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HALOGEN DERIVATIVE OF ALKANES AND ARENES

INTRODUCTION:

When one or more hydrogen atoms of aliphatic or aromatic hydrocarbon are replaced by corresponding
number of halogen atoms ( chlorine , bromine , iodine), the resulting compounds are called halogen
derivatives of alkanes or of arenes.
X2
G.R. R–H R -X + HX
Aliphatic or Alkyl or
aromatic Aryl
hydrocarbon halide

 Classification based on number of halogen attached

one hydrogen atom of alkanes is
Methyl chloride CH3 – C l
1. Monohalogen derivatives substituted by one halogen
Ethyl Bromide CH3 – CH2 -Br
atom.
More than one hydrogen atoms
of alkanes are substituted by
2. Polyhalogen derivatives
corresponding number of
halogen atoms.

Two hydrogen atoms of alkanes

Methylene dichloride CH2 – Cl2
A) Dihalogen derivatves are substituted by two halogen
ethylene dichloride C2H4Cl2
atoms

Three hydrogen atoms of

B) Trihalogen derivatives alkanes are substituted by three Chloroform CHCl3
halogen atoms

four hydrogen atoms of alkanes

C) Tetrahalogen derivatives are substituted by four halogen Carbon tetra chloride CCl4
atoms

 Classification based on type of carbon atom

n – propyl chloride
Halogen atom is bonded to a
A) primary alkyl halide
primary carbon atom
CH3CH2CH2 - Cl

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 Br
H3C
Halogen atom is bonded to a
B) secondary alkyl halide CH3
secondary carbon atom
Iso – propyl bromide

CH3
Halogen atom is bonded to a H3C
C) tertiary alkyl halides
tertiary carbon atom Br CH3
tert- butyl bromide

 ( A ) PREPARATION OF MONOHALOGEN
DERIVATIVES ( ALKYL HALIDES )
5 C2H6 +2 I2 + HIO3 5 C2H5I + 3 H2O
1. HALOGENATION OF ALKANES 2. From Alkenes

I. CHLORINATION – Carried out in presence of a. H2C CH2 + HBr CH3CH2 Br

diffused sunlight or ultraviolet light or at high ethene Ethyl bromide
temperature on alkane. b.
dark
Br
H3C
Eg. Diffused
+ HBr H3C
CH2 CH3
sunlight
CH4 + Cl Cl H3C Cl + HCl
Propene 2- Bromopropane
( or U.V.) Chloromethane
Methane
) Above addition is according to Markownikoffs
rule.
II. BROMINATION - It is carried out in presence of
anhydrous aluminum bromide. c. when same reaction carried out in presence
of peroxide primary product is obtained as a
Eg.
Anhydrous AlBr3 major product. ( Antimarkownikoofs rule )
C2H6 + Br2 C2H5 Br + HBr peroxide
H3C
Ethane ∆ Ethyl bromide CH2
+ HBr H3C
Br
It is not a very perfect method for preparation of Propene n- propyl bromide
alkyl chlorides or alkyl bromides as it gives
mixture of product which contains very less d.
amount of alkyl chlorides or bromides.
CH3 CH3
iii. IODINATION – reaction carried out in presence H3C
of oxidizing agent like iodic acid , nitric acid or + HCl
H3C CH3
mercuric oxide. CH2 Cl

isobutylene Tert-butyl chloride

Eg.

2 C2H6 +2 I2 + HgO 2C2H5I + HgI2 + H2O

Ethane Mercuric oxide Ethyl iodide

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 3. FROM ALCOHOL : same reaction also written for secondary and
tertiary alcohols.
1. primary and secondary reactant required
Lucas reagent for completion of reaction.

