Class 12 Haloalkanes Notes

Unit – 10 HALOALKANES & HALOARENES
The main topics covered in this part are:
1. Introduction to haloalkanes and haloarenes

2. Classification of haloalkanes
3. Nature of C─X bond in haloalkanes
4. Preparation of haloalkanes
5. Physical properties of haloderivatives
6. Reactions of Haloalkanes
7. Stereoisomerism
8. Definition: Enantiomers, Racemic mixture, Racemisation
9. Reactions of haloarenes
Haloalkane and Haloarene:
In aliphatic or aromatic compounds, the replacement of hydrogen atom(s) by

halogen atom(s) results in the formation of alkyl halide (haloalkane) and aryl
halide (haloarene), respectively.
In case of haloalkanes, halogen atom is attached to the sp3 hybridised carbon

atom of an alkyl group whereas in haloarenes, halogen atom is attached to sp2
hybridised carbon atom of an aryl group.
Classification of Haloalkanes:
The halogen derivatives of hydrocarbons may be classified as fluoro, chloro,

bromo or iodo compounds according to the type of halogen present.
Depending upon the number of halogens present, the halogen derivatives can be
classified as mono, di, tri or polyhalo compounds.
On the basis of the nature of the carbon to which halogen atom is attached,
halogen derivatives are classified as 1o, 2o, 3o, allylic, benzylic, vinylic and aryl
derivatives.
For example:
1o, 2o and 3o halides: halogen atom is bonded to primary, secondary or tertiary

carbon atom of an an alkyl group.
Allylic halides: Halogen atom is bonded to an sp3-hybridised carbon atom next
to carbon-carbon double bond (C=C) i.e. to an allylic carbon.
Benzylic halides: Halogen atom is attached to an sp3 - hybridised carbon atom

next to an aromatic ring.
Vinylic halides: Halogen atom is bonded to an sp2-hybridised carbon atom of a

carbon-carbon double bond (C = C).
Aryl halides: Halogen atom is bonded to the sp2-hybridised carbon atom of an

aromatic ring.
Note: Here X represents a halogen atom, i.e., X= F, Cl, Br, I.
Nature of C-X bond in haloalkanes:
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.
Preparation of Haloalkanes:
Haloalkanes can be prepared by a number of methods:
1. By free radical halogenation of alkanes:
Chlorination or bromination of alkane usually gives a complete mixture of

isomeric mono and poly halo alkanes.
2. By electrophilic addition of HX to alkene:
An alkene is converted to corresponding alkyl halide by reaction with

hydrogen chloride, hydrogen bromide or hydrogen iodide.
3. From alcohol:
The hydroxyl group of an alcohol is replaced by halogen on reaction with

concentrated halogen acids, phosphorus halides or thionyl chloride to give
the corresponding alkyl halide.
4. By halogen exchange:
(a) Finkelstein reaction:
Alkyl iodides can be prepared by the reaction of alkyl chlorides/

bromides with NaI in dry acetone.
(b) Swarts reaction:
Alkyl fluorides can be prepared by heating an alkyl

chloride/bromide in the presence of a metallic fluoride such as AgF,
Hg2F2, CoF2 or SbF3.
Preparation of Haloarenes:
Haloarenes can be synthesized by any of the following reactions:
1. By electrophilic substitution reaction:
This involves the direct halogenation of benzene ring in the presence of

Lewis acid catalysts like iron or iron (III) chloride.
2. By Sandmeyer’s reaction:
Aniline is treated with sodium nitrite to give a diazonium salt which is

then treated with cuprous chloride or cuprous bromide to produce the
corresponding aryl halide:
Physical properties of Haloalkanes derivatives:
Physical properties of halo-derivative are different than those of the simple

hydrocarbons. These are described below:
1. Alkyl halides are colourless when pure but bromides and particularly
iodides develop colour when exposed to light.
2. The alkyl halides have higher molecular mass as compared to alkanes.
3. Halogen compounds have higher boiling points than the corresponding

hydrocarbon. This is because the greater polarity as well as higher
molecular mass as compared to the parent hydrocarbon causes the
intermolecular forces of attraction (dipole-dipole and van der Waals) to be
stronger in the halogen derivatives.
4. For monohalogen compounds, the boiling point increases with increasing

molecular mass of the halogen group with a fixed hydrocarbon group.
R‒F < R‒Cl < R‒Br < R‒I
5. All halogen derivatives of hydrocarbon are insoluble in water as they are

incapable of forming hydrogen bonds with water but alkyl halides are
soluble in non-polar solvents.
6. The density increases with increasing number and the atomic mass of the
halogen.
7. Halogen compounds are less inflammable than the hydrocarbons. The

inflammability decreases with increasing halogen content.
Reactions of Haloalkanes:
The reactions of haloalkanes may be divided into the three main categories:
(i) Nucleophilic substitution

(ii) Elimination reactions
(iii) Reaction with metals
Nucleophilic substitution:
A nucleophile attacks the haloalkane which is having a partial positive charge on

the carbon atom bonded to halogen. Halide ion separates following a
substitution reaction.
Reactivity of Haloalkanes towards nucleophilic substitution:
For the same alkyl group, as we move from F to I, strength of C−X bond
decreases, therefore, the reactivity order is: R− I > R−Br > R−Cl > R−F
Mechanism of nucleophilic substitution reaction:
The nucleophilic substitution reaction can proceed via SN1 mechanism or

