15 Halogen Compounds

15.1 Halogenoalkanes

Halogenoalkanes are formed when H of an is replaced by a halogen, the haloakanes are

important intermediates in organic synthesis.

The general formula of halogenoalkanes : Cn H2n+1 X

Homologous series CH3 X – Halomethane

C2H5 X – Haloethane

C3H7 X – Halopropane

C4H9 X – Halobutane

C5H11 X – Halopentane

IUPAC Names:

2-bromo-2-methylbutane 1-chloro-3,3-dimethylhexane 3-iodopentane

Halogenoalkanes can be classified as primary, secondary and tertiary

Primary halogenoalkanes

The halogen attached carbon is directly attached to 1C atom or 2 or 3 H atoms

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Secondary halogenoalkanes

The halogen attached carbon is directly attached to 2C atoms and a single H atom

Tertiary halogenoalkanes
The halogen attached carbon is directly attached to 3C atoms and no hydrogen atoms.

Physical properties of halogenoalkanes.

I The lower members of the homologous series are gases and the higher members are
liquids (Exception: iodomethane is a liquid)
II The boiling melting points are higher than the corresponding alkanes because
they contain more electrons, resulting in stronger dispersion forces/Van der
Waals’ force . They also contain permanent dipole- dipole attractions as the C-X
bond is polar.
III Most of them are colourless liquids, which are immiscible inH2O. Even though
they are polar they are insoluble in H2O as + ‘H’ is not available. Therefore they
cannot form ‘H’ bonds with H2O, but they are soluble in organic solvents.

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Preparation of halogenoalkanes

➢ The free-radical substitution of alkanes by chlorine, Cl2, or bromine, Br2, in

ultraviolet light:

➢ The electrophilic addition of an alkene with a halogen, X2, or a hydrogen halide,

HX(g), at room temperature:

➢ substitution of an alcohol.
For example, by reactions:
• with HX(g) (or with KX and Concentrated H2SO4 or Concentrated H3PO4
to make HX),

• with PCl3 and heat:

• with PCl5 at room temperature:

• or with SOCl2:

Explain why a metal halide and concentrated H2SO4 should not be used in the
preparation of a bromoalkane or an iodoalkane.

In the preparation of bromoalkanes, KBr and H2SO4 cannot be used directly as most of
the HBr produced initially would be oxidized to Br2. This is the same reason why metal
halides and concentrated H2SO4 cannot be used to prepare iodoalkanes. Therefore
H2SO4 should be slowly added to the alcohol upon cooling. The mixture is then added to
solid KBr and heated. This prevents the oxidation of hydrogen halide to halogen.

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 Reactions of Haloalkanes

Halogenoalkanes undergo nucleophilic substitution reaction

The C-X bond is polar due to halogen being more electronegative than carbon. The
partial + charge on the ‘C’ atom attracts nucleophiles, resulting in substitution. Hence
halogenoalkanes undergo a Nucleophilic substitution reaction.

The relative reactivity is based on the hydrolysis of the C-X bond. The rate of
hydrolysis is related to the strength of the C-X bond. The stronger the bond, the slower
will be the reaction. The C-I bond is the longest and the weakest. The C-Cl bond is the
shortest and the strongest. The C-I bond can be broken easily when compared to the C-
Cl bond.

Therefore the rate of hydrolysis of iodoalkanes is greater than the rate of hydrolysis of
bromoalkanes, which is greater than the rate of hydrolysis of chloroalkanes.

C-I > C-Br > C-Cl

Nucleophilic substitution

Mechanism for primary halogenoalkanes (SN2)

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The ‘S’ stands for substitution and the ‘N’ stands for nucleophilic. The ‘2’ tells us that
the rate of the reaction, which is determined by the slow step in the mechanism,
involves two reacting species. Experiments show us that the rate depends on both the
concentration of the halogenoalkane and the concentration of the hydroxide
ions present.

Mechanism for tertiary halogenoalkanes (SN1)

The ‘1’ tells us that the rate of the reaction only depends on one reagent, in this case the
concentration of the halogenoalkane, as shown in the first (slow) step of the
mechanism

The SN1 mechanism and the SN2 mechanism are both likely to play a part in the
nucleophilic substitution of secondary halogenoalkanes,Because

• The opposite of the halogen is not cluttered by CH3 group(s)

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 • The secondary carbocation formed is more stable than primary carbocation

Relative reactivities of haloalkanes based on the primary secondary and tertiary

structure.

The reactivity depends on the stability of the carbocation formed during the reaction. If
the carbocation formed is stable then this will result in the more stable compound,
thereby showing the highest rate of reaction. If the carbocation is less stable, then the
product will be less stable and less produced, thus exhibiting a lower rate of reaction.

Carbocations are classified according to the number of alkyl substituents that are
bonded to the positive carbon. A primary carbocation has one substituent, a secondary
has two, and a tertiary has three.

