UNIT- 10

HALOALKANES AND HALOARENES

Introduction:
Haloalkanes and haloarenes are obtained by replacing one or more number of hydrogen
atom(s) in a aliphatic / aromatic hydrocarbon by halogen atom(s). [X = F, Cl, Br, I
(Group-17 elements)].

Importance:
1. Many halogen containing organic compounds occur in nature, some of them are clinically
useful.
 Chlorine containing antibiotic, chloramphenicol, produced by soil microorganisms is
very effective for the treatment of typhoid fever.
 Our body produces iodine containing hormone thyroxine, the deficiency of which
causes a disease called goiter.
 Synthetic halogen compounds, viz. chloroquine is used for the treatment of malaria;
halothane is used as an anaesthetic during surgery.
 Certain fully fluorinated compounds are being considered as potential blood
substitutes in surgery.
2. These classes of compounds find wide applications in industry as well as in day-to-day
life.
3. They are used as solvents for relatively non-polar compounds and as starting
materials for the synthesis of wide range of organic compounds.
In this Unit, you will study the important methods of preparation, physical and
chemical properties and uses of organohalogen compounds.

CLASSIFICATION:

I) On the Basis of Number of Halogen Atoms:

They are classified as mono, di, or polyhalogen (tri, tetra, etc.) compounds depending on
whether they contain one, two or more halogen atoms in their structures.
Example:
CH2 X
CH X
CH2 X
CH3 X CH2 X CH2 X
Mono haloalkane di haloalkane poly haloalkane
(Tri haloalkane)
X X X
X X

X
Mono haloarene di haloarene poly haloarene
(Tri haloarene)
Note: Dihaloalkanes are of two types namely:

SKCH COMP. PU COLLEGE 1 DEPARTMENT OF CHEMISTRY

 a) Geminal dihaloalkane: If two halogen atoms are bonded to the same C- atom then they
are said to be geminal dihalides.(Gemini = twins)

CH CH3
X
Geminal di haloalkane

b) Vicinal dihaloalkane: If two halogen atoms are bonded to the neighbouring C- atoms
then they are said to be vicinal dihalides. (Vicinal = neighbours)

CH2 CH2
X X
Vicinal di haloalkane

Note: Geminal and vivinal dihalides are position isomers.

II) Classification of monohalo compounds on the Basis of hybridisation of the

carbon atom to which the halogen atom is bonded:

Monohalo compounds may further be classified according to the hybridisation of the

carbon atom to which the halogen is bonded.

i. Compounds containing sp3 C—X Bond (X= F, Cl, Br, I);

a) Monohaloalkanes OR Alkyl halides:

Mono halogen derivatives of alkanes are called haloalkanes. They form a homologous
series represented by CnH2n+1X (G.F).
They are generally represented as R-X or R-CH2-X or R-CH2-CH2-X.
They are further classified as primary, secondary and tertiary alkylhalides based
on the nature of carbon atom to which halogen is bonded.
Example:
H R'' R''
R' C X R' C X R' C X
H H R'''
primary secondary tertiary
0
(1)
0
(2 ) ( 30 )

b) Allylic halides: These are the compounds in which the halogen atom is bonded to an
sp3-hybridised carbon atom next to carbon-carbon double bond (C=C) i.e. to an allylic
carbon.
Example: X

CH2 X

SKCH COMP. PU COLLEGE 2 DEPARTMENT OF CHEMISTRY

 c) Benzylic halides: These are the compounds in which the halogen atom is bonded to
an sp3-hybridised carbon atom next to an aromatic ring i.e to a benzylic carbon
Example: X
R'
CH2X
R''

0
R' = CH3, R'' = H (2 )
0
R' = R'' = CH3 (3 )

d) Alkargyl halides These are the compounds in which the halogen atom is bonded to
an sp3-hybridised carbon atom next to carbon-carbon triple bond (C=C).
Example: X

CH2 X

ii. Compounds containing sp2 C—X Bond (X= F, Cl, Br, I):
a) Vinylic halides: These are the compounds in which the halogen atom is bonded to an
sp2-hybridised carbon atom of a carbon-carbon double bond (C=C).
Example:
X

b) Aryl halides: These are the compounds in which the halogen atom is bonded to an sp2-
hybridised carbon atom of an aromatic ring.
X X
Example:

CH3

iii. Compounds containing sp C—X Bond (X= F, Cl, Br, I): These are the compounds in
which the halogen atom is directly bonded to a sp-hybridised carbon atom carbon-
carbon triple bond (C=C).

Example:
X
Haloacetylene / Acetylene halides / haloethyne

Nomenclature:
1. Monohaloalkanes:
Trivial system: They are named as alkylhalides.
IUPAC system: They are named as haloalkanes.

SKCH COMP. PU COLLEGE 3 DEPARTMENT OF CHEMISTRY

 Example:
CH3 CH CH3 CH3
CH3CH2CH2Br CH3 CH CH2 Cl
Cl
1-Bromopropane 2-Chloropropane 1-chloro-2-methylpropane
(n-Propyl bromide) (Isopropyl chloride) (Isobutyl chloride)

2. Dihaloalkanes:
Trivial system:
i) Geminal dihalides are named as alkylidene dihalides or alkylidene halides
Example:
X CH3
I
C X CH3CHCl 2 CH3CH2CH2Cl 2 CH3 C Cl
I
Cl
gem dihalides 1,1-dichloroethane 1,1-dichloropropane 2,2-dichloropropane
(Ethylidene dichloride) (propylidene dichloride) (Iso-propylidene dichloride)

ii) Vicinal dihalides are named as alkylene dihalides or alkylene halides.

Example:
CH3
X X Cl Cl Cl Cl
C CH3 C CH2
C CH2 CH2 CH3 CH CH2
Br Br
vicinal dihalides 1,2-dichloroethane 1,2-dichloropropane 1,2-dibromo-2-methylpropane
(Ethylene dichloride) (propylene dichloride) (Isobutylene dibromide)

iii) Polymethylene dihalides (terminal dihalides) are the dihalo compounds

containing halogen atoms at the terminal ends of the chain and are named as
polymethylene dihalides.

