Note Haloalkanes

Haloalkanes:
Physical Properties
1. Physical state
State: Lower members CH3Cl, CH3CH2Cl, CH3Br are gaseous, other alkyl halide up to C18 are liquid
and beyond C18 are solid.
Color: Colorless
2. Solubility
Even the C – X bond in haloalkane in polar in nature but due to inability to form intermolecular H-bond.
They are insoluble in water.
They mainly dissolve in organic solvents like, alcohol, ether, benzene etc.
3. Boiling Point
Haloalkanes have higher boiling point than corresponding alkanes.
I) for same alkyl group but different halogen atom, increasing order of boiling point is
RCl< RBr <RI
because with increase in the size and mass of halogen atom, magnitude of van der Waal’s force of attraction
increases and boiling point also increases.
Example: CH3CH2Cl < CH3CH2Br < CH3CH2I
II) For different alkyl group but same halogen atom (i.e. for Isomeric alkyl halide) , Boiling point
decrease with the increase in the branching in alkyl group because with the increase in branching, the
haloalkane molecule attain spherical shape with less surface area thus strength of van der Waal’s
force of attraction also decreases and boiling point also decreases.
Example:
Chemical Properties
Haloalkanes are highly reactive organic compounds. They mainly undergo substitution, elimination and reduction
reactions. Also, they react with metals and form organometallic compounds.
(A) Nucleophilic substitution reactions in Haloalkanes:
The C – X bond in haloalkane is polar in nature. Since halogen atom is more electronegative as compared
to carbon. Hence the C - atom to which halogen is present is electron deficient in nature. Therefore it is a
good site for a nucleophile to attack. Infact, the nucleophilic substitution reactions are the most common
reactions for Haloalkanes.
Haloalkanes undergo nucleophilic substitution reactions by two mechanism;
i. SN1 Mechanism
1|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

It refers to unimolecular nucleophilic substitution reaction. In SN1 mechanism, the rate of reaction depends
upon the concentration of only haloalkane.
Rate = K [ Haloalkanes]
This reaction mechanism proceeds through two steps; (i) Heterolytic fission of C – X bond which results
the formation of carbocation.
ii. The nucleophile then attach the carbocation and results the substituted product.
The order of reactivity in Haloalkane for SN1 reaction follows the order;
ii. SN2 Mechanism:

It refers to bimolecular nucleophilic substitution reaction. In SN2 mechanism, the rate of reaction depends
upon the concentration of both haloalkanes and the nucleophile.
Rate = K [ Haloalkanes] [Nucleophile]
Here, the attack of the nucleophile and the removal of halogen atom takes place simultaneously.
The order of reactivity in haloalkane for SN2 reaction follows the order;

Examples of Nucleophilic substitution reactions
1. Reaction with aq. NaOH or aq. KOH or with moist Ag2O
Haloalkanes when heated with aq. NaOH, aq. KOH, or moist silver oxide give the corresponding
monohydric alcohols.
 
R X + aq. NaOH  R OH + NaX
Example:
  
CH3 CH2 Br + aq. NaOH CH3 CH2 OH + NaBr
Bromoethane Ethanol
Note: Moist Ag2O + H2O  2AgOH, it can produce –OH nucleophile.
2. Reaction with alcoholic KCN solution

When a haloalkane is allowed to react with an alcoholic KCN solution, an alkanenitrile is obtained.
It is one of the best method to increase a carbon atom in an organic compound.
Alkanenitriles are used for the synthesis of various organic compounds.

Example:
i. Partial Hydrolysis of alkanenitriles in the presence of conc. HCl gives an amide.
O
conc. HCl II
R – C  N + H2O  R – C – NH2
Alkanamide
ii. Complete hydrolysis of alkanenitriles with the help of dil HCl or H+/H2O gives carboxylic acid.
O O
H2O / dil HCl II H2O / dil HCl II
R – C  N  R – C – NH2  R – C – OH
Amide Carboxylic acid

iii. Reduction of alkane nitriles by LiAlH4 or Zn / HCl or Na / C2H5OH etc. give 1° amine.
LiAlH4
R – C  N + [H]  R – CH2 – NH2
1° amine
Note: Reduction of nitriles to 1° amine with the help of Na and C2H5OH is referred as Mendius
reaction.
3. Reaction with silver cyanide (AgCN)

When a haloalkane is allowed to react with an alcoholic solution of AgCN, an isocyanide is obtained.
An isocyanide on reduction with the help of LiAlH4 gives 2° amine.

