REACTIONS OF
HALOGENOALKANES
Learning Objective
16.1.a
recall the chemistry of halogenoalkanes as exemplified by:
(i) the following nucleophilic substitution reactions of bromoethane:
hydrolysis, formation of nitriles, formation of primary amines by reaction with
ammonia
(i) the elimination of hydrogen bromide from 2-bromopropane
16.1.b
describe the SN1 and SN2 mechanisms of nucleophilic substitution in
halogenoalkanes including the inductive effects of alkyl groups (see LO 15.2.c)
16.1.c
recall that primary halogenoalkanes tend to react via the SN2 mechanism; tertiary
halogenoalkanes via the SN1 mechanism and secondary halogenoalkanes by a
mixture of the two, depending on structure
Key concepts
Experiments and evidence,
Patterns in chemical behaviour and reactions,
Chemical bonds
Learning Objectives
Keywords
Electrophile/nucleophile
Addition
Substitution
Elimination
Curly arrow
Mechanism
What are halogenoalkanes?
Introduction
► Halogenoalkanes are used in many industrial
chemical processes.
► Unlike some of the elements from which they are
formed, such as fluorine and chlorine, many
halogenoalkanes are relatively unreactive under
normal conditions.
This leads to their use
as flame retardants
and anaesthetics.
Figure 16.1 An anaesthetist
putting a patient to sleep
before an operation
► If you have ever had an operation, you may have a
halogenoalkane to thank for putting you to sleep.
► You might have heard of an early anaesthetic called
chloroform. Its systematic name is trichloromethane.
Nowadays you may receive a gas known as ‘halothane’:
► However, under other conditions, such as high in the
Earth’s stratosphere, some halogenoalkanes react in
completely different ways.
► We can think of the halogenoalkanes
as alkanes that have one or more
hydrogen atoms replaced by halogen
atoms.
► 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. The
presence of the halogen atom has a
huge effect on the reactivity of the
halogenoalkanes compared with that of
the alkanes.
Types of halogenoalkanes
Figure shows Reflux apparatus for hydrolysis of a
halogenoalkane.
e.g. bromoethane + aqueous NaOH
Nucleophilic
substitution
e.g. 2-chloropropane + aqueous NaOH
Nucleophilic
substitution
e.g. 1-bromopropane + aqueous NaOH
Nucleophilic
substitution
e.g. 2-iodo-3-methylbutane + aqueous NaOH
Nucleophilic
substitution
Nucleophilic
substitution
e.g. 2-chloropropane + ethanolic
KCN
Nucleophilic
substitution
e.g. 1-bromobutane + ethanolic
KCN
Nucleophilic
substitution
e.g. HX + aqueous ammonia
Nucleophilic
substitution
e.g. 2-chloropropane + excess hot conc NH3
Nucleophilic
substitution
e.g. 2-bromo-3-methylbutane + excess hot conc NH3
Nucleophilic
substitution
Chemsheet 1198,1139
Mechanism notes for A level
•Hot, ethanolic KOH (not warm,
aq NaOH)
•Lose X and H from adjacent C
(if there is one)
•Forms alkene(s)
•Can get different alkenes
depending which adjacent C the
H comes from
•OH- acts as base (not Elimination
nucleophile)
e.g. 2-chloropropane + hot ethanolic
KOH
Elimination
e.g. 2-bromobutane + hot ethanolic
KOH
Elimination
Sn1 and Sn2 mechanisms –refer slides
Exit Task:
primary halogenoalkanes react mainly by S N
2
mechanism
tertiary halogenoalkanes react mainly by S N
1
mechanism.
WHY?
-inductive effect?
-consider how the inductive effect would stabilise an
intermediate cation if the mechanism is SN1?
An inductive effect is an electronic effect due to
the polarisation of σ bonds within a molecule or ion.
This is typically due to an electronegativity
difference between the atoms at either end of the
bond.
tertiary stable so Sn1-slow fast step
Primary polar so nucleophile can attack.
