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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 alkanes

B) Trihalogen derivatives
C) Tetrahalogen derivatives
are substituted by three halogen Chloroform CHCl3
atoms
four hydrogen atoms of alkanes
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 5 C2H6 +2 I2 + HIO3 5 C2H5I + 3 H2O

DERIVATIVES ( ALKYL HALIDES )
2. From Alkenes
1. HALOGENATION OF ALKANES
a. H2C CH2 + HBr CH3CH2 Br
I. CHLORINATION – Carried out in presence of ethene Ethyl bromide
diffused sunlight or ultraviolet light or at high b.
dark
Br
temperature on alkane. H3C
+ HBr H3C
CH2 CH3
Eg.
Diffused Propene
CH4 + Cl Cl
sunlight H3C Cl + HCl 2- Bromopropane
Above addition is according to Markownikoffs
( or Chloromethane rule.
II.Methane
BROMINATION - It is carried out in presence of
U.V.) )
anhydrous aluminum bromide.
c. when same reaction carried out in presence
Eg. of peroxide primary product is obtained as a
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
alkyl chlorides or alkyl bromides as it gives
mixture of product which contains very less
amount of alkyl chlorides or bromides. d.
Propene CH3 CH3
n- propyl bromide
iii. IODINATION – reaction carried out in presence
of oxidizing agent like iodic acid , nitric acid or
mercuric oxide.
H3C
+ HCl
H3C CH3
CH2 Cl
Eg. isobutylene Tert-butyl chloride

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 & ZnCl 2 and it is iiI. 3CH3CH2 OH + PI3 3CH3CH2l + H3PO3
used to distinguished primary, secondary &
same reaction also be explain for secondary and
tertiary alcohols.
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
2. formed.

OH An.ZnCl2 Cl OH Cl
H3C CH3
+ HCl
H3C CH3
+ H2O
H3C + PCl5
H3C
CH3
+
POCl3 + HCl
Conc. CH3
Isopropyl alcohol Isopropyl chloride
Isopropyl alcohol
isopropyl chloride

3. tertiary alcohols don’t need ZnCl 2 to react

7. Reaction with thionyl chloride.
with HCl.
CH3 OH PYRIDINE Cl

H3C CH3
+ HCl
H3C
H3C + SOCl2 H3C
+ SO2 ↑ +
HO H3C
Cl
CH3 + H2O CH3 REFLUX CH3
HCl
t- butyl alcohol Isopropyl alcohol isopropyl chloride
t- butyl chloride

4. 4. FROM HALOGEN EXCHANGE REACTION

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

5.
B. SWARTS REACTION
2 P + 3 X2 2 PX 3S
∆
i. 3CH3CH2 OH + PCl3 3CH3CH2 Cl + H3PO3 H3C Cl
Methyl chloride
+ Ag F H3C F + Ag Cl
same reaction also written for secondary and Methyl fluoride
tertiary alcohols. CH3CH2I + Ag-F CH3CH2F + Ag-I
II. 3CH3CH2 OH + PBr3 3CH3CH2 Br + H3PO3 Ethyl iodide Ethyl fluoride

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 here first alcohol converted into sodium
alkoxide by treating it with sodium metal and
( B ) REACTION OF ALKYL HALIDES : then it reacted with alkyl halide to give
Alkyl halides being very reactive, undergo a formation of ether.
variety of reaction. In presence of silver salt cyanide attacks
( 1 ) Substitution reactions of alkyl halides : through nitrogen & in strong basic solution
cyanide attack through carbon.
a. Formation of alcohol. ∆
boil Eg. C2H5-O-Na + C2H5–Br C2H5-O-C2H5 +NaBr
CH3 – Br + KOH CH3 – OH + KBr Sodium ethoxide Diethyl Ether
∆
Methyl bromide (Aq.) Methyl Alcohol
C2H5-O-Na + CH3-Br C2H5-O-CH3+ NaBr
Ethyl methyl ether
CH3- CH2 – Br + KOH CH3- CH2– OH + KBr
e. Ammonolysis reaction:
ethyl bromide (Aq.) ethyl Alcohol
∆
Moist CH3- CH2 – Br + NH3 C2H5 NH2 + HBr
Br Ag2O Alc. presssure Ethyl amine
OH
H3C
+ Ag OH H3C
CH3 + Ag Br
CH3 CH3-Cl + NH3 CH3-NH2 + HCl
Isopropyl bromide Isopropyl alcohol pressure
Methyl amine

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

Alc. Br

Note : when alkyl halide react with KCN it gives + K OH

H3C CH3
H3C
+ K Br + H2O
formation of alkyl cyanide but If it react with CH2

AgCN it gives formation of alkyl isocyanide. 2-bromo propane propene

In above reaction β is similar and hence
d. Williamson’s Synthesis of Ether obtained only one product.