SN2mechanism.
1. Unimolecular nucleophilic substitution, SN1:
This type of nucleophilic substitution takes place in two steps, first step
being the rate determining step involves the formation of carbonium ion.
The reactivity order of haloalkanes towards SN1reaction is:

1° R−X < 2° R−X < 3° R−X
2. Bimolecular nucleophilic substitution, SN2:
This type of nucleophilic substitution takes place in one step. The

incoming nucleophile interacts with alkyl halide causing the C−X bond
bond to break while forming a new C−OH bond.
The reactivity of alkyl halide towards SN2 reaction is:

3° R−X < 2° R−X < 1° R−X

Elimination reactions:
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 resulting in the formation of an alkene.
The reaction follows the Saytzeff rule which 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.”
Reaction with metals:
Reaction with Magnesium:
Alkyl halides react with magnesium in the presence of dry ether to form
corresponding alkyl magnesium halide which is also known as Grignard’s
reagent.
Recation with sodium:
Alkyl halides react with sodium to form an alkane with double number of carbon
atom than that present in alkyl halide. This reaction is also known as Wurtz
reaction.
2R‒X + 2 Na → R‒R + 2NaX
Reactions of Haloarenes:
Nucleophilic substitution:
Aryl halides are almost unreactive towards nucleophilic substitution reaction.

This is because of double character of C – X bond due to resonance. Therefore, it
is difficult to remove X from C – X bond.
Effect of - NO2 group on the reactivity of aryl halide towards nucleophilic
substitution reactions:
Presence of an electron withdrawing group like NO2 group increases the

reactivity of aryl halides towards nucleophilic substitution reaction.
NO2 group increases the reactivity more when present at o- and p- position due
to the increased delocalization of negative charge involving NO2 group.

Class 12 Haloalkanes Notes

Uploaded by

Copyright:

Available Formats

Class 12 Haloalkanes Notes

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Class 12 Haloalkanes Notes

Uploaded by

Copyright:

Available Formats

Unit – 10 HALOALKANES & HALOARENES

The main topics covered in this part are:

1. Introduction to haloalkanes and haloarenes

Haloalkane and Haloarene:

In aliphatic or aromatic compounds, the replacement of hydrogen atom(s) by

In case of haloalkanes, halogen atom is attached to the sp3 hybridised carbon

The halogen derivatives of hydrocarbons may be classified as fluoro, chloro,

1o, 2o and 3o halides: halogen atom is bonded to primary, secondary or tertiary

Benzylic halides: Halogen atom is attached to an sp3 - hybridised carbon atom

Vinylic halides: Halogen atom is bonded to an sp2-hybridised carbon atom of a

Aryl halides: Halogen atom is bonded to the sp2-hybridised carbon atom of an

Note: Here X represents a halogen atom, i.e., X= F, Cl, Br, I.

Nature of C-X bond in haloalkanes:

Haloalkanes can be prepared by a number of methods:

1. By free radical halogenation of alkanes:

Chlorination or bromination of alkane usually gives a complete mixture of

2. By electrophilic addition of HX to alkene:

An alkene is converted to corresponding alkyl halide by reaction with

The hydroxyl group of an alcohol is replaced by halogen on reaction with

(a) Finkelstein reaction:

Alkyl iodides can be prepared by the reaction of alkyl chlorides/

(b) Swarts reaction:

Alkyl fluorides can be prepared by heating an alkyl

Haloarenes can be synthesized by any of the following reactions:

1. By electrophilic substitution reaction:

This involves the direct halogenation of benzene ring in the presence of

Aniline is treated with sodium nitrite to give a diazonium salt which is

Physical properties of halo-derivative are different than those of the simple

2. The alkyl halides have higher molecular mass as compared to alkanes.

3. Halogen compounds have higher boiling points than the corresponding

4. For monohalogen compounds, the boiling point increases with increasing

R‒F < R‒Cl < R‒Br < R‒I

5. All halogen derivatives of hydrocarbon are insoluble in water as they are

7. Halogen compounds are less inflammable than the hydrocarbons. The

(i) Nucleophilic substitution

A nucleophile attacks the haloalkane which is having a partial positive charge on

Reactivity of Haloalkanes towards nucleophilic substitution:

Mechanism of nucleophilic substitution reaction:

The nucleophilic substitution reaction can proceed via SN1 mechanism or

1. Unimolecular nucleophilic substitution, SN1:

The reactivity order of haloalkanes towards SN1reaction is:

1° R−X < 2° R−X < 3° R−X

2. Bimolecular nucleophilic substitution, SN2:

This type of nucleophilic substitution takes place in one step. The

The reactivity of alkyl halide towards SN2 reaction is:

3° R−X < 2° R−X < 1° R−X

When a haloalkane with β-hydrogen atom is heated with alcoholic solution of

Reaction with metals:

Reaction with Magnesium:

Recation with sodium:

2R‒X + 2 Na → R‒R + 2NaX

Aryl halides are almost unreactive towards nucleophilic substitution reaction.

Presence of an electron withdrawing group like NO2 group increases the

You might also like