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HALOALKANES
HALOARENES

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 Course content
➢ Introduction, Nomenclature, Classification and isomerism
➢ Preparation of mono haloalkanes from alkanes, alkenes,
and alcohols
➢ Physical properties
➢ Chemical properties
▪ Reactivity of different alkyl halide
▪ Nucleophilic substitution reactions (Reactions with KOH,
RONa, KCN, AgCN, AgNO2, Alc. NH3, CH3COOAg, KSH)
▪ Elimination reaction (Dehydro-halogenation)
▪ Grignard’s reaction
▪ Reduction reaction
▪ Wurtz’s reaction
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❑Polyhaloalkane
➢ Laboratory preparation of chloroform
(Trichloromethane)
➢ Physical properties
➢ Chemical properties: Action with air
(Oxidation), silver powder, aqueous alkali,
acetone, nitric acid, carbylamine reaction,
Reimer- Tiemann reaction, reduction reaction
➢ Uses of chloroform
➢ Iodoform and iodoform test or reaction

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❑Haloarene
➢Preparation of chlorobenzene from
i. Benzene
ii. Benzene diazonium chloride
iii.Phenol
➢ Physical properties
➢ Chemical properties
▪ Reactivity of haloarene relatives to haloalkane
▪ Nucleophilic substitution reactions
▪ Reduction of chlorobenzene
▪ Electrophilic substitution reaction
▪ Action with metals (Na and Mg)
▪ Action with chloral
➢ Uses
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 Haloalkanes (Alkyl halides)
Introduction
Haloalkane are the halogen derivatives of alkane, which
are obtained by replacing one or more H-atom by halogen atoms.
Or
The organic compound containing halogen atom (X = -F, -
Cl, -Br, -I) as functional group are called haloalkanes.
+X
R-H -H
R-X
Alkane Haloalkane

They are also called alkyl halides.

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Classification of haloalkane
a. On the basis of number of halogen atoms
According to the number of halogen atoms
present in the molecule, haloalkanes can be classified
into mono, di, tri, tetra halogen derivatives and so on.
Example:
i. Monohaloalkane
CH3-Cl CH3CH2-Cl
Chloromethane Chloroethane
ii. Dihaloalkane Cl Cl
CH2-Cl2 CH2-CH2
Dichloromethane 1,2-dichloroethane
(Geminal dihalide) (Vicinal dihalide) 6
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iii. Trihaloalkane
CHCl3 Cl2-CH-CH2-Cl
Trichloromethane 1,1,2-trichloroethane
(Chloroform)

iv. Tetrahaloalkane
CCl4 Cl2-CH-CH2-Cl2
Tetrachloromethane 1,1,2,2-tetrachloroethane

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b. On the basis of nature of carbon atom
Depending upon the nature of carbon atom
bonded with halogens, haloalkane are classified
into primary (10), secondary (20), tertiary (30)
haloalkane.
i. Primary (10) haloalkane
The haloalkane in which carbon atom carrying
halogen atom further bonded to one carbon atom
(one alkyl group) is called primary haloalkane.

R-CH₂−X CH₃−CH₂−Cl
(10-Carbon) Chloroethane
primary haloalkane (ethyl chloride)
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ii. Secondary haloalkane (20)
The haloalkane in which the halogen containing
carbon is further bonded to two carbon atom (two
alkyl group) is called secondary haloalkane.

R CH₃
R−CH−X CH3-CH-Cl
(20-Carbon)
0 2
2-chloropropane
(isopropyl chloride)

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3. Tertiary haloalkane (30)
The haloalkane in which the halogen containing
carbon is further bonded to three carbon atom
(three alkyl group) is called tertiary haloalkane.
CH₃
R
R−C−X CH₃−C−Cl
30

R CH₃
(30-Carbon) 2-chloro-2-methylpropane
(tert-butyl chloride)

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… Nomenclature of haloalkanes
A. Common system:
▪ In common system, haloalkane are named by
adding the word halide after the name of alkyl
group.
▪ The words n-, sec-, tert-, iso- and neo- are
usually used in writing common names.
Common name of alkyl halide is always written as two
separate words.