Lucas reagent is mixture of HCl & ZnCl2 and it is iiI. 3CH3CH2 OH + PI3 3CH3CH2l + H3PO3
used to distinguished primary, secondary &
tertiary alcohols. same reaction also be explain for secondary and
tertiary alcohols.
An.ZnCl2
H3C OH + HCl
+ H2O 6. when isopropyl alcohol is refluxed with
H3C Cl
Ethyl alcohol Conc. phosphorus pentachloride, isopropyl chloride is
Chloroethane
formed.
2.
OH Cl
An.ZnCl2 H3C POCl3 + HCl
OH Cl H3C + PCl5 +
H3C CH3
+ HCl
H3C
+ H2O CH3 CH3
CH3
Conc. Isopropyl alcohol
Isopropyl alcohol Isopropyl chloride isopropyl chloride

7. Reaction with thionyl chloride.

3. tertiary alcohols don’t need ZnCl2 to react
OH PYRIDINE
with HCl. Cl
H3C + SOCl2 H3C
+ SO2 ↑ + HCl
CH3 CH3 REFLUX CH3
H3C
H3C Isopropyl alcohol isopropyl chloride
HO
CH3
+ HCl
H3C CH3 + H2O
Cl
t- butyl alcohol 4. FROM HALOGEN EXCHANGE REACTION
t- butyl chloride

A. FINKELSTEINS REACTION
Dry acetone
4.
OH NaBr + H2SO4 Br
H3C Br + NaI H3C I + NaBr
H3C
+ HBr H3C + H2O
Ethyl bromide
Ethyl iodide
CH3
CH3

Isopropyl alcohol Iso propyl bromide

B. SWARTS REACTION
∆
5. H3C Cl
Methyl chloride
+ Ag F H3C F + Ag Cl
Methyl fluoride
2 P + 3 X2 2 PX 3S

i. 3CH3CH2 OH + PCl3 3CH3CH2 Cl + H3PO3 CH3CH2I + Ag-F CH3CH2F + Ag-I

Ethyl iodide Ethyl fluoride
same reaction also written for secondary and
tertiary alcohols.

II. 3CH3CH2 OH + PBr3 3CH3CH2 Br + H3PO3

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 ( B ) REACTION OF ALKYL HALIDES : In presence of silver salt cyanide attacks
through nitrogen & in strong basic solution
Alkyl halides being very reactive, undergo a cyanide attack through carbon.
variety of reaction.
∆
Eg. C2H5-O-Na + C2H5–Br C2H5-O-C2H5 +NaBr
( 1 ) Substitution reactions of alkyl halides :
Sodium ethoxide Diethyl Ether
∆
a. Formation of alcohol. C2H5-O-Na + CH3-Br C2H5-O-CH3+ NaBr
boil
Ethyl methyl ether
CH3 – Br + KOH CH3 – OH + KBr
Methyl bromide (Aq.) Methyl Alcohol e. Ammonolysis reaction:
∆
CH3- CH2 – Br + NH3 C2H5 NH2 + HBr
CH3- CH2 – Br + KOH CH3- CH2– OH + KBr Alc. presssure Ethyl amine
ethyl bromide (Aq.) ethyl Alcohol

CH3-Cl + NH3 CH3-NH2 + HCl

Moist
Br pressure
Ag2O Methyl amine
OH
H3C
+ Ag OH H3C
CH3 + Ag Br
f. Formation of ester.
CH3
Isopropyl bromide Isopropyl alcohol
O
O
Moist
+ Br
+ Ag Br
H3C O Ag CH3 H3C
CH3 Ag2O CH3 O CH3
H3C I + Ag OH H3C OH + Ag I Silver acetate
Ethyl acetate
CH3 CH3
O O
t- butyl iodide t – butyl alcohol
+ I CH3 + Ag I
H3C O Ag H3C O CH3
b. formation of alkyl cyanide.
Methyl acetate
boil
CH3-CH2-Br + KCN CH3-CH2-CN + KBr
( 2 ) Elimination reaction of alkyl halide:
Alc. ∆
H3C
CH3-CH2-CH2-Br + KCN CH3-CH2-CH2-Br+ KBr
Br
+ K OH H2C CH2 + K Br + H2O
Alc. Alc. ethene
Ethyl bromide
c. Formation Of Alkyl Isocyanide
Br
CH3-CH2-Br + AgCN CH3-CH2-NC + AgCN + K OH
H3C CH3
H3C
+ K Br + H2O
Alc. CH2

Note : when alkyl halide react with KCN it gives 2-bromo propane propene

formation of alkyl cyanide but If it react with In above reaction β is similar and hence
AgCN it gives formation of alkyl isocyanide. obtained only one product.
d. Williamson’s Synthesis of Ether Secondary butyl bromide when heated with
alcoholic solution of potassium hydroxide forms
here first alcohol converted into sodium
But – 2 – ene
alkoxide by treating it with sodium metal and CH3-CH=CH-CH3 +
But - 2-ene
then it reacted with alkyl halide to give 2 CH3-CH-CH2-CH3 + 2 KOH
CH2=CH-CH2-CH3 + 2KBr +
formation of ether. Br 2H2O

