HALOALKANES

&
HALOARENES
 HALOALKANES AND HALOARENES

These are compounds containing halogen atoms

attached to an alkyl or aryl group.

The general representation of haloalkanes is R-X and

that of haloarenes is Ar-X [where X = F, Cl, Br, I].
CH₃-Cl chlorometham

CH₃-CH₂-Br Bromoethane.

CH₃-CH₂-CH₂-Cl I-chloropropane

CH₃-CH-CH₃ 2-chloropropane
Cl
CH₃-CH₂-CH₂-CH₂-Br ↓- Bromobutane
-
C₆H₅-Cl chlorobenzene.

michlorobenzene
Cl Cl Cl Cl

Cl

Cl

0- Cl
P-
z-dichlorobenzene. 1,4-dichlorobenzene
 Primary haloalkane: R-CH₂-X

⑱
Secondary haloalkane: R₂CH-X
- x -

Tertiary haloalkane: R₃C-X

CH3
2 - -
X
CP2⑧
I

CH-c
B X

CH-2
-

dis ⑲ ⑧y4
3
BK

- X
-

I
Methods of preparation
HALOALKANES
I) From alcohols: Lucas Reagent.
-
HCI
R-OH + HX
anhy.ZnCl₂
R -ch

c1
3R-OH + PCl₃ 3R -

HPOs
+

R-OH + PCl₅ R -c + Hcl+pod

R-OH + SOCl₂ R-
C HCl SO2
+ +

↑ a

Darzensethode
A
II) From Hydrocarbons :

a) From Alkanes
Ac
CH₄ + Cl₂
hv
Ctyc +

CH₃Cl + Cl₂ hw
Click Acl
+

CH₂Cl₂ + Cl₂
hv
CH2+ Hal

cal Acl
hv
CHCl₃ + Cl₂ +
a) From Alkenes
i) Addition of hydrogen halide (HX):

-
chic-ct
CH₃-CH=CH₂ + HBr

Markownikoff’s rule
“when an unsymmetrical reagent is added to an unsymmetrical
alkene, the negative part of the adding molecule gets attached to
the carbon containing lesser number of hydrogen atoms”
III) Halogen Exchange Reactions :
a) Finkelstein reaction: Alkyl chlorides or bromides when treated with
NaI in dry acetone, alkyl iodides are formed.
This reaction is known as Finkelstein reaction.

dry acetone
R-X + NaI R-I + NaX (where X = Cl, Br)

b) Swarts reaction: Alkyl chloride or bromide is treated with a metallic

fluoride like AgF, Hg₂F₂, CoF₂ or SbF₃, to get alkyl
fluoride. This reaction is known as Swarts reaction.

R-X + AgF R-F AgY

=>
+
Methods of preparation
HALOARENES
II) From Aromatic amines :
Aromatic primary amines when treated with mineral acids like HCl
and sodium nitrite (NaNO₂) at cold condition (0 – 5⁰C), an aromatic
diazonium salt is formed. This reaction is called Diazotisation.

NH₂ N₂X
NaNO₂ / HX
0 – 5⁰C

Aniline
a) Sandmeyer’s reaction
When a diazonium salt is treated with HX in presence of cuprous halide
(Cu₂X₂), we get a halobenzene. This reaction is called Sandmeyer’s reaction.

N₂X c
Cu₂Cl₂ / HCl

N₂X
c Cu₂Br₂ / HBr
Be
b) Gattermann’s reaction
If the cuprous halide is replaced by copper powder, the reaction is called
Gattermann’s reaction.

N₂X d
HCl / Cu

N₂X
c HBr / Cu
By
c) For the preparation of iodobenzene, the diazonium salt is treated
with potassium iodide (KI).

