6-Haloalkanes and Haloarenes - Notes

CHAPTER NOTES
CH(10): HALOALKANES AND HALOARENES
1. Nature of C-X bond in alkyl halides: X is more electronegative than carbon. So, the C-X bond
is polarized with C having a partial positive charge and X having a partial negative charge
2. Preparation of haloalkanes:
3. Preparation of haloarenes:
a) By electrophilic substitution reaction:

b) Sandmeyer’s reaction:
c) Gattermann reaction:
d)
e) Balz – Schiemann reaction:
4. Physical properties of haloalkanes:

a) Solubility:
Although haloalkanes are polar in nature, yet they are practically very slightly soluble in water. In
order for a haloalkane to dissolve in water, energy is required to overcome the attractions
between the haloalkane molecules and break the hydrogen bonds between water molecules,
However, Haloalkanes are not able to form hydrogen bonds with water and therefore, less
energy is released when new attractions are set up between the haloalkane and the water
molecules because these are not as strong as the original hydrogen bonds in water molecules.
As a result, solubility of haloalkanes in water is low.
b) Density:
- Simple fluoro and chloroalkanes are lighter than water while bromides and polychloro
derivatives are heavier than water.
- With the increase in number of carbon atoms, the densities go on increasing.
- With the increase in number of halogen atoms, the densities go on increasing.
- The densities increase in the order: Fluoride < chloride < bromide < iodide
- The density also increases with increasing number and atomic mass of the halogen.
c) Method and Boiling points:

- Molecules of organic halogen compounds are generally polar. Due to the polarity as well as
higher molecular mass as compared to the parent hydrocarbon, the intermolecular forces of
attraction (dipole – dipole and van der Waals) between the molecules are stronger in
halogen derivatives of alkanes. As a result, melting and boiling points of chlorides, bromides
and iodides are considerably higher than those of the parent hydrocarbon of comparable
molecular mass.
- Amongst themselves, the following trends are observed:
o For the same alkyl group the boiling points of alkyl chlorides, bromides and iodides follow the
order RI > RBr > RCl > RF where R is an alkyl group. This is because with the increase in the
size of the halogen, the magnitude of van der Waals force increase.
o In general, the boiling points of chloro, bromo and iodo compounds increase with increase in
the number of halogen atoms.
o For the same halogen atom, the boiling points of haloalkanes increase with increase in the
size of alkyl groups.
o For isomeric alkyl halides, the boiling points decrease with branching. This is because
branching of the chain makes the molecule more compact and, therefore, decrease the
surface area. Due to decrease in surface area, the magnitude of van der Waals forces of
attraction decreases and consequently, the boiling points of the branched chain compound is
less than those of the straight chain compounds.
5. Physical Properties of Haloarenes:

a) These are generally colourless liquids or crystalline solids.
b) These are heavier than water.
c) Melting and boiling points of haloarenes:
Melting and boiling points of haloarenes are nearly the same as those of alkyl halides
containing the same number of carbon atoms.
The boiling points of monohalogen derivatives of benzene are in the order:
iodo > bromo > chloro > fluoro
For the same halogen atom, the melting and boiling points increase as the size of the aryl
group increases.
The melting point of para isomer is quite higher than that of ortho or meta isomers. This is due
to the fast that is has symmetrical structure and therefore, its molecules can easily pack
loosely in the crystal lattice. As a result, intermolecular forces of attraction are stronger and
therefore, greater energy is required to break its lattice and it melts at higher temperature.
6. Chemical properties of haloalkanes:
a) Nucleophilic substitution reaction:
b) Elimination reaction: Dehydrohalogenation (ß - elimination):

When a haloalkane with β-hydrogen atom is heated with alcoholic solution of potassium
hydroxide, there is elimination of hydrogen atom from β-carbon and a halogen atom from the
α-carbon atom. As a result, an alkene is formed as a product. Zaitsev rule (also pronounced as
Saytzeff) is followed.
Saytzeff Rule: It states that “In dehydrohalogenation reactions, the preferred product is that
alkene which has the greater number of alkyl groups attached to the doubly
bonded carbon atoms.”
c) Reaction with metals:

Reaction with Magnesium: Grignard’s reagent is formed:
Wurtz reaction: R-X + 2 Na + X-R → R-R + 2 NaX
Fittig reaction: Ar-X + 2 Na + X-Ar → Ar-Ar + 2 NaX

Wurtz – fittig reaction: R-X + 2 Na + X-Ar → R-Ar + 2 NaX
7. Chemical properties of haloarenes:
Dow’s process:
8. Some important reactions for conversions:
From Grignard’s reagent:

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CHAPTER NOTES

CH(10): HALOALKANES AND HALOARENES

a) By electrophilic substitution reaction:

e) Balz – Schiemann reaction:

4. Physical properties of haloalkanes:

c) Method and Boiling points:

5. Physical Properties of Haloarenes:

b) Elimination reaction: Dehydrohalogenation (ß - elimination):

c) Reaction with metals:

Wurtz reaction: R-X + 2 Na + X-R → R-R + 2 NaX

Fittig reaction: Ar-X + 2 Na + X-Ar → Ar-Ar + 2 NaX

From Grignard’s reagent:

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