IUPAC system: They are named as dihaloalkanes (with appropriate locants according
to lowest sum rule).
Example: BrCH2CH2CH2Br ClCH 2CH2CH2CH2Cl

1,3-dibromopropane 1,4-dichlorobutane
(Trimethylene dibromide) (Tetramethylene dichloride)

3. Polyhaloalkanes:
Trivial system: They are named as haloforms (Trihaloalkanes are called as
haloforms).
IUPAC system: They are named as polyhaloalkanes

CHCl 3 CHI 3 CCl 4

Example:
(chloroform) (Iodoform) (carbon tetrachloride)
Trichloromethane Triiodomethane Tetrachloromethane

SKCH COMP. PU COLLEGE 4 DEPARTMENT OF CHEMISTRY

 Note: Fully halogenated compounds are called perhalohydrocarbons, which
are obtained by replacing all the H- atoms of a hydrocarbon by halogen atoms.

Example:
CF 3-CF 2-CF 3 CCl 3-CCl 3
octafluoropropane hexachloroethane
(perfluoropropane) (perchloroethane)

4. Haloarenes: Haloarenes or aryl halides are named by adding the prefix halo (fluro,
Chloro, bromo, iodo) before the name of the aromatic hydrocarbon.
In case of disubstituted compounds, the relative positions of the substituents 1, 2; 1,3
and 1,4 are indicated by the prefixes ortho(o-), meta(m-), para(p-) respectively.
Monohaloarenes: They are named as halobenzene.
Example:
Cl Br

chlorobenzene Bromobenzene Iodobenzene

CH3
CH3 CH3
Cl

Cl
Cl
2-chlorotoluene 3-chlorotoluene 4-chlorotoluene
(o-chlorotoluene) (m-chlorotoulene) (p-chlorotoluene)
Dihaloarenes: They are named as dihalobenzene. .
Example: Cl Cl
Cl

Cl
1,2-dichlorobenzene 1,4-dichlorobenzene
(o-Dichlorobenzene) (p-Dichlorobenzene)

Trihaloarenes: They are named as Trihalobenzene.

Example: Br

Br Br
1,3,5-tribromobenzene
(sym-Tribromobenzene)

SKCH COMP. PU COLLEGE 5 DEPARTMENT OF CHEMISTRY

 Compound Common name IUPAC name
CH3Cl Methyl chloride Chloromethane
CH3 -CH2 -Cl Ethyl bromide Bromo ethane
CH3 -CH2 - CH2 -l n-propyl iodide 1-iodo-propane
CH3-CH-CH3
Iso-propyl iodide 2-iodo-propane
I
CH3 -CH2 - CH2 - CH2 -Cl n-butyl chloride 1-chloro-butane
CH3-CH-CH 2-Cl
iso-butyl chloride 1-chloro-2-methyl-propane
CH3
CH3-CH-CH 2-CH3
Sec-butyl chloride 2-chloro-butane
Cl
CH3
CH3-C-Cl Ter-butyl chloride 2-chloro-2-methyl propane
CH3
CH3 -CH2 - CH2 - CH2 - CH2 -Cl n-pentyl chloride 1-chloropentane
CH3
1-chloro-2,2—dimethyl-
CH3-C-CH2-Cl Neo-pentyl chloride
propane
CH3
CH2Cl2 Methylene dichloride Dichloromethane
CHCl3 Chloroform Trichloromethane
CHl3 Iodoform Triiodomethane
CCl4 Carbontetrachloride Tetrachloromethane
Cl -CH2 - CH2 -Cl Ethylenedichloride 1,2-dichloroethane
CH3-CH-CH2
Propylene dichloride 1,2-dichloropropane
Cl Cl
CH3-CH-Cl
Ethylidine dichloride 1,1-dichloroethane
Cl
CH3-CH2-CH-Cl
Propylidine dibromides 1,1-dibromopropane
Cl
Br

CH3-C-CH3 Isopropylidine dibromides 2,2-dibromo-propane

Br
Cl -CH2 - CH2 - CH2 -Cl Trimethylene dichloride 1,3-dichloropropane
CH2 = CH -Cl Vinyl chloride Chloroethene
CH2 = CH - CH2 -Cl Allyl chloride 3-chloro-1-propene
CH C-Br Acetylene bromide Bromoethyne
CH C-CH 2-Br Propargyl bromide 3-bromoethyne
Cl

Chlorobenzene Chlorobenzene

SKCH COMP. PU COLLEGE 6 DEPARTMENT OF CHEMISTRY

 Cl
CH3
1-chloro-2-methylbenzene
o-chloro toluene or
1-chloro-toulene
Cl
Cl
o-dichloro benzene 1,2-dichlorobenzene

Cl

m-dichloro benzene 1,3-dichlorobenzene

Cl
Cl

p-dichloro benzene 1,4-dichlorobenzene

Cl
Cl

Sym-trichloro benzene 1,3,5-trichloro-benzene

Cl Cl
Cl
Br
o-bromochloro benzene 1-bromo-2-chloro-benzene

CH 2 Cl

Benzyl chloride 1-chloro-1-phenylmethane

CHCl 2

1,1-dichloro-1-phenyl-
Benzal chloride
methane
CCl 3

1,1,1-trichloro-2-
Benzotrichloride
phenylethane
CH2 CH 2 Cl

β-phenyl ethyl chloride 1-chloro-2-phenylethane

Cl
Cl Cl
1,2,3,4,5,6-
Hexachlorobenzene
hexachlorobenzene
Cl Cl

Cl
Cl
Cl Cl
1,2,3,4,5,6-hexachloro-
Benzene hexachloride
cyclohexane
Cl Cl

Cl

SKCH COMP. PU COLLEGE 7 DEPARTMENT OF CHEMISTRY

Isomerism in haloalkanes and haloarenes:

Haloalkanes show two types of isomerism.

1) Structural Isomerism: Two or more compounds have same molecular formula but
different structural formulaare called structural isomers and the phenomenon is called as
structural isomerism.

a) Chain Isomerism: The haloalkanes containing four or more carbon atoms exhibit chain
isomerism in which the isomers differ in the number of carbon atoms in the parent chain.
Example:
CH3 CH3
CH3CH2CH2CH2Br CH3 CH CH2 Br CH3 C Br
CH3
1- Bromobutane 1-Bromo-2-methylpropane 2-Bromo-2-methylpropane

b) Position Isomerism: The haloalkanes containing three or more carbon atoms exhibit
position isomerism in which the isomers differ in the position of halogen atoms in the
parent chain.
Example:
CH3CH2CH2I CH3 CH CH3
I
1-Iodopropane 2-Iodopropane

2) STEREO ISOMERISM:
Two or more compounds have same molecular formula and structural formula but
differ in the spatial arrangement of atoms or group of atoms and exhibit different
physical and chemical properties are called stereo isomers and the phenomenon is
called stereo isomerism.
There are two types of stereo isomerism namely:
a) Geometrical isomerism b)Optical isomerism

OPTICAL ISOMERISM:
Compounds having same molecular formula and structural formula but differ in the
direction of rotation of plane polarized light are called optical isomers and the
phenomenon is called as optical isomerism.

