Halogenalkanes

Halogenalkanes
The simplest halogenoalkanes, whose molecules contain

just one halogen atom, will have the general formula
CnH2n+ 1X, where X is F, Cl, Br or I.
Nucleophilic substitution reactions
1. Substitution reactions with aqueous alkali, OH –(aq)
When an aqueous solution of sodium hydroxide is added

to a halogenoalkane, the halogen atom in the halogenoalkane
is replaced by an OH.
The aqueous hydroxide ion behaves as a nucleophile because

it is donating a pair of electrons to the carbon atom bonded
to the halogen in the halogenoalkane.
This why the reaction is called a nucleophilic substitution.
2. Substitution with cyanide ions, CN– (in ethanol)
In this reaction the nucleophile is the cyanide, CN –, ion. To

carry out the reaction, a solution of potassium cyanide, KCN,
in ethanol (known as an ethanolic or alcoholic solution of
potassium cyanide) is made up. This is then heated under
reflux with the halogenoalkane.
3. Substitution with ammonia, NH3 (in ethanol)
If a halogenoalkane is heated with an excess of ammonia

dissolved in ethanol under pressure, an amine is formed
Mechanism for primary halogenoalkanes (SN2)
In primary halogenoalkanes containing one halogen atom, the
halogen atom is bonded to a carbon atom, which is itself
bonded to one other carbon atom and two hydrogen atoms.
This means that the carbon atom bonded to the halogen is
attached to one alkyl group.
The mechanism of nucleophilic substitution in a primary halogenoalkane.

The OH– ion donates a pair of electrons to the δ+ carbon
atom, forming a new covalent bond. At the same time,
the C-Br bond is breaking.
This mechanism is called an SN2 mechanism. The ‘S’ stands for
substitution and the ‘N’ stands for nucleophilic.
The ‘2’ tells us that the rate of the reaction, which is determined
by the slow step in the mechanism involves two reacting
species.
Experiments show us that the rate depends on both the
concentration of the halogenoalkane and the concentration of
the hydroxide ions present.
Outline a mechanism for each this following reaction
Mechanism for tertiary halogenoalkanes (SN1)
A tertiary halogenoalkane reacts with a hydroxide ion by a

two-step mechanism. The first step in the mechanism is
the breaking of the carbon–halogen bond. This forms a
tertiary carbocation, which is attacked immediately by the
hydroxide ion
The ‘1’ tells us that the rate of the reaction only depends on
one reagent, in this case the concentration of the
halogenoalkane, as shown in the first (slow) step of the
mechanism.
The Br– ion forms again, as in the SN2 mechanism, but in this
mechanism a carbocation ion forms. This does not happen
with primary halogenoalkanes. This is because tertiary
carbocations are more stable than primary carbocations due
to the inductive effect of the alkyl groups attached to the
carbon atom bonded to the halogen.
The SN1 mechanism and the SN2 mechanism are both likely
to play a part in the nucleophilic substitution of
secondary halogenoalkanes.
Note that:
■■ the fastest nucleophilic substitution reactions take place
with the iodoalkanes
■■ the slowest nucleophilic substitution reactions take place
with the fluoroalkanes.
The substitution reaction involves the breaking of the carbon
halogen bond. Looking at the bond energies
Iodoalkanes are the most reactive because they have the
weakest bond of C-I, thus they are most easily
broken,making them most reactive.
The mechanism for the reaction between
2-bromo-2-methylpropane and hydroxide ions
OH-
Elimination reactions
Halogenoalkanes also undergo elimination reactions.
An elimination reaction involves the loss of a small molecule
from the original organic molecule
The original 2-bromopropane molecule has lost an H atom and

a Br atom. We can think of it as HBr being eliminated from the
halogenoalkane. The ethanolic OH– ion acts as a base,
accepting an H+ from the halogenoalkane to form water.
The Role of Nucleophile Vs Base
Substitution: Elimination:
The lone pairs on the oxygen can The hydroxide ion hits
attack the slightly positive one of the hydrogen
carbon. This leads on to the loss atoms in the CH3 group
of the bromine as a bromide ion, and pulls it off resulting
and the -OH group becoming the formation of a C=C
attached in its place. and the loss of the
bromine as Br-.
The Zaitsev Rule
Elimination reactions usually occur such that they are

removing a hydrogen from the carbon attached to the fewest
hydrogens.
This is called “Zaitsev’s rule”.
So when you form an alkene in an elimination reaction, make

sure you form the most substituted alkene as the major
product.
Practice
1 Give the mechanism for the following reactions
2 2-bromobutane reacts with sodium hydroxide solution
under suitable conditions to give a mixture of but-1-ene
and but-2-ene.
a) Write the mechanism for the formation of but-1-ene.
b) Write the mechanism for the formation of but-2-ene
3 Give two possible products of this elimination reaction and

assigns both major and minor product
CH3CH2OH
4 Identify whether the following substrate is more likely
to participate in an SN2 or SN1 reaction:
5 The more-substituted alkene is called the Zaitsev product,
and the less-substituted alkene is called the Hofmann
product. Usually, the Zaitsev product is the major product:
Give the mechanism for the following reactions
OH, ethanol
-
b OH
CH3CH2OH
c
CH3CH2OH

Halogenalkanes

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Halogenalkanes

The simplest halogenoalkanes, whose molecules contain

When an aqueous solution of sodium hydroxide is added

The aqueous hydroxide ion behaves as a nucleophile because

In this reaction the nucleophile is the cyanide, CN –, ion. To

If a halogenoalkane is heated with an excess of ammonia

The mechanism of nucleophilic substitution in a primary halogenoalkane.

A tertiary halogenoalkane reacts with a hydroxide ion by a

The original 2-bromopropane molecule has lost an H atom and

Elimination reactions usually occur such that they are

This is called “Zaitsev’s rule”.

So when you form an alkene in an elimination reaction, make

3 Give two possible products of this elimination reaction and

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