Example : n- = straight chain

CH₃-CH₂-CH₂-Br CH₃- CH₂- CH₂-CH₂-I

n-Propyl bromide n-Butyl iodide
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sec- = 20 (At least C4) tert- = 30
Br CH₃
CH₃-CH2-CH-CH CH₃-C-Cl
30
3
20
sec-butyl bromide CH₃
tert-butyl chloride
iso- = (If second last carbon contains one methyl group and
no other branches) second last carbon
CH3
CH3
CH₃-CH-Cl CH₃-CH-CH2-Br

iso-propyl chloride iso-butyl bromide

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neo- = (If second last carbon contains two methyl group and no
other branches i.e. one 40 carbon)
second last carbon
CH3 CH3
CH₃-C-CH2-Br CH₃-C-CH2-CH2-Br
0 4 40
CH3 CH3
neo- Pentyl bromide neo- Hexyl bromide

B. IUPAC system:
▪ In IUPAC system, haloalkane are named by
adding prefix ‘halo-’ before the name of parent
alkane.
IUPAC name of any monohalo alkane is always written as one
words.
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Formula Common name IUPAC name
CH₃-I Methyl iodide Iodomethane

CH₃-CH₂-Cl Ethyl chloride Chloroethane

CH₃-CH₂-CH₂-Br n-Propyl bromide Bromopropane

Cl
CH₃-CH-CH iso-propyl chloride 2-chloropropane
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Br
CH₃-CH2-CH-CH3 sec-butyl bromide 2-bromobutane
CH₃
CH₃-C-Cl tert-butyl chloride 2-Chloro-2-
CH₃ methylpropane
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CH₃-CH-CH2-Br iso-butyl bromide 1-bromo-2-

methylpropane

CH3
CH₃-C-CH2-Br neo- pentyl bromide 1-bromo-2,2-
4
0
dimethylpropane
CH3

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Polyhalogen compounds:
Organic compounds containing more than one halogen
atom in their molecules are known as polyhalogen
compounds.
Example:
Cl Cl

H-C-Cl Cl-C-Cl

Cl Cl
IUPAC: Trichloromethane IUPAC: Tetrachloromethane
Common: Chloroform Common: Carbon tetrachloride

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Cl
CH2-CH
Cl
Note: Geminal dihalide is
IUPAC: 1,1-dichloroethane a compounds have
Common: Ethylidene dichloride halogens on same
( Geminal dichloride ) carbon atom.

Cl Cl
CH2-CH2 Note: Vicinal dihalide is a
IUPAC: 1,2-dichloroethane compounds have
Common: Ethylene dichloride halogens on adjacent
( Vicinal dihalide )
carbon atoms.
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 Isomerism in haloalkanes
1. Chain isomerism
Haloalkanes having same molecular formula but
differ in the nature of carbon chain are called chain
isomers.
Example: C5H11Br CH₃
CH₃CH₂CH₂CH₂CH₂-Br CH₃CHCH₂CH₂-Br
1-bromopentane 1-bromo-3-methylbutane
(n-pentyl bromide) (iso-pentyl bromide)
CH3
CH3-C-CH2-Br

CH3
1-bromo-2,2-dimethylpropane
(neo-pentyl bromide)
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 2. Position isomerism
Haloalkanes having same molecular formula but
different position of halogen atom on carbon chain
are called position isomers.
Examples: Cl
CH₃CH₂CH₂−Cl CH₃−CH−CH₃
1-chloropropane 2-chloropropane
(n-propyl chloride) (isopropyl chloride)

Q. Write down all the possible isomers of molecular formula-

i) C4H9Br ii) C5H11Br.
Give their IUPAC names and also specify them as 10, 20 and 30
haloalkanes.
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General methods of preparation of haloalkane