CONDITIONS FOR A MOLECULE TO EXHIBIT OPTICAL ISOMERISM:

1. The molecule should contain atleast one chiral C-atom.
2. The molecule should not contain any plane of symmetry.

PLANE POLARIZED LIGHT:

The light which has vibrating waves in only one plane is called a plane polarized light.
Ordinary light consists of waves vibrating in different plane. When this light is passed
through nicol prism made of CaCO3, plane polarized light is obtained.

SKCH COMP. PU COLLEGE 8 DEPARTMENT OF CHEMISTRY

MEASUREMENT OF OPTICAL ACTIVITY:

----
----
----
----
----
----
OR
----
----
Source Nicol prism Plane polarised light Sample Dextro rotatory laevo rotatory Polarimeter
OR OR
Clockwise anticlockwise
d/+ l/-

DEXTRO ISOMER:
Optically active compounds that rotates plane polarized light in clockwise direction or
towards right are called as dextro isomers.
It is represented by writing + or d before the name of compound.
Example:
CH3
I
H *C Br
I
C2H5
(+)-2-Bromo-butane

LAEVO ISOMER:
Optically active compounds that rotates plane polarized light in anti clockwise
direction or towards left are called as laevo isomers.
It is represented by writing – or l before the name of compound.
Example:
CH3
I
Br *C H
I
C2H5
(-)-2-Bromo-butane

CHIRAL C-ATOM / ASYMMETRIC C-ATOM / CHIRALITY CENTRE:

The carbon atom bonded to four different atoms or group of atoms in a molecule is
called as a chiral C-atom / asymmetric C-atom / chirality centre.
Example:
Chirality center
CH3
I OR
*
Br C H asymmetric center
I
C2H5
(-)-2-Bromo-butane

If the molecule contains only one chirality centre, then it is optically active.
If the molecule contains 2 or more chirality centers, then it is need not be optically active.
Optically activity depends only on the absence of plane of symmetry when a molecule
contains 2 or more chirality centers.
SKCH COMP. PU COLLEGE 9 DEPARTMENT OF CHEMISTRY
PLANE OF SYMMETRY OR MIRROR PLANE OR SIGMA PLANE:
It is an imaginary line which divides the molecules into two identical halves which are
mirror images of each other.
Example:
CH3
I Plane of symmetry
*
H C Br
I
H *C Br
I
CH3
Meso-2,3-dibromobutane

One half of the molecule rotate plane polarized light in clockwise direction and another half
rotate plane polarized light in anti clockwise direction. Both the halves rotates plane
polarized light to the same extent but in opposite direction hence the net rotation becomes
zero. This type of compensation of specific rotation is called internal compensation.
The compounds containing plane of symmetry are optically inactive.

OPTICAL ACTIVITY:
The property of some organic compounds to rotate plane polarized light in clockwise
or anticlockwise direction in their solution state is called optical activity.
The substances which rotate plane polarized light in clockwise or in anticlockwise direction in
solution state are called optically active substances.

The optical activity of a substance is determined by using an instrument called polarimeter.

The optical activity is expressed in terms of specific rotation.

SPECIFIC ROTATION:
The rotation produced by a solution of an optically active of length 1 dm (decimeter)
having unit concentration (1g/cm3) for a plane polarized light of given wavelength at a
given temperature is called specific rotation.

It is given by t 
lxc

Where, α = angle of rotation

t = given temperature, λ = wave length of light
l = length of polarimeter tube, c = concentration of solution of substance in g/cm3.

CHIRAL MOLECULES:
Molecules which are non-super imposable mirror images of each other are called as
chiral molecules.
 All chiral molecules are optically active because they do not contain any plane of
symmetry.
 The molecules having super imposable mirror images are called achiral molecules.
 All achiral molecules are optically inactive.

SKCH COMP. PU COLLEGE 10 DEPARTMENT OF CHEMISTRY

RACEMIC MIXTURE:
Equimolar mixture of d and l isomers is called as a racemic mixture.
It is optically inactive because the rotations produced by d and l isomers are equal
and opposite. Hence the net rotation becomes zero. This type of compensation of rotation of
plane polarized light is called external compensation.

Ex: (±) 2 – Bromobutane.

ENANTIOMERS:
A pair of optically active isomers which are non-super imposable mirror images of
each other are called enantiomers.

CH3 CH3
I I
Example: H *C Br *
Br C H
I I
C2H5 C2H5
(+)-2-Bromo-butane Mirror (-)-2-Bromo-butane

Note:

Vant Hoff’s rule: The total no. of possible optical isomers for a molecule containing ‘n’ no. of
chirality centre is given by 2n. and number of mesocompounds is 2n-1.

DIASTEROMERS:
Stero isomers which are non-superimposable non mirror images of each other are
called as diastereomers.

MESO COMPOUNDS:
Organic compounds having more than one chiral C-atom but are optically in active
due to presence of plane of symmetry which causes internal compensation are called
as mesocompounds.
CH3
I
H *C Br
I
*
H C Br
I
CH3
Meso-1,2-dibromobutane

Methods of Preparation:
Preparation of Haloalkanes: (alkyl halides)
1) From Alcohols: Alkyl halides are best prepared from alcohols, which are easily
accessible. The hydroxyl group of an alcohol (-OH) is replaced by halogen (-X) on
reaction with concentrated halogen acids/phosphorus halides/thionyl chloride.