N₂X I

KI
D
Chemical Reactions Of Haloalkanes
I) Elimination Reactions :
Alkyl halides having β-hydrogen atom when treated with alcoholic
solution of KOH, they undergo elimination of one hydrogen halide
molecule to form alkenes. [ Dehydrohalogenation / β-elimination ]

CH₃-CH₂-Br + KOH (alc) CH2= CH2

B <

CH₃-CH₂-CH-CH₃ + KOH (alc) Ctly-CH=CH -

CIs
Br I May a)
C

Cty-CHy-CH=CH2
Saytzeff rule
The rule states that “in dehydrohalogenation reactions, if there is
possibility of formation of more than one alkene the preferred
product is that alkene which contains greater number of alkyl
groups attached to the doubly bonded carbon atoms.”
II) Reaction with metals :
a) Reaction with Mg
Alkyl halides react with Mg metal in ether medium to form alkyl
magnesium halide commonly called Grignard reagent.

ether
R-X + Mg RMgX [Grignard reagent]

CH₃-CH₂-Br + Mg
ether
CH-CH2-Mg-By
-
b) Wurtz reaction - Reaction with Na
Alkyl halides react with sodium in dry ether to give alkanes with double
the number of carbon atoms. This reaction is known as Wurtz reaction.

dry ether
R-X + 2Na + X-R R-R + 2NaX

CH₃-Br + 2Na + Br-CH₃

dry ether
CH-CH
& NaBu
III) Nucleophilic Substitution Reactions : Nu:
These are reactions in which a weak nucleophile is replaced by
a strong nucleophile.
1) Reaction with aqueous alkali :
Haloalkanes react with aq. NaOH or KOH to form alcohols.
+-

CH₃-CH₂-Br + KOH(aq) CHy-CHEOlt

2) Reaction with water : Haloalkanes react with water to form alcohols.

f
H. OH-
CH₃-CH₂-Br + H₂O Ctz-CH2-Ol
-
--
3) Reaction with Sodium alkoxide (R-ONa) [Williamson’s ether synthesis] :
Haloalkanes react with sodium alkoxide to give ethers (R-O-R).
I
Nau
-

CH₃-Br + CH₃-CH₂-ONa
Hers
+

--
5) Reaction with KCN :
Alkyl halides react with alcoholic KCN to give alkyl cyanides (R-CN).
+-

R-X + KCN R-CN+ KX #: CN

6) Reaction with Silver cyanide (AgCN):

Alkyl halides react with AgCN to give alkyl isocyanides or
carbyl amines (R-NC).

R-X + AgCN R-NC + AgX Ag.

7) Reaction with Potassium nitrite (KNO₂) :
Alkyl halides react with KNO₂ to give alkane nitrite (R-ONO).

R-X + KNO₂ R-ONO + KX I-N 0 =

8) Reaction with Silver nitrite (AgNO₂) :

Alkyl halides react with AgNO₂ to give nitroalkane (R-NO₂)

R-X + AgNO₂ R-NO₂ + AgX

208

N0
1 ·.0 - =

g
-
 Mechanism of
Nucleophilic Substitution
Reactions
Mechanism of Nucleophilic Substitution Reactions
There are two types of mechanisms :

Substitution Nucleophilic unimolecular (SN1)

Substitution Nucleophilic bimolecular (SN2)

Substitution Nucleophilic Unimolecular (SN1)

Slow

Fast

Retention of configuration

The order of reactivity of alkyl halides towards SN1 reaction is:

3⁰ > 2⁰ > 1⁰
Substitution Nucleophilic bimolecular (SN2)

The configuration of carbon atom inverts and hence this process is

called as inversion of configuration.

The order of reactivity of alkyl halides towards SN-

1 reaction is:
C
I
1⁰ > 2⁰ > 3⁰ C-C -
X
d
 SN1 Reactions SN2 Reactions
Proceeds in 2 steps Proceeds in a single step

An intermediate
(carbocation) is formed No intermediate is formed

Retention of configuration Inversion of configuration

The order of reactivity of The order of reactivity of

alkyl halide is 3⁰ > 2⁰ > 1⁰ alkyl halide is 1⁰ > 2⁰ > 3⁰
thank youare
 SN1 Reactions SN2 Reactions
Proceeds in 2 steps Proceeds in a single step

An intermediate
(carbocation) is formed No intermediate is formed

Retention of configuration Inversion of configuration

The order of reactivity of The order of reactivity of

alkyl halide is 3⁰ > 2⁰ > 1⁰ alkyl halide is 1⁰ > 2⁰ > 3⁰