Halogenoalk

anes
Aliza Puri
Introduction
General Formula is CnH(2n+1)X,

where n= Number of carbon atom X= Halogen( F, Cl, Br, I)

H= Hydrogen C= Carbon

Example -: 1,2-dichloropropane, 1-bromo-2-chloroethane,

Chloroethane
Displayed formula of some
Halogenoalkanes

1,2-dibromo-1-chlorobutane 1,3-dibromo-3-chlorobutane

1-Bromopropane 1,2-dichlorobutane
2-chloro-2-methylpropane
2
Polarity in Halogenoalkanes
● C-Cl bond is polar
● Chlorine is more electronegative
than carbon so electrons are more
pulled toward Chlorine.
● Becomes less polar as its chain
length increases
● Insoluble in water due to the
absence of hydrogen bond
● Presence of Permanent dipole-
dipole force
● Undergo nucleophilic substitution.
Types of Halogenoalkanes
● Halogen bonded Carbon atom is bonded with 2 or
3 hydrogen atom. It is also called first degree
halogenoalkanes

● Halogen Bonded carbon atom is bonded with 2 R

group and 1 Hydrogen atom. It is also called second
degree halogenoalkanes

● Halogen bonded carbon atom is bonded with 3 R

group. It is not attached with hydrogen atom. It is
aslo called 3 degree halogenoalkanes
Reactions of
Halogenoalkanes
● Hydrolysis
● Reaction with NaCN/KCN
● Reaction with Ammonia
● Elimination Reaction
Hydrolysis
● Hydrolysis with water cannot be done commercially because
1.Yield is less
2.Needs to be heated for several days
● Therefore, Hydrolysis recommended with NaOH with ethanol as a co-
solvent
● Alcohols are produced
Hydrolysis with AgNO3
Iodoalkanes gives yellow ppt immediately. Bromoalkanes gives cream white
ppt of AgBr on heating. Chloroalkanes form white ppt of AgCl on heating for 5
minutes. Fluoroalkanes gives no ppt at all.

‘The reaction is useful in differentiating organic chlorides, Bromide or Iodide

Reaction with NaCN/KCN
Nitriles are produced

Nucleophilic substitution reaction

Increases chain length by 1 carbon atom

Cyano group replace Halogen

Refluxing needs to be done

Cyanide ion is the nucleophile

Further Reaction of Nitriles
1. Hydrolysis
Carboxylic acid is produced
along with ammonia
Heated in acidic solution
2. Reduction
Amines are produced
The reagents used could be Na in
ethanol, NaBH4 or LiAlH4
Reaction with Ammonia
Primary amines are produced

Nucleophilic Substitution. Halogen is replaced by amine group

Heated in a sealed metallic container:Bomb where pressure is generated and reaction

takes place

Ammonia act as nucleophile as it contain lone pair of electron. Excess ammonia is used.

In this case ethylamine is also a nucleophile so it can futher react to form secondary
amine i.e. diethylamine.
Elimination Reaction
Alkenes are produced.

Halogenoalkane when react with NaOH in alcoholic

ethanol, elimination reaction takes place. Reflux
needs to be done

Loss of water molecules

Hydrogen halide is removed from the

halogenoalkanes. H combines with OH from NaOH
to form water while halogen combines with Na to
form the salt.

Potassium hydroxide is used in place of NaOH

because it is more soluble than NaOH.
 Substitution
SN1
Double step
Tertiary Halogenoalkanes
Rates of reaction= = [Tertiary
halogenoalkanes
First step is the heterolysis of Carbon
halogen bond. It is a slow step
Second step is the formation of C-OH
bond. It is fast step.
SN2
Single step
Primary Halogenoalkanes undergo this
mechanism
Rate of reaction= [primary
halogenoalkanes] [NaOH]
Breaking of carbon halogen bond and
formation of C-OH bond occurs at the
same time. In intermediate compound, one
of the carbon is seemed to have five bond.
Reactivity trend of Halogenoalkanes
Relative reactivities of halogenoalkanes

Reactivity of Halogenoalkanes
C-F 467 KJ per mol increases down the group

Iodo Compounds are most reactive

while fluorocompunds are least
C-Cl 346 KJ per mol reactive

The bond energy of C-F is greatest

C-Br 290 KJ per mol so it is least reactive while the
bond energy of C-I is least so it is
most reactive
C-I 228 KJ per mol
Uses of Halogenoalkanes
Important in chemical industry

Used as an intermediate compound

Various insecticides such as BHC, DDT are halogenoalkanes

It is used to make plastics such as PVC and tetrafluoroethene. These plastics

are used to make utensils, pipes and many more.

Halogens such as 2-bromo-2-chloro-1,1,1-fluoroethane are used as

anaesthesia.
 CFC ( Chlorofluorocarbon)
Dibromo dichloroethane

Ideal properties to use as an aerosol

propellant and refrigerant heat
transfer fluids

Chemically inert and hence safe to

use in earth’s surface

However it was found to react with

ozone layer in stratosphere resulting
in the depletion of ozone layer