SKCH COMP. PU COLLEGE 11 DEPARTMENT OF CHEMISTRY

a) Using Hydrogen halides (HX) (Halogen acids):
Alcohols upon treatment with halogen acids give respective alkyl halides.
i) On passing through hydrogen chloride gas through 10 and 20 alcohols in presence of
anhydrous ZnCl2 respective chloroalkanes (alkyl chlorides) are obtained.
anhy. ZnCl2
General reaction: R-OH + HCl (g) R-Cl + H2O (Grooves process)
Chloroalkane

anhy. ZnCl2
Example: CH3-CH2-OH + HCl (g)
CH3-CH2-Cl + H2O (Grooves process)
Chloroethane
(Ethyl chloride)

Note:
1) Order of reactivity of alcohols is 30 >20 >10
2) 30 alcohols react with HCl (g) at room temperature itself and in absence of anhydrous
ZnCl2.
2) Mixture of Conc.HCl+ anhy.ZnCl2 is called Lucas reagent.

ii) When alcohols are refluxed with Hydrobromic acid in presence of conc.H2SO4
respective bromoalkanes (alkyl bromides) are obtained.
conc. H2SO4
General reaction: R-OH + H-Br R-Br + H2O
Heat
Bromoalkane

conc. H2SO4 CH3-CH2-Br + H2O

Example: CH3-CH2-OH + H-Br
Heat
Bromoethane
(Ethyl bromide)
HBr can also be generated in situ (during the reaction) by the action of bromide salts like
KBr or NaBr with conc.H2SO4.
Heat
General reaction: R-OH + NaBr + H2SO 4 R-Br + NaHSO 4 + H2O
Bromoalkane

Example: R-OH + KBr + H2SO 4 Heat

R-Br + KHSO 4 + H2O
Bromoalkane
iii) When alcohols are heated with Hydroiodic acid (57%) respective iodoalkanes (alkyl
iodides) are obtained.
Reflux
General reaction: R-OH + H-I R-I + H2O
Iodoalkane

Reflux CH3-CH2-I + H2O

Example: CH3-CH2-OH + H-I
Iodoethane
(Ethyl iodide)
HI is also generated in situ (during the reaction) by the action of 95% phosphoric acid on
KI.
Heat
General reaction: R-OH + KI + H3PO4 R-I + KH2PO4 + H2O
Phosphoric acid Iodoalkane Potassium dihydrogen
Phosphate

Example: Heat
CH3-CH2-OH + KI + H3PO4 CH3-CH2-I + KH2PO4 + H2O
Ethanol Phosphoric acid Iodoethane Potassium dihydrogen
(ethyl alcohol) Ethyl iodide Phosphate

SKCH COMP. PU COLLEGE 12 DEPARTMENT OF CHEMISTRY

b) Using Phosphorous halides (PX3/PX5): Haloalkanes are prepared by the action of
phosphorous halides on alcohols.
General reaction: R-OH + PCl 5 R-Cl + POCl 3 + HCl
Alcohol Phosphorous Chloroalkane
penta chloride (Alkyl chloride)

3 R-OH + PX3 3 R-X + H3PO 3 (X=Cl,Br,I)

Alcohol Phosphorous
trihalide

Red P/ X 2
3 R-OH 3 R-X
X = Br 2, I2
Alcohol
Note: Since PBr3 and PI3 are not very stable compounds these are prepared insitu (with
in the reaction) by the action of red phosphorous on Br2 and I2 respectively.

c) Using Thionyl chloride (SOCl2) (Darzens process): Chloroalkanes are best prepared
from alcohols by refluxing alcohols with thionyl chloride in presence of pyridine.
General reaction: Reflux
R-OH + SOCl 2 R-Cl + SO 2 + HCl
C5 H5 N
Reflux
Example: CH3-CH2-OH + SOCl 2 CH3-CH2-Cl+ SO 2 + HCl
C5 H5 N
Chloroethane
(Ethyl chloride)
Note:
1. This method is the best method to prepare pure alkyl chlorides because the other two by
products obtained are escapable gases.
2. In this process pyridine is used to neutralise the HCl formed during the course of the
reaction and make the reaction to proceed in the forward direction.

2) From Alkenes:
a) Using hydrogen halides:
Alkenes upon treatment with hydrogen halides (HX) X= F, Cl, Br, I, hydrohalogenation
takes place according to Markownikoff’s rule leading to the formation of alkyl halides.

MARKOWNIKOFF’S RULE:
When an unsymmetrical reagent is added to an unsymmetrical alkene the positive
part of the adding reagent adds on to the doubly bonded carbon atom containing
more number of hydrogen atoms.

General reaction: R-CH=CH 2 + HX R-CH-CH 2

alkene X H
Halo alkane
(Alkyl halide)

Example: CH3-CH=CH 2 + HCl CH3-CH-CH 3 + CH -CH -CH -Cl

3 2 2
Propene Cl
2-Chloropropane 1-Chloropropane
(Iso-propyl chloride) (Propyl chloride)
Major Minor

SKCH COMP. PU COLLEGE 13 DEPARTMENT OF CHEMISTRY

Using halogens:
Alkenes upon treatment with halogens such as Br2 in presence of CCl4 at room
temperature addition reaction takes place to form vicinal dibromo alkane and the
orange red colour of bromine is discharged. Hence this reaction is used as a test for
unsaturated compounds.

CCl 4
General reaction: R-CH=CH 2 + Br 2 R-CH-CH 2
Room temperature
alkene Br Br
Vicinal dibromoalkane
CCl 4
Example: CH3-CH=CH 2 + Br 2 Room temperature
CH3-CH-CH 2
Propene Br Br
1,2- Dibromopropane
3) Halogen Exchange:
a) Finkelstein Reaction:
Alkyl chlorides or alkyl bromides up on reaction with NaI in dry acetone form respective
alkyl iodides. This reaction is called Finkelstein reaction.
Dry acetone
General reaction: R-X + NaI R-I + NaX
Reflux
Halo alkane Iodoalkane
(Alkyl iodide)

Dry acetone
Example: CH3-CH2-Br + NaI CH3-CH2-I + NaBr
Reflux
Bromo ethane Iodoethane
(Ethyl bromide) (Ethyl iodide)

Note: NaX formed during the reaction gets precipitated in dry acetone as NaX insoluble in
organic solvent; this facilitates the reaction to proceed forward according to Le chatelier’s
principle.

b) Swarts reaction:
Alkyl chlorides or alkyl bromides up on heating in presence of a metallic fluoride such as
AgF/Hg2F2/CoF2/SbF3 alkyl fluorides are obtained. This reaction is called Swarts
reaction.
General reaction: R-X + AgF R-F + AgX
Halo alkane Fluroalkane
(Alkyl fluoride)

Example: CH3-CH2-Br + AgF CH3-CH2-F + AgBr

Bromo ethane Fluroethane
(Ethyl bromide) (Ethyl Fluoride)

Preparation of Haloarenes: (aryl halides)

1) By Electrophilic substitution reaction:

Aryl chlorides or aryl bromides are prepared by reaction of arenes with halogens (X2=Cl2,
Br2) in presence of lewis acid as catalyst such as FeCl3/FeBr3/AlCl3.

