorobenzene takes place

at 623 K.

(i) NaOH, 623K

(ii) H+
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Effect of presence of electron withdrawing group:

● When an electron withdrawing group is attached to the

para-position, the nucleophilic substitution of chlorobenzene takes
place at 443 K.

(i) NaOH, 443K

(ii) H+
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Reason for increase in reactivity:

● Electron withdrawing group stabilises the intermediate carbanion

formed during the reaction.

● In case of o-and p-chloronitrobenzene, one of the resonating

structure contains a negative charge on the carbon atom bearing
the electron withdrawing –NO2 group.

● NO2 group as well as the -electrons of the benzene contributes in

the resonance stabilisation of the carbanion.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Reason for increase in reactivity:
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Case 1: When an electron withdrawing group is present at p-position.

● It is clear from the above resonating structures that –NO2 group is

contributing in the dispersal of the negative charge.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Step 2-

− Cl
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Case 2: When an electron withdrawing group is present at the o-position.

Step 1-

Carbanion
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:

● It is clear from the above resonating structures that –NO2

group present at the ortho position is also contributing in the
dispersal of the negative charge.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Step 2-

o- Nitrophenol
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Case 3: When an electron withdrawing group is present at the m-position.

Step 1-

Carbanion
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:

● –NO2 group present at the m-position does not stabilise the carbanion by
the resonance effect.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Mechanism of the Nucleophilic Substitution Reactions of Haloarenes:
Step 2-

m- Nitrophenol

● Hence, we can conclude that the presence of the electron withdrawing

group at the o- and p-positions (but not at m-positions) in haloarenes,
increases the reactivity of the ring towards the nucleophilic substitution
reaction.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Electrophilic Substitution Reactions:
● Haloarenes undergo the usual electrophilic substitution reactions of
the benzene ring such as halogenation, nitration, sulphonation,
Friedel-Craft alkylation and Friedel-Craft acylation.

● The halogen atom attached to the aromatic ring directs the incoming
electrophile to the ortho- and para- position.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Electrophilic Substitution Reactions:

● Presence of halogen atom in benzene ring increases the electron

density at the 2,4 and 6 positions.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Electrophilic Substitution Reactions:
● The halogen atom of haloarenes has –I effect.

● Due to its –I effect, the halogen atom has some tendency to

withdraw electrons from the ring. Thus, it will deactivate the ring
also.

● As a result, chlorobenzene undergoes electrophilic substitution

reaction less readily as compared to benzene.
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Example of Electrophilic Substitution Reaction of Haloarenes:
Halogenation Reaction-

● Haloarenes react with halogens in the presence of ferric chloride to

form o- and p-substituted dihalogen compounds.

Example

Anhyd. FeCl3

Chlorobenzene
1,4- Dichlorobenzene 1,2- Dichlorobenzene
Major Minor
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Example of Electrophilic Substitution Reaction of Haloarenes:
Nitration Reaction-

● Chlorobenzene reacts with conc. HNO3 in the presence of conc. H2SO4

to form o- and p-chloronitrobenzene.

Example

HNO3

Conc. H2SO4
Chlorobenzene 1-Chloro-2-nitrobenzene
Minor
1-Chloro-4-nitrobenzene
Major
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Example of Electrophilic Substitution Reaction of Haloarenes:
Sulphonation Reaction-

● In sulphonation SO3H acts as an electrophile. It attacks the electron-rich

haloarene at Ortho and Para positions. The reaction results in the
formation of Para and Ortho Chlorobenzenesulfonic acids, where Para
isomer forms the major product and Ortho isomer forms the minor
product.

conc.
conc.HH2SO
SO
2 44
⃤⃤
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Example of Electrophilic Substitution Reaction of Haloarenes:
Friedel-Crafts Reaction-

● There are generally two types of Friedel-Crafts reaction

1. Friedel-Crafts Alkylation Reactions

2. Friedel-Crafts Acylation Reactions

CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Example of Electrophilic Substitution Reaction of Haloarenes:
Friedel-Crafts Alkylation Reactions-

● Haloarenes and suitable alkyl halides in the presence of a Lewis acid

catalyst form alkyl derivatives of benzene.

AlCl3

Lewis Acid
Toulene By
Benzene Alkyl halide
(main product) product
CLASS 12th CHEMISTRY (IIT-JEE/NEET) - CHAPTER - HALOALKANES AND HALOARENES
Example of Electrophilic Substitution Reaction of Haloarenes:
Friedel-Crafts Acylation Reactions-

● In Friedel-Crafts acylation, benzene derivatives are treated with acid

chlorides(−COCl) or acid anhydrides ((−CO2)O) to produce aromatic
ketones

Benzene Acetyl chloride Acyl group

added to
aromatic
compound