16 Halogenoalkanes

Naming Halogenoalkanes H H H
H

H C H
H H
Based on original alkane, with a prefix indicating halogen atom:
H
H C C C H
Fluoro for F; Chloro for Cl; Bromo for Br; Iodo for I. H C C C C H

Br H H H Cl H H
Substituents are listed alphabetically
1-bromopropane 2-chloro-2-methylbutane
Classifying halogenoalkanes
Haloalkanes can be classified as primary, secondary or tertiary depending on the
number of carbon atoms attached to the C-X functional group.
H
H H H H H H
H C H
H H H
H C C C H H C C C H
H C C C C H

Br H H H Br H H Cl H H

Primary halogenoalkane Secondary halogenoalkane Two Tertiary halogenoalkane Three

One carbon attached to the carbon carbons attached to the carbon carbons attached to the carbon
atom adjoining the halogen atom adjoining the halogen atom adjoining the halogen

Reactions of Halogenoalkanes Halogenoalkanes undergo either Organic reactions are

substitution or elimination reactions classified by their
mechanisms
1. Nucleophilic substitution reactions
Substitution: swapping a halogen atom for another atom or groups of atoms

Nucleophile: electron pair donator e.g. :OH -, :NH3, CN-

:Nu represents any nucleophile – they always
The Mechanism: We draw (or outline) mechanisms to show have a lone pair and act as electron pair
in detail how a reaction proceeds donators

Nu:-
The nucleophiles
H H The carbon has a small
attack the positive H H positive charge because of
carbon atom
the electronegativity
H C C δ+ X δ- H C C Nu + X- difference between the
carbon and the halogen
H H
H H

We use curly arrows in mechanisms (with

A curly arrow will always start from
two line heads) to show the movement of
a lone pair of electrons or the centre
two electrons
of a bond

The rate of these substitution reactions depends on the strength of the C-X Bond enthalpy /
bond kJmol-1
The weaker the bond, the easier it is to break and the faster the reaction.
C-I 238
C-Br 276
The iodoalkanes are the fastest to substitute and the fluoroalkanes are
the slowest. The strength of the C-F bond is such that fluoroalkanes are C-Cl 338
very unreactive
C-F 484

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 Comparing the rate of hydrolysis reactions

Hydrolysis is defined as the splitting of a molecule ( in this case a Water is a poor nucleophile but it can react
haloalkane) by a reaction with water slowly with haloalkanes in a substitution
reaction
CH3CH2X + H2O  CH3CH2OH + X- + H+

Aqueous silver nitrate is added to a haloalkane and the halide CH3CH2I + H2O  CH3CH2OH + I- + H+
leaving group combines with a silver ion to form a SILVER HALIDE
Ag+ (aq) + I-(aq)  AgI (s) - yellow precipitate
PRECIPITATE.
The precipitate only forms when the halide ion has left the The iodoalkane forms a precipitate with the
haloalkane and so the rate of formation of the precipitate can be silver nitrate first as the C-I bond is weakest
used to compare the reactivity of the different haloalkanes. and so it hydrolyses the quickest

The quicker the precipitate is formed, the faster the substitution AgI (s) - yellow precipitate
reaction and the more reactive the haloalkane AgBr(s) – cream precipitate forms faster
The rate of these substitution reactions depends on the strength of the AgCl(s) – white precipitate
C-X bond . The weaker the bond, the easier it is to break and the faster
the reaction.

Nucleophilic substitution with aqueous hydroxide ions

Change in functional group: halogenoalkane  alcohol H H H
H H H
Reagent: potassium (or sodium) hydroxide
H C C C Br + KOH  + KBr
Conditions: In aqueous solution; Heat under reflux H C C C OH

Mechanism:Nucleophilic Substitution H H H H H H

Role of reagent: Nucleophile, OH- 1-bromopropane propan-1-ol

The OH– is a stronger nucleophile than water as it has a full negative The aqueous conditions needed is
charge and so is more strongly attracted to the Cδ+ an important point. If the solvent is
changed to ethanol an elimination
reaction occurs

SN2 nucleophilic substitution mechanism for halogenoalkanes

H CH3 H - H
δ+ δ-
H3C C Br HO C Br H3C C OH + :Br -
-HO:
H H
H
transition state.