SKCH COMP. PU COLLEGE 14 DEPARTMENT OF CHEMISTRY

 X

Anhy. FeCl 3
General reaction: + X2
+ HX

Benzene Halobenzene
Cl

Anhy. FeCl 3
Example: + Cl 2
+ HCl

Benzene Chlorobenzene
CH3 CH3 CH3
Br
Anhy. FeBr 3
Example: 2 + 2 Br2 + + 2 HBr

Br
Toulene o-Bromo toulene p-Bromo toulene
Note:
 Iodination is reversible require an oxidizing reagent like HNO3/HIO3 to oxidize the HI
formed during the reaction.
 Fluro compounds are not prepared by this method due to high reactivity of fluorine.

2) Sandmeyer’s Reaction:
When an aromatic primary amine such as aniline is dissolved in a mineral acid (HX) and
then treated with sodium nitrite at 00C to 50C Benzene diazonium halide is obtained
which upon treating with cuprous chloride (Cu2Cl2) or cuprous Bromide (Cu2Br2), gives
Bromo benzene/chloro benzene respectively.
NH2 + -
N2X

0 0
0 C-5 C
General reaction: + NaNO 2 + 2HX
+ NaX + 2 H2O

Aniline Benzene diazonium halide

+ -
N2X X

X = Cl,Br

Cu 2X 2 / HX + N2
Halobenzene (Aryl halide)
Note: Iodobenzene is just obtained by adding Benzene diazonium halide salt to aqueous
solution of potassium iodide and shaking/warming. This is the best method to introduce
iodine to benzene ring.

SKCH COMP. PU COLLEGE 15 DEPARTMENT OF CHEMISTRY

 + -
N 2X I

warm
Example: + KI
+ N2 + KX

Benzene diazonium halide Iodobenzene

Physical Properties:
1. Appearance: Alkyl halides are colourless when pure. However, bromides and iodides
develop colour when exposed to light.
2. Odour: Many volatile halogen compounds have sweet smell.

3. Physical state: Methyl chloride, methyl bromide, ethyl chloride and some
chlorofluoromethanes are gases at room temperature. Higher members are liquids or
solids.

4. Melting and boiling points:

 Haloalkanes/ Haloarenes have considerably higher m.pP and b.p than those of the
hydrocarbons of comparable molecular mass.
Reason: Haloalkanes/ Haloarenes are generally polar. Due to greater polarity as well
as higher molecular mass as compared to the parent hydrocarbon, the intermolecular
forces of attraction (dipole-dipole and van der Waals) are stronger in the halogen
derivatives.

 Boiling points of haloalkanes containing the same alkyl group, decrease in the order:
RI> RBr> RCl> RF.
Reason: The attractions get stronger as the molecules get bigger in size and have
more electrons. This is because with the increase in size and mass of halogen atom,
the magnitude of Van der Waal forces of attraction increases as they have more
electrons.
 The boiling points of isomeric haloalkanes decrease with increase in branching
Reason: With increase in branching surface area decreases as a result the
magnitude of Van der Waal forces of attraction decreases.
Example: 2-bromo-2-methylpropane has the lowest boiling point among the three
isomers.
CH3
I
CH3-CH2-CH2-CH2-Br CH3-CH2-CH-CH 3 CH3-C-CH3
I I
Br Br
B.P in K 375K 364K 346K
 Boiling points of isomeric dihalobenzenes are nearly the same. However, the para-
isomers have high melting point as compared to their ortho and meta-isomers. It is
due to symmetry of para-isomers that fits in crystal lattice better as compared to
ortho- and meta-isomers.

SKCH COMP. PU COLLEGE 16 DEPARTMENT OF CHEMISTRY

 Cl Cl Cl

Cl

Cl

Cl

B.P in K 453 446 448

M.P in K 256 249 323

5. Density
Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than water. The
density increases with increase in number of carbon atoms, halogen atoms and atomic
mass of the halogen atoms.

6. Solubility: The haloalkanes are slightly soluble in water.

Reason: For a haloalkane to dissolve in water, energy is required to overcome the
attractions between the haloalkane molecules and break the hydrogen bonds between
water molecules. Less energy is released when new attractions are set up between the
haloalkane and the water molecules, as these are not as strong as the original hydrogen
bonds in water. As a result, the solubility of haloalkanes in water is low.
However, haloalkanes tend to dissolve in organic solvents because the new
intermolecular attractions between haloalkanes and solvent molecules have much the
same strength as the ones being broken in the separate haloalkane and solvent
molecules.

Nature of C-X Bond:

Since halogen atoms are more electronegative than carbon, the carbon-halogen bond of
alkyl halide is polarised; the carbon atom bears a partial positive charge. (δ+) whereas the
halogen atom bears a partial negative charge.(δ-)

δ+ δ
C X

Since the size of halogen atom increases as we go down the group in the periodic table,
fluorine atom is the smallest and iodine atom, the largest. Consequently the carbon-halogen
bond length also increases from C-F to C-I. Some typical bond lengths, bond enthalpies and
dipole moments are given in following table.
Bond C-X Bond enthalpies( in kJ Dipole moment
Bond
length(pm) mol-1) (Debye)
CH3–F 139 452 1.847
CH3– Cl 178 351 1.860
CH3–Br 193 293 1.830
CH3–I 214 234 1.636

SKCH COMP. PU COLLEGE 17 DEPARTMENT OF CHEMISTRY

Chemical Properties:
Reactions of Haloalkanes:
1) Elimination reaction:
a) Reaction with alcoholic KOH: (Dehydrohalogenation)
When haloalkanes with β-H-atom are heated with alc. KOH solution, elimination of H-atom
takes place at β-carbon atom and halogen from α-carbon atom leading to the formation of
alkenes. Elimination takes places according to Saytzeff’s rule.
General reaction: R-CH2-CH2-X + KOH(alc.) R-CH=CH 2 + KX + H2O

Halo alkane alkene
(Alkyl halide)

Example: CH3-CH2-CH2-Cl + KOH(alc.) CH3-CH=CH 2 + KCl + H2O


1-Chloropropane Propene
(Propyl chloride)

Note:
 This reaction is often called β-elimination because β-H-atom is eliminated.
 If more than one β-H-atom is available for elimination, then the elimination takes place
according to Saytzeff rule.
 Saytzeff rule: In dehydrohalogenation reaction, the preferred product is that alkene
which has the greater number of alkyl groups attached to the doubly bonded C-atoms.
OR
During dehydrohalogenation, hydrogen atom is removed from the β-carbon atom
containing lesser number of hydrogen atoms.
Example: CH3-CH2-CH-CH 3 + KOH(alc.) CH3-CH=CH-CH 3 + CH3-CH2-CH=CH 2 + KBr + H2O