1. From alkanes (Halogenation of alkanes)

In this method, haloalkanes are prepared by the
action of alkane with limited amount of halogen in
presence of sunlight or heat or oxidizing agent.
Example:
R-H + X₂ ⟶ R-X + HX
Alkane Haloalkane
a. Chlorination
hν
CH₃CH₃ + Cl₂ CH₃CH₂Cl + HCl
ethane chloroethane
On excess supply of chlorine polysubstituted
products are formed.
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 …
CH₄ + Cl₂ CH₃Cl CH₂Cl₂ CHCl₃
(excess) chloromethane hϑ -HCl

CCl₄
tetrachloromethane
In case of higher alkanes two or more possible products
are formed.
Cl
CH₃CH₂CH₃ + Cl₂ CH₃CHCH₃ + CH₃CH₂CH₂-Cl
Propane 2-chloropropane 1-chloropropane
major product (55%) (45%)
(more stable)
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 b.
… Bromination
Bromine reacts with alkanes slowly, so heat is
required to increase the rate of the reaction.
Heat
CH4 + Br₂ CH3Br + HBr
Methane
Bromoethane
c. Iodination
CH3-H + I₂ CH3 -I + HI
The iodination of alkane is reversible reaction
because HI produced during the reaction is a strong
reducing agent which reduces CH3I back to the
methane (CH4) . So this reaction is carried out in the
presence of strong oxidizing agent like conc. HNO₃ or
HIO₃ etc. These oxidizing agent can oxidize HI to I2 and
prevent the backward reaction.
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CH₄ + I₂ CH₃I + HI
Methane Iodomethane

2HNO₃ + 2HI ⟶ 2H₂O + 2NO₂ + I₂

HIO₃ + 5HI ⟶ 3H₂O + 3I₂
Iodic acid

Reactivity of alkane = 3˚ > 2˚ > 1˚

Reactivity of halogen = F > Cl > Br > I

Note: Fluorination of alkane occurs violently.

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2. From alkenes (Hydrohalogenation of alkenes)
The haloalkane are prepared by the reaction of
alkene with halogen acid (HF HCl, HBr, HI). This
reaction is called Hydrohalogenation reaction.
CH₂=CH₂ + HCl ⟶ CH₃CH₂Cl
Ethene Chloroethane
If unsymmetrical alkene is taken then two possible
product are formed.
Cl
CH₃CH=CH₂ + HCl ⟶ CH₃CHCH₃ + CH₃CH₂CH₂Cl
Propene 2-chloropropane 1-chloropropane

The formation and stability of these two products

can be explained by following two rules:
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 [A] Markovnikov’s rule:
According to this rule “Addition of acid halide HX ( HCl,
HBr, HI) on unsymmetrical alkene follows in such a way that
the positive part of HX added to that double bonded carbon
containing greater number of hydrogen atoms”.
Example:
Cl
CH₃-CH=CH₂ + HCl ⟶ CH₃-CH-CH₃ + CH₃CH₂CH₂-Cl
Propene 2-chloropropane (20%)
(major product)
(80%)(more stable)

Why??
This reaction proceeds through the formation of more
stable (2˚) carbocation @BishalThapa 25
 Mechanism: @BishalThapa
+ -
Step-I: H-X H + X
Electrophile
+ - + +
Step-II: CH₃-CH=CH₂ ⟶ CH₃-CH-CH2+ H CH₃-CH-CH3
20 carbocation
If, (More stable)

- + + +
CH₃-CH=CH₂ ⟶ CH₃-CH-CH2+ H CH₃-CH2-CH2
10 carbocation
(Less stable)
Since, 20 carbocation is more stable due to the presence of
electron releasing group (+I effect) on its either sides.
+ +
CH₃ CH CH3 electron releasing group CH₃-CH2 CH2
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+ -
CH₃-CH-CH3 + X CH₃-CH-CH3
It follows Electrophilic addition mechanism.

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