Monday, 04 January 2021

NUCLEOPHILIC SUBSTITUTION
Starter:
1. Draw all isomers of pentanol using skeletal formulae

Draw 3-bromo-2-chloro-2,3-dimethylbutanoic acid

Lesson Objectives
◦ Understand that halogenoalkanes undergo
nucleophilic substitution with nucleophiles
◦ Be able to outline the mechanism with
nucleophiles
◦ Be able to explain why the C – X bond enthalpy
influences the rate of reaction
Definitions
◦ A nucleophile is a chemical species that donates
an electron pair to form a chemical bond in relation
to a reaction. It either has a negative charge or
lone pair.
◦ A nucleophilic substitution reaction is where one
functional group is replaced (substituted) by
another.

Keywords: halogen, halogenoalkane, alkane,

nucleophilic substitution, functional group, amine,
hydroxide, nitrile
MEET THE ATTACKERS

I HAVE A LONE PAIR WHICH I CAN

USE TO FORM A NEW BOND.
I ATTACK ELECTRON DEFICIENT
AREAS (with a + or d+)
MEET THE ATTACKERS

I HAVE AN UNPAIRED ELECTRON

WHICH I WANT TO PAIR UP. I AM
VERY REACTIVE AND DON’T MIND
WHERE I ATTACK… WATCH OUT!
WHO IS ATTACKED?
THE BONDING IN A MOLECULE
INFLUENCES WHAT WILL ATTACK IT

Bond has twice as many electrons – species

MULTIPLE which like electrons will be attracted
WHO IS ATTACKED?
THE BONDING IN A MOLECULE
INFLUENCES WHAT WILL ATTACK IT

Bond has twice as many electrons – species

MULTIPLE
which like electrons will be attracted

Similar atoms have an equal attraction for

NON-POLAR the shared pair of the covalent bond
 WHO IS ATTACKED?
THE BONDING IN A MOLECULE
INFLUENCES WHAT WILL ATTACK IT

Bond has twice as many electrons –

MULTIPLE species which like electrons will be
attracted
Similar atoms have an equal attraction
NON-POLAR for the shared pair of the covalent bond
d+ d- Atoms have different electronegativity's
and the shared pair will be attracted
POLAR more to one end – species known as
nucleophiles will be attracted to the
slightly positive end
Polar bonds and nucleophiles
The carbon–halogen bond in halogenoalkanes is polar
δ+ δ- δ+ δ- δ+ δ- δ+ δ-

The polar bond means that the carbon atom has a small positive charge,
which attracts substances with a lone pair of electrons. These are
nucleophiles, meaning nucleus loving.

ammonia cyanide hydroxide

 TIP: Always draw the arrow
coming from the lone pairs to
Reaction basics…. gain the mark
◦ You need to know the mechanism of nucleophilic substitutions for
halogenoalkanes.
◦ The general equation is: CH3CH2X + Nu- CH3CH2Nu + X-

The lone pair of electrons on the nucleophile attack the

slightly positive carbon heterolytically. As carbon can
only have 4 bonds and the X is already slightly negative
it heterolytically removes itself to form a halide with a
lone pair.
Halogenoalkane and hydroxide ions
The reaction between warm aqueous sodium or potassium hydroxide is a
much quicker substitution then that of water.
Generic Equation : R-X +OH- R-OH + X-
2 step process
1. The nucleophile attacks the delta positive carbon (polar C-X bond) with
its lone pairs.
2. The electrons close to the delta negative halogen jump onto the
bromine breaking the C-Br bond heterolytically.

