HALOALKANES

Introduction:
Haloalkanes are the halogen derivatives of alkanes, which are formed by replacing one or more hydrogen
atoms by same number of halogen atoms.
+X
R-H R-X
-H
Alkane Haloalkane
or
X = F, Cl, Br or I
Alkyl halide

Classification of Haloalkanes:
Depending upon the number of halogen atom present in haloalkane, haloalkanes are divided into,
1. Monohaloalkanes: Haloalkane containing one halogen atom.
Monohaloalkanes are further classified into primary haloalkanes ( 1o haloalkanes ), secondary haloalanes ( 2o
haloalkanes and tertiary haloalkanes ( 3o haloalkanes ).

a) Primary haloalkanes ( 1o haloalkanes ) : Halogen atom attached with primary carbon atom.

Primary carbon

CH3 - CH2 - Cl
Chloroethane

b) Secondary haloalanes ( 2o haloalkanes) : Halogen atom attached with secondary carbon atom

Secondary carbon
CH3 - CH - CH3
Br
2-bromopropane

c) Tertiary haloalkanes ( 3o haloalkanes ) : Halogen atom attached with tertiary carbon atom

Br Tertiary carbon
CH3 - C - CH3
CH3
2-bromo-2-methylpropane

2. Dihaloalkanes: Haloalkane containing two halogen atom.

Dihaloalkanes are further classified into vicinal dihalides, geminal dihalides and polymethylene diahlides,
a) Vicinal dihalides: Two halogen atoms are attached on the adjacent carbon atoms.

Br Br
CH2 - CH2
1,2-dibromoethane
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 b) Geminal dihalides: Two halogen atoms are attached on the same carbon atom.

Cl
CH3 - C - H
Cl
1,1-dichloroethane

c) Polymethylene dihalides: Two halogen atoms are attached on terminal carbon atoms of the chain.

CH2 - CH2 - CH2

Br Br
1,3-dibromopropane

3. Polyhaloalkanes: Haloalkane containing more than two halogen atom.

Cl
Cl
H - C - Cl
CH3 - C - Cl
Cl Cl
Trichloromethane 1,1,1-trichloroethane

Nomenclature of Haloalkanes
IUPAC Name
The IUPAC name is Haloalkane. In IUPAC system, the name of halogen atom is written first followed by the name of
alkane from which it is derived.
[ Halo + alk + ane]
Common Name:
In common system, they are called alkyl halides. In common system, the name of the alkyl groups are written first,
followed by the word halide. [Alkyl + halide]
Prefix n- is used for linear haloalkane containing carbon 3 or more
Prefix Iso – is used for haloalkane containing carbon 3 or more
Prefix Sec – is used for haloalkane containing carbon 4 or more
Prefix Tert – is used for haloalkane containing carbon 4 or more
Prefix Neo – is used for haloalkane containing carbon 5 or more

Structural formula IUPAC name Common name

CH3 – Cl Chloromethane Methyl chloride
CH2 CH2 – Br Bromoethane Ethyl bromide
CH3 CH2 CH2 – I Iodopropane n – propyl iodide
CH3 – CH – CH3 2-chloropropane Isopropyl chloride
|
Cl
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 CH3 CH2 CH2 CH2 – Cl Chlorobutane n – butyl chloride
CH3 – CH – CH2 – Cl 1-chloro -2-methylpropane Isobutyl chloride
|
CH3
CH3 – CH2 – CH – Cl 2-chlorobutane Sec-butylchloride
|
CH3
CH3
|
CH3 – C – Cl 2-chloro-2-methylpropane Tert-Butyl chloride
|
CH3
CH3
|
CH3 – C – CH2 - Cl 1-chloro-2,2-dimethylpropane Neo-pentylchloride
|
CH3
CHCl3 Trichloromethane Chloroform
CHBr3 Tribromomethane Bromoform
CHI3 Triiodomethane Iodoform

Isomerism:
Compounds having same molecular formula but different physical and chemical properties are called isomers
and the phenomenon is called isomerism. Isomerism is broadly divided into two types, Structural and Stereo
isomerism.
Compounds having same molecular formula but different structures are known as structural isomers.
Haloalkanes exhibit two types of structural isomerism.

1. Chain isomerism:
Same molecular formula but differ in length of carbon chain. Haloalkanes containing 4 or more carbon atoms
show chain isomerism.
Chain isomers of C4H9Cl are,
CH3 - CH - CH2 - Cl
CH3 - CH2 - CH2 - CH2 - Cl CH3
Chlorobutane 1-chloro-2-methylpropane

2. Position isomerism:
Same molecular formula but differ in position of functional group. Haloalkanes containing 3 or more carbon
atom show position isomerism.
Position isomers of C3H7Br are,
CH3 - CH - CH3
CH3 - CH2 - CH2 - Br Br
Bromopropane 2-bromopropane

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