C13.

1 Halogenoalkanes – Introduction

Objectives:

 Explain why halogenoalkanes are more reactive than alkanes.

 Explain why carbon-halogen bonds are polar.
 Explain the trends in bond enthalpy and bond polarity of the carbon-halogen
bond.

Not many halogenoalkanes occur naturally but they are the basis of many synthetic
compounds.
Some examples of these are FVC (used to make drainpipes), Teflon (the non-stick
coating on pans), and a number of anaesthetics and solvents.
The general formula

 The general formula of a halogenoalkane with a single halogen atom is

<^H2n+ix where X is the halogen. This is often shortened to R—X.
 How to name halogenoalkanes
The prefixes fluoro-, chloro-, bromo-, and iodo- tell us which halogen is
present.
 Numbers are used, if needed, to show on which carbon the halogen is
bonded:

 The prefixes di-, tri-, tetra-, and so on, are used to show how many atoms of
each halogen are present.
When a compound contains different halogens they are listed in alphabetical
order, not in order of the number of the carbon atom to which they are
bonded. For example:


is 3-chloro-2-iodopentane not 2-iodu-3-chloropentane. (C is before Tin the
alphabet.)

Bond polarity
Halogenoalkanes have a C — X bond. This bond is polar, CB+—Xs”, because
halogens are more electronegative than carbon.

 The electronegativities of carbon and the halogens are shown in Table 1.

Notice that as you go down the group, the bonds get less polar.

Physical properties of halogenoalkanes

Solubility

• The polar C&+—XB- bonds are not polar enough to make the halogenoalkanes
soluble in water.

 The main intermolecular forces of attraction are dipole-dipole attractions and

van der Waal forces.

* Halogenoalkanes mix with hydrocarbons so they can be used as dry-cleaning

fluids and to remove oily stains. (Oil is a mixture of hydrocarbons.)

Boiling point

The boiling point depends on the number of carbon atoms and halogen atoms.
* Boiling point increases with increased chain length.
• Boiling point increases going down the halogen group.
Both these effects are caused by increased van der Waals forces because the
larger the molecules, the greater the number of electrons.
How the halogenoalkanes react-the reactivity of the C—X bond
When haloeoalkanes react it is almost always the C—X bond that breaks. There
are two factors that determine how readily the C—X bond reacts. These are:
• the C8+—X8′ bond polarity
• the C—X bond enthalpy.

Bond polarity

The halogens are more electronegative than carbon so the bond polarity will be
C6+—Xs”, This means that the carbon bonded to the halogen has a partial positive
charge – it is electron deficient. This means that it can be attacked by reagents that
are electron rich or have electron-rich areas. These are called nucleophiles. A
nucleophile is an electron pair donor.
The polarity of the C—X bond would predict that the C—F bond would be the most
reactive.
Bond enthalpies

 C—X bond enthalpies are listed in Table 2. The bonds gel weaker going
down the group. Fluorine is the smallest atom of the halogens and the
shared electrons in the C—F bond are strongly attracted to the fluorine
nucleus.
 This makes a strong bond. Going down the group, the shared electrons in
the C—X bond get further and further away from the halogen nucleus, so
the bond becomes weaker.

The bond enthalpies would predict that to do-compounds, with the weakest bonds,
are the most reactive, and fluoro-compounds, with the strongest bonds, are the lea
ST reactive.

 Experiments confirm that reactivity increases going down the group. This
means that bond enthalpy is a more important factor than bond polarity.
 Click here for Complete AQA AS Chemistry Revision

13.2 Nucleophilic substitution in halogenoalkanes

Objectives:

 State the definition of a nucleophile.

 Describe nucleophilic substitution.
 Explain why ~OH, ~CN, and NH3 behave as nucleophiles.
 Describe the mechanism of nucleophilic substitution.

Most reactions of organic compounds take place via a series of steps.

You can often predict these steps by thinking about how electrons are likely to
move. This can help you understand why reactions take place as they do and this
can save a great deal of rote learning.

Nucleophiles

Nucleophiles are reagents that attack and form bonds with positively or partially
positively charged carbon atoms.

 A nucleophile is either a negatively charged ion or has an atom with a &-

charge.
 A nucleophile has a lone (unshared) pair of electrons which it can use to
form a covalent bond.
 The lone pair is situated on an electro negative atom.

So, in organic chemistry a nucleophile is a species that has a lone pair of electrons
with which it can form a bond by donating its electrons to an electron deficient
carbon atom. Some common nucleophiles are:

 The hydroxide ion, ~:OH

 Ammonia, SNH^
 The cyanide ion, ~;CN.

They will each replace the halogen in a halogenoalkane. These reactions are
called nucleophilic substitutions and they all follow essentially the same reaction
mechanism.
A reaction mechanism describes a route from reactants to products via a series of
theoretical steps. These may involve short-lived intermediates.

Nucleophilic substitution

The general equation for nucleophilic substitution, using Wu” to represent any
negatively charged nucleophile and X to represent a halogen atom, is:
Reaction mechanisms and curly arrows

 Curly arrows are used to show how electron pairs move in organic
reactions. These are shown here in red for clarity. You can write the above
reaction as:


 The lone pair of electrons of a nucleophile is attracted towards a partially
positively charged carbon atom, A curly arrow starts at a lone pair of
electrons and moves towards C .
 The lower curly arrow shows the electron pair in the C—X bond moving lo
the halogen atom, X, and making it a halide ion. The halide ion is called the
leaving group.
 The rate of substitution depends on the halogen.