The alkyl groups are electron releasing (because ‘C’ is more negative than ‘H’) hence
alkyl groups decrease the concentration of the positive charge on the ‘C’. Decreasing the
positive charge increases the stability of the carbocations. Therefore the greater the
number of alkyl groups attached to positive carbon, the greater the stability. So
tertiary carbocations are more stable than the secondary, and the secondary
carbocations are more stable than the primary.

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Typical reactions of halogenoalkanes

•
Substitution with hydroxide ions,OH-
•
Substitution with cyanide ions,CN-
•
Substitution with ammonia NH3

• Elimination

• Reaction with water containing AgNO3

Halogenoalkanes undergo Nucleophilic substitution reactions and elimination

reactions.666

➢ Reactions with aqueous alkali:

When a halogenoalkane is mixed with a solution of KOH or NaOH and heated under
reflux, an alcohol is produced. The halogen atom is substituted with the nucleophile
OH – to produce the alcohol.

Thus haloalkanes undergo Nucleophilic substitution with aqueous alkali. The ionic
equation is:-

➢ Reaction with alcoholic Ammonia to form amines

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 Haloalkanes undergo nucleophilic substitution with ammonia to produce amines.
Amines contain –NH2 , -NH- or –N-group.
When a solution of haloalkanes in ethanol is warmed with NH3 in a sealed vessel,
an amine is produced.

The solution must be heated in a sealed container as NH3(g) would be liberated in a

reflux condenser. The product HX produced will react with the excess ammonia to
form the ammonium salt.

The product Primary amine can react with more haloalkanes to produce secondary
and tertiary amines.
C2H5Br + C2H5NH2 (C2H5)2NH +HBr
C2H5Br + (C2H5)2NH (C2H5)3N +HBr

➢ Reaction with ethanolic potassium cyanide ( KCN) to form nitriles

When a haloalkane is heated under reflux with a solution of KCN in ethanol
ethanolic KCN ) produces a nitrile (cyanide) via Nucleophilic substitution reaction.

➢ Reaction with alcoholic potassium hydroxide (Elimination reaction)

A different reaction is observed if haloalkane is refluxed with a concentrated
solution of KOH or NaOH dissolved in ethanol. The ethanolic KOH causes
elimination of a H2O molecules resulting an unsaturated alkene. The halogen atom
is removed with a ‘H’ atom attached to the adjacent carbon.
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 OH- under the above conditions acts as a base & extracts H+ from the carbon adjacent
to the halogen attached carbon. The oH - ion provides both the electrons needed to form
the bond with H+ resulting H2O. When the C-H bond breaks, the C-X bond breaks
heterolytically resulting X- ions. Therefore there must be at least one ‘H’ atom
adjacent to the C-X atom to undergo elimination.

The KOH/NaOH used should not contain any H2O if so, hydrolysis leading to
substitution takes place resulting alcohol. Elimination of 2-chlorobutane produces
two products.

➢ Reaction with water containing silver nitrate solution

Haloalkanes are hydrolysed by cold water replacing the halogen atom with the
-OH group to form alcohols and solution which contain halide anion. As water is
not a good nucleophile, the reaction is slower than that with aqueous NaOH
R-X AgNO3/H2O R-OH + AgX(s)
∆
This halide ion produced by hydrolysis reacts with AgNO3 to form a precipitate of
silver halide.

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 The above reaction can be used to compare the rate of reaction of haloalkanes by
comparing the time taken for the precipitate to appear.
AgCl White ppt (Soluble in ammonia sol.)
AgBr Cream ppt (partially soluble in ammonia sol)
AgI Yellow ppt (Insoluble in ammonia sol)

USES OF HALOGENOALKANES

a. Halogenoalkanes are used as solvents.

Eg: di chloromethane
b. Refrigerants
Chloroflourocarbon(CFC) are used as coolants in refrigerators & in air conditioning
systems. They contain chlorine, Fluorine & carbon. They are unreactive,
nonflammable & nontoxic. The use of CFC is banned due to its effects on the
environment. CFC damages the ozone layer & causes global warming. Alternatives
to CFC such as hydrocholoroflourocarbon (HCFC) & hydrofluorocarbon (HFC) does
not harm the ozone layer as they breakdown before reaching the ozone layer.
c. Manufacture of herbicides

In the manufacture of plant killers halogenoalkanes are used.

d. Manufacture of pesticides
Insect killers mainly contain haloalkanes. The problems associated with the use of
halogeno pesticides & herbicides that they persist in the environment for a long
period of time due to the strength of the C-Cl bond. Therefore can enter in to the food
chain & cause cancer.
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e. Manufacture of fire extinguishers
Eg: CBr2ClF, CF2BrCl & CF3Br
f. Used in the manufacture of plastics

Eg: poly vinyl Chloride (PVC)

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