Naming Halogenoalkanes

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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

1
 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
leaving group combines with a silver ion to form a SILVER HALIDE
PRECIPITATE.
The precipitate only forms when the halide ion has left the
haloalkane and so the rate of formation of the precipitate can be
used to compare the reactivity of the different haloalkanes.
CH3CH2I + H2O  CH3CH2OH + I- + H+
Ag+ (aq) + I-(aq)  AgI (s) - yellow precipitate
The iodoalkane forms a precipitate with the
silver nitrate first as the C-I bond is weakest
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

2
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

3
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-