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 Formation of major product in above reaction 2.by electrophilic substitution. –
is done by using Saytzeffs Rule.
CH3
CH3 H3C
Which explains that in a dehydrohalogenation Fe Cl
reaction the major product is that which 2 + 2 Cl2
+ + 2 HCl
contains more number of alkyl group attached Dark
to doubly bonded carbon atom . Cl

( 3) Reaction with metals :

REACTIONS OF HALOARENES : by using this
a. Wurtz reaction :
Dry ether
we get mixture of O & P product.
2 CH3- Br + 2Na CH3-CH3 + 2 NaBr
Halogenation:
ethane
Methyl bromide
Dry ether Cl Cl Cl
An . FeCl3 Cl
2 C2H5Cl + 2 Na C4H10 +2 NaBr
Ethyl chloride
butane 2 + 2 Cl Cl
+ +2HCl

chlorobenzene o-dichlorobenzene Cl
b. Formation of Grignard Reagent :( R –Mg –X )
p- dichlorobenzene
Dry ether
CH3- Br + Mg CH3-Mg - Br Nitration:
Methyl bromide Methyl magnesium bromide
Cl Cl O
Conc Cl
Dry ether
+
H2SO4 N
C2H5 – I + Mg C2H5 –Mg – I 2HNO3 O
-
2 +
Ethyl iodide Ethyl magnesium iodide + + 2 H2O
+
o-chloronitrobenzene N
 HALOARENES
-
O O

p-chloronitrobenzene

( A ) Preparation of haloarenes ( C6H5 –X ) Sulphonation:

2 Cl Cl
NH2
+
Cl- SO3H
Cl
N
+ NaNO2+ 2 HCl N + 2 H2SO4 +
conc + H2O
+NaCl + 2H2O
aniline Chlorobenzene o-chlorobenzene
Benzene diazonium Chloride SO3H
sulphonic acid
-
+ Cl p- chlorobenzene
N
N CuCl Cl

sulphonic acid
Cl
Friedel craft Alkylation :
+ N2 ↑
Cl
Chlorobenzene Cl
Cl
An. AlCl3 CH3
above reaction is known as Sandmeyer 2 + 2H3C Cl
+ + 2 HCl
reaction.
Chlorobenzene o-chloro toluene CH3

p-chlorotoluene

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 Friedel craft acylation : 6. Identify the product of given reaction.
Na C2H5Br
Cl
Cl O  Ethanol A B
O An. Cl
2 AlCl3
2 + CH3 Ag C2H5Br
H3C Cl + + HCl Acetic acid A B
-HCl
Acetyl chloride o-chloro
acetophenone Na Cl2
H3C O  Propyl chloride A CCL B
p- chloro Acetophenone

Reaction with Sodium Metal :  Propene reacts with hydrogen bromide to

give compound A which on further
Wurtz fittig reaction
treatment with alcoholic KOH gives
In This reaction one alkyl halide and one aryl halide compound B. identify A & B.
react together to give formation of alkyl benzene.  Aniline undergoes diazotization reaction to
form A which on further reaction ith
Br
Dry H3C
cuprous salt gives B along with evolution of
ether nitrogen. Write down complete reaction.
+ Br CH3
+ 2 Na  What happens when isobutyl chloride
+ 2 Na Br
reacts with sodium ethoxide.
Bromo benzene  Explain peroxide effect.
Toluene
……………………………………………………………………
For rough work
Br
Dry
Ether
2 + 2Na + 2NaBr ----------------------------------------
Dipheyl ----------------------------------------
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Exercises ----------------------------------------
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1.Prepare isopropyl iodide using isopropyl alcohol.
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2. convert chloropropane to propene.
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3. prepare aniline from chlorobenzene.
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4.How will youconvert 1-chloro, 2-4 dinitro benzene to ----------------------------------------
2,4-dinitrophenol.
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5. prepare cyanobenzene from chlorobenzene.
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