LiAlH4
 C + [H] 
CH3 – CH2 – N = CH3 – CH2 – NH – CH3
ethyl isocyanide Ethyl methyl amine
(2° amine)
Ambident Nucleophiles
The word ambident is derived from two Latin words. ambi = on both sides and dens = tooth. Thus, an
ambident nucleophile has teeth on two sides. This means, it can attack from two different orientations to
give two different products.
Those nucleophiles which can attack the electron deficient centre through two possible sites to give two
different products are called ambident nucleophiles.
Examples:
4. Reaction with potassium nitrite (KNO2)

When a haloalkane is allowed to react with an aqueous solution of KNO2, alkyl nitrite is obtained.

5. Reaction with silver nitrite (AgNO2)
When a haloalkane is allowed to react with an alcoholic solution of AgNO2, a nitroalkane is obtained.
⊝⊕
6. Reaction with sodium alkoxide (RO Na)
When a primary haloalkane is allowed to react with alcoholic solution of sodium or potassium alkoxide,
an ether is obtained.
This reaction is referred as Williamson synthesis reaction.
Therefore, Williamson synthesis reaction is applicable for the synthesis of both symmetrical as well as
unsymmetrical ether.
7. Reaction with ammonia (NH3)

When a haloalkane is allowed to react with an alcoholic solution of NH3 at about 100°C temperature, a
mixture of 1°, 2°, 3° and 4° amine is obtained.
This reaction is called Hoffmann's ammonolysis reaction.
If haloalkane is excess,

Note:

Tetra-alkyl ammonium ion (R4 N) is referred as 4° amine.
8. Reaction with potassium hydrosulphide (KSH)

When a haloalkane is allowed to react with sodium or potassium hydrosulphide, an alkanethiol (alkyl
thioalcohol) is obtained.
9. Reaction with sodiumalkanethionate (NaSR)

When a haloalkane is allowed to react with sodium or potassium alkanethionate, a thioether is obtained.
B. Reaction with metals

1. Reaction with sodium (Wurtz reaction)
When a haloalkane is allowed to react with sodium in presence of dry ether, an alkane having even number
of carbon atoms is obtained. This reaction is referred as Wurtz reaction.
Especially this process is useful for the synthesis of an alkane having even number of carbon atoms. But,
if a mixture of two different haloalkanes are taken then an alkane with odd number of carbon atoms is also
obtained. But the percentage of yield is quite low.
E.g.

3° haloalkanes donot undergo this reaction, because instead of undergoing wurtz reaction, 3° haloalkanes
undergo dehydrohalogenation reaction in presence of strong base eg Na.
This reaction is useful for the preparation of higher symmetrical alkanes.
C. Elimination reaction (Dehydrohalogenation)

Dehydrohalogenation is an example of elimination reaction.
When a haloalkane is heated with an alcoholic solution of KOH or NaOH an alkene is obtained due to
dehydrohalogenation.
e.g.
The order of reactivity of different haloalkanes towards elimination reaction is given by,
3° haloalkane > 2° haloalkane > 1° haloalkane
Saytzaff's rule
If more than one products are obtained during dehydrohalogenation of a haloalkane, then the major product
is given by saytzaff's rule.
This rule states, during dehydrohalogenation of a haloalkane, if more than one products i.e. alkenes are
obtained, then the highly substituted alkene is the major product.
Eg.: Dehydrohalogenation of 2-chlorobutane gives two products i.e. but-1-ene and but-2-ene.
Out of these two products but-2-ene is highly substituted alkene. Hence, it is the major product according
to Saytzaff's rule.
D. Reduction reaction
When a haloalkane is reduced by Zn/HCl or HI/red P or Na/C2H5OH or H2/Ni or LiAlH4 etc, alkane is
obtained.

Note Haloalkanes

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Haloalkanes:

Haloalkanes undergo nucleophilic substitution reactions by two mechanism;

1|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

ii. SN2 Mechanism:

2|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

2. Reaction with alcoholic KCN solution

Alkanenitriles are used for the synthesis of various organic compounds.

3|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

3. Reaction with silver cyanide (AgCN)

An isocyanide on reduction with the help of LiAlH4 gives 2° amine.

4. Reaction with potassium nitrite (KNO2)

4|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

7. Reaction with ammonia (NH3)

5|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

8. Reaction with potassium hydrosulphide (KSH)

9. Reaction with sodiumalkanethionate (NaSR)

B. Reaction with metals

6|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

C. Elimination reaction (Dehydrohalogenation)

7|P age© Jay P rakas h P audel || Depart m ent of Chemi st ry

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