Br
-
2 Bromobutane 2-butene 1-butene
(major) (minor)

2) Reaction with metals:

a) Reaction with Sodium(Na) metal: (Wurtz reaction)
Alkyl halides react with Na metal in dry ether medium to give higher alkanes (double
the number of c-atoms present in alkyl group of alkyl halides)
Dry ether
General reaction: R-X + 2Na + R-X 
R-R + 2NaX
Halo alkane Halo alkane alkane
(Alkyl halide)
(Alkyl halide)

Dry ether
Example: CH3Cl + 2Na + CH3Cl CH3-CH3 + 2NaCl

Chloromethane Chloromethane Ethane
(Methyl Chloride) (Methyl Chloride)

Note:
 When two different alkyl halides react mixture of three alkanes are obtained.
 30 alkyl halides do not undergo Wurtz reaction instead they undergo
dehydrohalogenation.
 This reaction is used for ascent in series ( i.e. to increase the number of c-atoms).

SKCH COMP. PU COLLEGE 18 DEPARTMENT OF CHEMISTRY

 Dry ether
General reaction: R-X + 2Na + R'-X R-R' + R'-R' + R-R + 2NaX

Dry ether
Example: CH3Cl + 2Na + CH3-CH2-Cl CH3-CH3 + CH3-CH2-CH3 + CH3-CH2-CH2-CH3
Chloromethane Chloroethane Ethane Propane Butane

b) Reaction with magnesium metal: (preparation of Grignard reagent)

When alkyl halides are treated with Mg metal in presence of dry ether, alkyl magnesium
halides are obtained, they are called as Grignard reagents. They belong to a class of
compounds called as organometallic compounds because they contain C-metal bond.

Dry ether
General reaction: R-X + Mg R-Mg-X
Halo alkane Alkyl magnesium halide
(Alkyl halide) (Grignard reagent)

Dry ether
Example: CH3Br + Mg CH3-Mg-Br
Bromomethane Methyl magnesium bromide
(Methyl Bromide)

Note:
 Grignard reagents are highly reactive and react with any source of proton to give
hydrocarbons, even water, alcohol; amines are sufficiently acidic to convert them to
corresponding hydrocarbons. Hence it is necessary to carry out the preparation of RMgX
in absence of moisture hence dry ether is used.

3) Nucleophile substitution reactions:

In this type of reaction, a nucleophile reacts with haloalkane (the substrate) having a
partial positive charge on the carbon atom bonded to halogen. A substitution reaction
takes place and halogen atom, called leaving group departs as halide ion. Since the
substitution reaction is initiated by a nucleophile, it is called nucleophilic substitution
reaction.

General reaction: Nu + δ
- δ- -
+ X Nu + X

Nucleophile Halo alkane

Substituted product
(Alkyl halide)
(Reagent) (Substrate)

It is one of the most useful classes of organic reactions of alkyl halides in which halogen
bonded to sp3 hybridised carbon. The products formed by the reaction of haloalkanes
with some common nucleophiles are given below

a) Reaction with Aqueous KOH/NaOH :( substitution by Hydroxyl group)

Haloalkane upon boiling with aqueous alkali such as KOH/NaOH corresponding alcohols are
obtained.

SKCH COMP. PU COLLEGE 19 DEPARTMENT OF CHEMISTRY

 General reaction: R-CH2-CH2-X + KOH(aq.) R-CH2-CH2-OH+ KX
Halo alkane Alchol
(Alkyl halide)

Example: CH3-CH2-CH2-Cl + KOH(aq.) CH3-CH2-CH2-OH + KCl

1-Chloropropane Propanol
(Propyl chloride)

b) Reaction with Water: (substitution by Hydroxyl group)

When halo alkanes are boiled with water corresponding alcohols are obtained.
Boil
General reaction: R-X + H2O R-OH + HX
Halo alkane Alchol
(Alkyl halide)
Boil
Example: CH3-CH2-Br + H2O CH3-CH2-OH + HBr
Bromoethane Ethanol
(Ethyl bromide) (Ethyl alcohol)

c) Reaction with Sodium alkoxide: (substitution by alkoxy group)

When halo alkanes are heated with sodium or potassium alkoxide corresponding ethers or
alkoxyalkanes are obtained. This reaction is called as Williamson’s ether synthesis.
Heat
General reaction: R-X + R'-O-Na R-O-R' + NaX
Halo alkane Sod. alkoxide Ether
(Alkyl halide)

Heat
Example: CH3-CH2-Br + CH3-O-Na CH3-CH2-O-CH3 + NaBr
Bromoethane Sod. methoxide Methoxy ethane
(Ethyl bromide) (Ethyl methyl ether)

c) Reaction with alcoholic Potassium cyanide: (substitution by cyano group)

When halo alkanes react with alcoholic KCN to form alkane nitriles or alkyl cyanides as
major product.
General reaction: R-X + KCN (alc.) R-CN + KX
Halo alkane

Alkane nitrile
(Alkyl halide) (Alkyl cyanide)

Example: CH3-CH2-Br + KCN(alc.) CH3-CH2-CN + KBr


Bromoethane Propanenitrile
(Ethyl bromide) (Ethyl cyanide)
Note:

 Isocyanides are also obtained as minor products.

 This reaction is used for ascent in series.

d) Reaction with alcoholic Silver cyanide: (substitution by isocyanide group)

When halo alkanes react with alcoholic AgCN to form alkyl isocyanides or carbylamines
which have extremely unpleasant or foul smell.

SKCH COMP. PU COLLEGE 20 DEPARTMENT OF CHEMISTRY

 General reaction: R-X + AgCN (alc.) R-NC + AgX
Halo alkane

Carbylamine
(Alkyl halide) (Alkyl isocyanide)

Example: CH3-CH2-Br + AgCN (alc.) CH3-CH2-NC + AgBr


Bromoethane Ethyl carbylamine
(Ethyl bromide) (Ethyl isocyanide)

Note:
 Ambident Nucleophile: A nucleophile which is capable of attacking through more than
one atom or site is called as ambident nucleophile. Eg: CN-, NO2- ….e.t.c..
 KCN is predominantly ionic therefore both C and N atoms are free to donate electron
pair because C-C bond is relatively stronger than C-N bond the attack mostly occurs
through the C-atom of the cyanide group to form alkyl cyanides as major product.
 AgCN is predominantly covalent therefore N-atom which is free to donate the electron
pair and hence the attack occurs mostly by the N-atom of cyanide group to form carbyl
amines as major product.

e) Reaction with ammonia: (substitution by amine group)

When halo alkanes are heated with alcoholic ammonia in a sealed glass tube to 110 0C
halogen atom is substituted by –NH2 (amine group) to form primary amine. The primary
amine formed react with haloalkane to form secondary amines, tertiary amines and
Quaternary ammonium halide salts. This reaction is known as Hoffmann ammonolysis
reaction OR Hoffmann alkylation.