Examples of nucleophilic substitution reactions

 All these reactions are similar. Remember the basic pattern, shown above.
Then work out the product with a particular nucleophilic. This is easier than
trying to remember the separate reactions.

Halogenoalkanes with aqueous sodium (or potassium) hydroxide

 The’ nucleophile is the hydroxide ion, ~:OH. This reaction occurs very slowly
at room temperature. To speed up the reaction it is necessary to warm the
mixture.
 Halogenoalkanes do not mix with water, so ethanol is used as a solvent in
which the halogenoalkane and the aqueous sodium (or potassium)
hydroxide both mix. This is called a hydrolysis reaction.
  The rate of the reaction depends on the strength of the carbon-halogen
bond C—F>C—Cl>C—Br>C—I.
 Fluoroalkanes do not react at all whilst iodoalkanes react rapidly.

Halogenoalkanes with cyanide ions

 When halogenoalkanes are warmed with an aqueous alcoholic solution of

potassium cyanide, nitriles are formed. The nucleophile is the cyanide ion, -
:CN.

 The reaction is:

 The product is called a nitrile. It has one extra carbon in the chain than the
starting halogenoalkane. This is often useful if you want to make a product
that has one carbon more than the starting material. Halogenoalkanes with
ammonia
 The nucleophile is ammonia, :NH3.
 The reaction of halogenoalkanes with an excess concentrated solution of
ammonia in ethanol is carried out under pressure. The reaction produces an
amine, RNH2.
 This is the mechanism:
  Ammonia is a nucleophile because it has a lone pair of electrons that it can
donate (although it has no negative charge) and the nitrogen atom has a 5-
charge. Because ammonia is a neutral nucleophile, a proton, H+, must be
lost to form the neutral product, called an amine. The H+ ion reacts with a
second ammonia molecule to form an NH+ ion.

The uses of nucleophilic substitution

 Nucleophilic substitution reactions are useful because they are a way of

introducing new functional groups into organic compounds.
 Halogenoalkanes can be convened into alcohols, amines, and nitriles.
 These in turn can be converted to other functional groups.

Click here for Complete AQA AS Chemistry Revision

13.3 Elimination reactions in halogenoalkanes

Objectives:

 State the definition of an elimination reaction.

  Describe the mechanism for elimination reactions in halogenoalkanes.
 Describe the conditions that favour elimination rather than substitution.

Show when and how isomeric alkenes are formed.

Halogenoalkanes typically react by nucleophilic substitution. But, under different
conditions they react by elimination. A hydrogen halide is eliminated from the
molecule, leaving a double bond in its place so that an alkene is formed.
OH~ ion acting as a base
Under different conditions, the OH~ ion can act as a base, removing an H+ ion
from the halogenoalkane. In this case it is an elimination reaction rather than a
substitution. In the example below, bromoethane reacts with potassium hydroxide
TO form ethene.
A molecule of hydrogen bromide, HBr, is eliminated then the hydrogen bromide
reacts with the potassium hydroxide. The reaction produces ethene, potassium
bromide, and water.

The conditions of reaction

 The sodium (or potassium) hydroxide is dissolved in ethanol and mixed with
the halogenoalkane. There is no water present. The mixture is heated. The
experiment can be carried out using the apparatus shown in Figure 1.
 The product is ethene. Ethene bums and also decolourises bromine
solution, showing that it has a C==C bond.

The mechanism of elimination

Hydrogen bromide is eliminated as follows. The curly arrows show the movement
of electron pairs:

 The OH~ ion uses its lone pair to form a bond with one of the hydrogen
atoms on the carbon next to the C—Br bond. These hydrogen atoms are
very slightly 6+.

* The electron pair from the C—H bond now becomes part of a carbon-carbon
double bond.
* The bromine takes the pair of electrons in the C—Br bond and leaves as a
bromide ion (the leaving group).
This reaction is a useful way of making molecules with carbon-carbon double
bonds.

Substitution or elimination?

Since the hydroxide ion will react with halogenoalkanes as a nucleophile or as a

base, there is competition between substitution and elimination. In general a
mixture of an alcohol and an alkene is produced. For example:

The reaction that predominates depends on two factors – the reaction conditions
(aqueous or ethanolic solution) and the type of halogenoalkanes (primary,
secondary, or tertiary).
The conditions of the reaction

 Hydroxide” ions at room temperature, dissolved in water (aqueous), favour

substitution.
 Hydroxide ions at high temperature, dissolved in ethanol, favour elimination.

The type of halogenoalkane

Primary halogenoalkanes tend to react by substitution and tertiary ones by
elimination. Secondary will do both.
Isomeric products
In some cases a mixture of isomeric elimination products is possible.

Halogenoalkanes and the environment

Chlorofluorocarbons
Chlorofluorocarbons are halogenoalkanes containing both chlorine and fluorine
atoms but no hydrogen, for example, trichlorofluoromethane, CCl3F.

 They are also called CFCs.

 They are very unreactive under normal conditions.
 The short chain ones arc gases and were used, for example, as aerosol
propellants, refrigerants, and blowing agents for foams like expanded
polystyrene.
 Longer chain ones are used as dry cleaning and de-greasing solvents.

CFC gases eventually end up in the atmosphere where they decompose to give
chlorine atoms. Chlorine atoms decompose ozone, Oy in the stratosphere, which
has caused a hole in the Earth’s ozone layer.