HANDOUT 7a – REACTIONS OF HALOGENOALKANES

Objectives:
recall the chemistry of halogenoalkanes as exemplified by the following nucleophilic substitution reactions of
bromoethane: hydrolysis, formation of nitriles, formation of primary amines by reaction with ammonia and by the elimination of hydrogen bromide from 2-bromopropane
describe the mechanism of nucleophilic substitution (by both SN1 and SN2 mechanisms) in halogenoalkanes

BOX 7a-A: REACTIONS OF HALOGENOALKANES Pure NaOH in ethanol BOX 7a-B contd.

Heat under reflux SN1 Mechanism

Halogenoalkanes
NH3(aq) in ethanol alkene This mechanism involves the substitution of a
nucleophile which is first order (one molecule in rate
determining step). This mechanism occurs in two stages:
Heat Heat under reflux
KCN(aq) in ethanol

Stage 1:

Primary amine Heat under reflux NaOH(aq) in ethanol or water in ethanol nitrile CH3 CH3
Nucleophilic Nucleophilic
substitution
H3 C C Br H3C C Br
substitution
alcohol
CH3 CH3
Nucleophilic
substitution
Stage 2:
BOX 7a-B: HETEROLYTIC NUCLEOPHILIC SUBSTITUTION
CH3 CH3
This mechanism is associated with polar covalent bonds (e.g. carbon-halogen).

The positive charge on the carbon H3 C C OH H3 C C OH

δ δ allows attack by nucleophiles such There are two mechanisms for
C Br as :OH− or :CN− which have lone pairs to nucleophilic substitution, (1) SN1 CH3 CH3
donate. and (2) SN2.

SN2 Mechanism
The mechanism involves the substitution of a nucleophile which is second order (two molecules in rate determining step).

The nucleophile attacks the Cδ+ and

H3 C H3 C CH3 starts to form a covalent bond with it. At
the same time the Cδ+-Halδ− bond starts
HO C Br HO C Br to break heterolytically.
HO C Br
This is one continuous process with the
H H H carbon-nucleophile bond getting
H H H stronger and the carbon-halogen getting
transition state weaker.
 HANDOUT 7b – RELATIVE STRENGTH OF C-HAL BONDS

Objectives:
Interpret the different reactivities of halogenoalkanes e.g. CFCs, anaesthetics, flame retardants, and plastics with particular reference to hydrolysis and to the relative strengths of the
C-Hal bonds)
explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative chemical inertness
recognise the concern about the effect of chlorofluoroalkanes on the ozone layernes

BOX 7b-A: REACTIVITIES OF HALOGENOALKANES BOX 7b-B contd.

The relative strength of C-Hal bond is C-Cl > C-F > C-Br > C-I.
In general the greater the bond strength the lower the reactivity so that
fluorocarbons are less reactive than alkanes and the other haloalkanes
increasingly more reactive and less stable from Cl to I.
BOX 7b-B: THE USES OF HALOGEN COMPOUNDS
Due to their inertness and stability, many halogenoalkanes are used in
several purposes.
Plastics
Poly(chloroethene) or PVC and poly(tetrafluoroethene)/PTFE, also
known as Teflon are polymers which are synthesised from
halogenoalkanes.
Anaesthetics
Trichloromethane (chloroform), CHCl3, was once used as anaesthetics.
It was a better anaesthetics than ethoxyethane (ether) which was also
used an Anaesthetics Since ether is highly flammable. However,
although chloroform is not flammable, it causes liver damage. Therefore,
it is seldom in use now.
Flame retardants
CFCs
Chlorofluorocarbons, for example dichlorodifluoromethane or
trichlorofluoromethane, have been used as refrigerant, aerosol
propellants or blowing agents.
The inertness and the high stability of CFCs are the reasons for
choosing these.
However, due to the stability, these agents accumulate in the
atmosphere and when they reach stratosphere, they undergo
photodissociation by ultraviolet radiation which produces chlorine free
radicals.
The radicals decompose ozone into oxygen, thus depleting ozone layer
in the atmosphere.
Therefore, some governments have decided to restrict the uses of CFCs
and change to alternatives such as 1,1,1,2-tetrafluoroethane (CF3CH2F).
The presence of hydrogen atom increases its reactivity so it is broken
down more easily in atmosphere. Even if it reaches stratosphere, it does
not produce the damaging chlorine free radicals.

Bromochlorodifluoromethane (BCF) is very effective at extinguishing fire.

However, it is not in beneral use because the breakdown products are
poisonous.