General reaction: R-X 1100c

+ NH3 R-NH 2 + HX
Halo alkane
 0
1 Amine
(Alkyl halide)

R-NH 2 + R-X R2-NH + HX

 0
2 Amine

R2-NH + R-X R3-N + HX

 0
3 Amine

+ -
R3-N + R-X [R4-N] X

Quarternary ammonium halide

Example: NH3 CH3-NH 2 + HBr

CH3-Br +  Methanamine
Bromomethane
(Methyl bromide) (Methyl amine)

CH3-NH 2 + CH3-Br (CH3)2-NH + HBr

 N-methyl Methanamine
(Dimethyl amine)

(CH3)2-NH + CH3-Br (CH3)3-N + HBr

 N,N-dimethyl Methanamine
(Trimethyl amine)
+ -
(CH3)3-N + CH3-Br [(CH3)4-N] Br

Tetramethyl ammonium bromide

SKCH COMP. PU COLLEGE 21 DEPARTMENT OF CHEMISTRY

f) Reaction with potassium nitrite: (Substitution by nitrite group)
Haloalkanes upon heating with sodium or potassium nitrite, gives corresponding alkyl
nitrites.
General reaction: R-X + KNO 2 R-O-N=O + KX
Halo alkane

Alkyl nitrite
(Alkyl halide)

Example: CH3-CH2-Br + KNO 2 CH3-CH2-O-N=O + KBr

Bromoethane

Ethyl nitrite
(Ethyl bromide)

g) Reaction with silver nitrite: (Substitution by nitro group)

Haloalkanes upon heating with silver nitrite (AgNO2), gives corresponding nitro alkanes.

General reaction: R-X + AgNO 2 R-NO 2 + AgX

Halo alkane

Nitro alkanes
(Alkyl halide)
Example: CH3-CH2-Br + AgNO 2 CH3-CH2-NO 2 + AgBr
Bromoethane

Nitro ethane
(Ethyl bromide)
h) Reaction with silver salt of carboxylic acid: (Substitution by carboxylic group)
Haloalkanes upon heating with ethonolic solution of silver salt of fatty acid esters are
obtained.

C2H 5OH
General reaction: R-X + R'-COOAg R'-COO-R + AgX
Halo alkane
 Ester
(Alkyl halide) (Alkyl alkanoates)
C 2H5OH
Example: CH3-CH2-Br + CH3-COOAg CH3-COO-CH2-CH3 + AgBr
Bromoethane

Silver acetate Ethyl ethanoate
(Ethyl bromide) (Ethyl acetate)
i) Reaction with Sodium alkynides: (Substitution by alkyl group)
Haloalkanes upon heating with Sodium salt of alkynides (sodium alkynides), higher
alkynes are obtained.
General reaction: R-X + R'-C=C-Na
_ R'-C=C-R
_ + NaX
Halo alkane Sodium alkynide Higher alkyne
(Alkyl halide)

Example: CH3-CH2-Br + CH=C-Na

_ CH=C-CH
_ 2-CH3 +
NaBr
Bromoethane Sodium acetylide 1-Butyne
(Ethyl bromide)

j) Reaction with lithium aluminium hydride: (Substitution by hydride ion (H-))

Haloalkanes on reduction with lithium aluminium hydride gives corresponding hydro
carbons.

SKCH COMP. PU COLLEGE 22 DEPARTMENT OF CHEMISTRY

 General reaction: 4 R-X + LiAlH 4 4 R-H + LiX + AlX 3
Halo alkane Alkane
(Alkyl halide) (Hydrocarbon)

Example: 4 CH3-CH2-Br + LiAlH 4 4 CH3-CH3 + LiBr + AlBr 3

Bromoethane Ethane
(Ethyl bromide)

Mechanisms of Nucleophilic substitution reactions:

Alkyl halide undergoes Nucleophilic substitution reactions by the following two different
mechanism.
SN1 mechanism and SN2 mechanism.
a) SN1 mechanism [Unimolecular reaction]:
Generally tertiary alkyl halide undergoes nucleophilic substitution reaction by SN1
mechanism. It involves 2 steps. The rate of the reaction depends only on the molar
concentration of alkyl halide it does not depend on the molar concentration of nucleophile.
Hence it follows first order kinetics.
Ex: When tertiary butyl bromide is treated with aqueous NaOH, t-butyl alcohol is obtained.
CH3 CH3
I I
CH3-C-Br + NaOH (aq.) CH3-C-OH + NaBr
I I
CH3 CH3
t-Butyl bromide t-Butyl alcohol
Mechanism: The mechanism involves the following two steps.
Step 1:
Formation of carbocation: t-butyl bromide undergoes ionization to form a t-butyl
carbocation.
CH3 CH3
I Slow I+ -
CH3-C-Br RDS CH3-C + Br
I I
CH3 CH3
t-Butyl bromide t-Butyl carbocation
(planar)
This step is the slowest step hence it is the rate determining step.

Step-2:
Attack of nucleophile on the carbocation: The nucleophile OH- can attack the
carbocation either from front side or back side to form t-butyl alcohol.
CH3 CH3
I+ - Fast I
CH3-C + OH CH3-C-OH
I I
CH3 CH3
t-Butyl carbocation t-Butyl alcohol

This step is fast.