This mechanism occurs with primary halogenoalkanes

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SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes

Tertiary haloalkanes undergo nucleophilic substitution in a different way

Tertiary halogenoalkanes
CH3 CH3 CH3 undergo this mechanism as the
+ tertiary carbocation is made
H3C C Br H3C C :OH- H3C C OH
stabilised by the electron
CH3 CH3 CH3 releasing methyl groups around it.
(see alkenes topic for another
The Br first breaks example of this).
The hydroxide Also the bulky methyl groups
away from the
nucleophile then prevent the hydroxide ion from
haloalkane to form
attacks the positive attacking the halogenoalkane in
a carbocation
carbon the same way as the mechanism
intermediate
above

Primary halogenoalkanes don’t do the SN1 mechanism because they would only form an unstable primary
carbocation.

Nucleophilic substitution with ammonia

Change in functional group: halogenoalkane 

amine H H H
H H H

Reagent: NH3 dissolved in ethanol

H C C C Br + 2NH3  H C C C NH2 + NH4Br
Conditions: Heating under pressure in a sealed
tube H H H
H H H

Mechanism: Nucleophilic Substitution propylamine

Type of reagent: Nucleophile, :NH3

Naming amines:
In the above example
H H H propylamine, the propyl shows
δ+ δ- the 3 C’s of the carbon chain.
CH3 CH2 C Br
+ :Br -
CH3 CH2 C N H Sometimes it is easier to use the
3HN: IUPAC naming for amines e.g.
H H H Propan-1-amine
:NH3

CH3 CH2 C NH2 + NH4Br

H

Further substitution reactions can occur between the haloalkane and the amines
formed leading to a lower yield of the amine. Using excess ammonia helps
minimise this.

H R
Further reactions H H
RX RX
RX R N:
H N: H N: R N:

H R R R

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Nucleophilic substitution with cyanide ions

Change in functional group: halogenoalkane  H H H H H H

nitrile
Reagent: KCN dissolved in ethanol/water mixture H C C C Br + :CN-  H C C C CN + Br-
Conditions: Heating under reflux H H H
H H H
Mechanism: Nucleophilic Substitution
1-bromopropane butanenitrile
Type of reagent: Nucleophile, :CN-

Note: the H H This reaction increases the length of

mechanism is δ+ δ- the carbon chain (which is reflected in
identical to the H3C C Br H3C C CN + :Br - the name) In the above example
above one -NC: butanenitrile includes the C in the
H H nitrile group

Naming Nitriles

Nitrile groups have to be at the end of a chain. Start

numbering the chain from the C in the CN Note the naming: butanenitrile and not
butannitrile.
CH3CH2CN : propanenitrile

H3C CH CH2 C N 3-methylbutanenitrile

CH3

Elimination reaction of halogenoalkanes Elimination: removal of small molecule

(often water) from the organic molecule
Elimination with alcoholic hydroxide ions
H H H H H H
Change in functional group: halogenoalkane 
alkene H C C C H + KOH  H C C C + KBr + H2O
Reagents: Potassium (or sodium) hydroxide H H
H Br H
Conditions: In ethanol ; Heat
2-bromopropane propene
Mechanism: Elimination
Type of reagent: Base, OH-

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Uses of Halogenoalkanes
chloroalkanes and chlorofluoroalkanes can be used as solvents Halogenoalkanes have also been
used as refrigerants, pesticides
CH3CCl3 was used as the solvent in dry cleaning
and aerosol propellants
Many of these uses depended on the unreactivity of Fluorine containing
compounds. They often had low flammability

Many of these uses have now been stopped due to the toxicity of
halogenoalkanes to the atmosphere and also their detrimental
effect on the atmosphere

Ozone Chemistry

The naturally occurring ozone (O3) layer in the upper Ozone in the lower atmosphere
atmosphere is beneficial as it filters out much of the sun’s is a pollutant and contributes
harmful UV radiation towards the formation of smog

Man-made chlorofluorocarbons (CFC’s) caused a hole to form in the ozone

layer.
Chlorine atoms are formed in the upper atmosphere when energy from
ultra-violet radiation causes C–Cl bonds in chlorofluorocarbons (CFCs) to CF2Cl2  CF2Cl  + Cl
break

The chlorine free radical atoms catalyse the

.
Cl + O3  ClO + O2
.
decomposition of ozone due to these reactions .
ClO + O3  2O2 + Cl
.
because they are regenerated. (They provide an
alternative route with a lower activation energy) Overall equation
2 O3  3 O2
They contributed to the formation of a hole in the
ozone layer. The regenerated Cl radical means
that one Cl radical could destroy
many thousands of ozone molecules

Legislation to ban the use of CFCs was supported by HFCs (Hydro fluoro carbons) e.g..
chemists and that they have now developed CH2FCF3 are now used for refrigerators
alternative chlorine-free compounds and air-conditioners. These are safer
as they do not contain the C-Cl bond

The C-F bond is stronger than the C-Cl bond and is not affected by UV

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