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 Secondary butyl bromide when heated with
alcoholic solution of potassium hydroxide forms
But – 2 – ene 2.by electrophilic substitution. –
CH3-CH=CH-CH3 +
But - 2-ene
2 CH3-CH-CH2-CH3 + 2 KOH CH3
CH2=CH-CH2-CH3 + 2KBr + CH3 H3C
Br Fe Cl
Formation of major product in2H 2O
above reaction 2 + 2 Cl2 + + 2 HCl
is done by using Saytzeffs Rule. Dark
Which explains that in a dehydrohalogenation Cl

reaction the major product is that which

REACTIONS OF HALOARENES : by using this
contains more number of alkyl group attached
we get mixture of O & P product.
to doubly bonded carbon atom .
Halogenation:
( 3) Reaction with metals :
Cl Cl Cl
a. Wurtz reaction : An . FeCl3 Cl
Dry ether
2 CH3- Br + 2Na CH3-CH3 + 2 NaBr 2 + 2 Cl Cl
+ +2HCl
ethane
Methyl bromide o-dichlorobenzene
Dry ether
chlorobenzene Cl

p- dichlorobenzene
2 C2H5Cl + 2 Na C4H10 +2 NaBr Nitration:
butane
Ethyl chloride Cl
Conc Cl O Cl
+
H2SO4 N -
b. Formation of Grignard Reagent :( R –Mg –X ) 2 + 2HNO3 O

Dry ether + + 2H2O

CH3- Br + Mg CH3-Mg - Br
+
Methyl bromide Methyl magnesium bromide o-chloronitrobenzene N
-
O O
Dry ether
p-chloronitrobenzene
C2H5 – I + Mg C2H5 –Mg – I Sulphonation:
Ethyl iodide Ethyl magnesium iodide
Cl Cl
Cl
SO3H
+ 2 H2SO4
 HALOARENES conc
+ + H2O

Chlorobenzene o-chlorobenzene
SO3H
( A ) Preparation of haloarenes ( C6H5 –X ) sulphonic acid
p- chlorobenzene
NH2 - 2 Friedel craft Alkylation : sulphonic acid
+
Cl
N
+ NaNO2+ 2 HCl N Cl
Cl
Cl
+NaCl + 2H2O An. AlCl3 CH3
aniline 2 + 2H3C Cl
Benzene diazonium Chloride + + 2 HCl
-
+ Clreaction is known as Sandmeyer reaction.
above Chlorobenzene CH3
N o-chloro toluene
N CuCl Cl

p-chlorotoluene
Cl + N2
Chlorobenzene
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 Friedel craft acylation : 6. Identify the product of given reaction.
Na C2H5Br
Cl  Ethanol A B
O Cl O
An. Cl
2  Acetic acid A B
AlCl3
2 + CH3  Ag
Propyl chloride CA
2H5Br B
H3C Cl + + HCl Propene reacts with hydrogen bromide to
-HCl give compound A which on further
Acetyl chloride o-chloro
acetophenone treatment with alcoholic Cl KOH gives
H3C O Na 2

compound B. identify A & B. CCL

p- chloro Acetophenone
Reaction with Sodium Metal :  Aniline undergoes diazotization reaction to
form A which on further reaction ith
Wurtz fittig reaction cuprous salt gives B along with evolution of
nitrogen. Write down complete reaction.
In This reaction one alkyl halide and one aryl halide  What happens when isobutyl chloride
react together to give formation of alkyl benzene. reacts with sodium ethoxide.
Br  Explain peroxide effect.
Dry H3C ……………………………………………………………………
+ Br CH3
+ 2 Na
ether
For rough work
+ 2 Na Br

Bromo benzene ----------------------------------------

Toluene
----------------------------------------
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. ----------------------------------------
4.How will youconvert 1-chloro, 2-4 dinitro benzene to
2,4-dinitrophenol.

5. prepare cyanobenzene from chlorobenzene.

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