TIP: Always ensure

the charges balance
Halogenoalkane and water
The same reaction can also happen with water and is called hydrolysis.
(DEFINITION: splitting of a molecule with water)
Cold water slowly hydrolyses halogenoalkanes, replacing the halogens
with –OH groups.
Water is acting as a nucleophile
E.g. CH3CH2CH2I + H2O  CH3CH2CH2OH + H+ + I-

Halogenoalkanes do not mix with aqueous solutions so the reaction is

carried out in ethanol.
Halogenoalkane and nitriles cyanide ions
Nitriles have CN
When HX is heated under reflux with a solution functional groups. It is
of KCN (Potassium cyanide) in ethanol a carbon triple bonded
nucleophilic substitution can take place. to a nitrogen. The
carbon has a lone
Very similar process where the nucleophile
pair and as a result a
attacks the delta positive carbon. The arrows negative charge.
must go from the carbon. The carbon halogen
bond then breaks

Very useful reaction as it is a way of increasing carbon

chain length by 1 carbon but why under reflux, what is
reflux explain?
Practice – Draw the mechanism for 2
methyl propane and OH- and CN- Challenge
include all
nomenclature
Does the nature of the halogenoalkane
affect the mechanism? 1°, 2°,3°
• Yes and predominantly due to steric hindrance
• We know that the C – X bond is electron withdrawing so we need to look at
the R groups connected to the C to see their effect once the X has been
removed.

• Groups of atoms with lots of electrons, high electron density like methyl
groups can push their cloud of electrons towards a positive charge stabilising
it. The more groups like this you have around a + charge the more stable it is
and the more likely to react it will be. This is the inductive effect.
1° Halogenoalkanes
• Due to the lack of an inductive effect there is no formation of a stable
cation intermediate. In fact the nucleophile attaches and this additional
bond forces the breaking of the C – X bond.

◦ Rather than completely breaking the bond, the polar bond between the
halogen and carbon produces a partial +ve charge on the carbon. This is
enough to attract a nucleophile to form a high energy transition state,
which effectively has 5 bonds, one to the nucleophile, one with
the halogen and 3 others.
This is the rate determining step (second step) , hence
the SN2.
3° Halogenoalkanes
• Due to the large inductive effect of the three R groups this allows the
formation if a stable cation intermediate

• Steric hindrance prevents nucleophile attacking.

There is no room on the δ+ C for the nucleophile to attack as the bulky
CH3 groups block access. It has to wait until the halogen falls off.
• The first step is rate determining so SN1
• (2° can do both)
• But this is more year 13 so don’t worry about it now.
Draw full mechanism for 1bromoethane
and 2 fluoropentane with hydroxide

SN2
Reaction
Halogenoalkane and Amines Ammonia can act
as a nucleophile
(ammonia molecules) because of
nitrogen's lone pair
Amines have the structure R3- N, where R can be H or of electrons.
another group.
• Warming a HX with excess ethanolic ammonia (in
ethanol) in a sealed test tube produces a primary
amine via substitution reactions.
• Very similar 2 step process where the nucleophile
attacks the delta positive carbon. The arrows must go
from the carbon. The carbon halogen bond then
breaks (step 1 as before)
• What is the reason for the next step?
 The problem with
Halogenoalkane and Amines the product is that
(ammonia molecules) it can still act as a
nucleophile as the
what is the reason for the next step?) product ahs a
lone pair and can
• This mechanism forms a cation on the nitrogen. A
undergo further
second ammonia is needed to remove the extra substitution
hydrogen forming an ammonium salt and an amine

Any issues with the final product?

Practice 1- Bromo-butane and ammonia

TIP: you could be

asked to draw this
mechanism so
make sure you
know it.
Finally why does the C – X bond
enthalpy influence the rate of reaction?
• The C – X bond strength (enthalpy) dictates reactivity as it needs to break
• Which is the strongest and why?
• C – F because of its size it has less shielding and so the nucleus of
protons can create a large bond polarity making it a very strong bond.
• This means more energy is required to break the bond and so will dictate
how easy it is to substitute.
• As with C – I having very little polarity it will be the easiest to substitute.
• The same is true ig there are multiple halogens.
Complete questions in textbook
p208
Answers