Rate  [t-butyl bromide]1 [OH- ]0
 Order = 1

SKCH COMP. PU COLLEGE 23 DEPARTMENT OF CHEMISTRY

Note:
1. The order of reactivity of different alkyl halides towards SN1 mechanism is tertiary >
secondary > primary alkyl halides.
2. It is favoured by weak nucleophile and polar solvents.
3. SN1 mechanism is a unimolecular reaction.
4. The product obtained is a racemic mixture if the reaction is carried at an asymmetric C-
atom.

b) SN2 mechanism [Bimolecular reaction]:

Generally primary alkyl halides undergo Nucleophilic substitution reaction by SN2
mechanism.
This involves only one step. The rate depends on molar concentrations of both alkyl halide
and nucleophile. Hence it follows a second order kinetics.
Ex: When methyl bromide is treated with NaOH sodium hydroxide, methanol is obtained
CH3 – Br + NaOH (aq.)  CH3OH + NaBr

Mechanism of SN2 mechanism:

The mechanism of above reaction involves the following step. The nucleophile OH- of NaOH
attack carbon atom of methyl bromide exactly from the opposite side to that of Br to form a
transition state. The transition state involves the formation of a partial C-OH bond and
cleavage of C-Br bond. The transition state attains stability by loosing Br- to form methanol.
H H H H
- -
OH + H C Br HO IIIIIIIIIIIIIII C IIIIIIIIIIIIIII Br HO C H + Br
H H
H
Nucleophile Methyl bromide Transition state Methanol

 Rate  [CH3Br]1 [OH- ]1

 Order = 2
Note:
1. The reactivity of different alkyl halides towards SN2 mechanism is as follows:
Primary > Secondary > tertiary alkyl halides
2. It is favoured by strong nucleophile and non polar solvents.
3. SN2 mechanism is a bimolecular reaction.
4. The product obtained has inverse configuration to that of alkyl halide if the reaction is
carried at an asymmetric C-atom.

Differences between SN1 mechanism and SN2 mechanism:

SN1 mechanism SN2 mechanism
a) It involves 2 steps It involves only one step
b) It follows first order kinetics It follows second order kinetics
c) Rate depends only on alkyl halide Rate depends on both nucleophile and
alkyl halide

SKCH COMP. PU COLLEGE 24 DEPARTMENT OF CHEMISTRY

d) The order of reactivity of different alkyl The order of reactivity of different alkyl
halides is 3o > 2o > 1o alkyl halides halides is 1o > 2o > 3o alkyl halides.
e) It is favoured by polar solvent and by It is favoured by non polar solvents and by
weak nucleophile strong nucleophile
f) The product is racemic The product obtained has inverse
configuration to that of alkyl halides.

STEREOCHEMICAL ASPECTS OF NUCLEOPHILIC SUBSTITUTION REACTIONS:

If in a reaction, no bond to the stereocentre is broken, the product will have the same
general configuration of groups around the stereocentre as that of reactant. Such a reaction
is said to proceed with retention of the configuration.

RETENTION:
Retention of configuration is the preservation of integrity of the spatial arrangement
of bonds at an asymmetric centre during a chemical reaction or transformation.
OR
It is the configurational correlation when a chemical species XCabc is converted into
the chemical species YCabc having the same relative configuration.
c c
-
Y
b X b Y
a a
Example: The reaction that takes place when (–)-2-methylbutan-1-ol is heated with
concentrated hydrochloric acid.
CH3 CH3
H CH2-OH H CH2-Cl
Heat
+ HCl + H2O
CH2 CH2

CH3 CH3
(-)-2-Methylbutan-1-ol (-)-1-Chloro-2-methylbutane
If the nucleophilic substitution reaction is carried for an optically active alkyl halide at the
stereo center then SN1 reaction proceeds with racemisation and a SN2 reaction proceeds with
complete stereochemical inversion.

INVERSION, RETENTION AND RACEMISATION: There are three outcomes for the
reaction that takes place at an asymmetric carbon atom.
Consider the replacement of a group X by Y in the following reaction;
 If (A) is the only compound obtained, the process is called retention of configuration.
 If (B) is the only compound obtained, the process is called inversion of configuration.
 If a 50:50 mixture of the above two is obtained then the process is called racemisation
and the product is optically inactive, as one isomer will rotate light in the direction
opposite to another.

SKCH COMP. PU COLLEGE 25 DEPARTMENT OF CHEMISTRY

 C2 H5 C2 H 5
C2 H5
Y Y
H Y Y H
CH3 X H CH3
CH3
B A
Inversion Retention
Y

A+B
50:50
Racemisation

Now let us have a fresh look at SN1 and SN2 mechanisms by taking examples of
optically active alkyl halides.

SN1 mechanism at an asymmetric C-atom:

In case of optically active alkyl halides, SN1 reactions are accompanied by racemisation.
Because the carbocation formed in the slow step (first step) being sp2 hybridised is planar
(achiral). The attack of the nucleophile on the carbocation may be accomplished from either
side resulting in a mixture of products, one having the same configuration i.e the –OH
attaching on the same position as halide ion and the other having opposite configuration i.e
the –OH attaching on the side opposite to halide ion.

Example:
In the hydrolysis of optically active 2-bromobutane, which results in the formation of (±)-
butan-2-ol.

Step-I: Formation of carbocation:

H CH3
H3C
Br + -
H + Br
H3C-H2C CH2-CH3
2-Bromo butane Carbocation

Step-II: Attack of nucleophile on the carbocation:

CH2-CH3 H3C H CH3
- + -
HO OH + + OH OH
H
H3C H CH2-CH3 H3C-H2C
(+)-2-Butanol Carbocation (-)-2-Butanol

SN2 mechanism at an asymmetric C-atom:

In case of optically active alkyl halides, the product formed as a result of SN2 mechanism has
the inverted configuration as compared to the reactant. This is because the nucleophile
attaches itself on the side opposite to the one where the halogen atom is present.

SKCH COMP. PU COLLEGE 26 DEPARTMENT OF CHEMISTRY

Example: When (-)-2-bromooctane is allowed to react with sodium hydroxide, (+)-octan-2-ol
is formed with the –OH group occupying the position opposite to what bromide had
occupied. Thus, SN2 reactions of optically active halides are accompanied by inversion of
configuration.
CH3 CH3

NaOH
H Br + HO H + NaBr
C6H13 C6H13

(-)-2-Bromooctane (+)-Octan-2-ol

Reactions of Haloarenes /Halo benzene:

1) Reaction with metals:
a) Wurtz Fittig reaction: When a mixture of alkyl halide and aryl halide are heated with
sodium metal in presence of dry ether alkyl arene or alkyl benzene is obtained. This reaction
is called Wurtz Fittig reaction.
R
X

Dry ether
General reaction: + 2Na + R-X + 2NaX


Haloarene Halo alkane Alkyl benzene

(Aryl halide) (Alkyl halide) (Alkyl arene)

CH3
Cl

Dry ether
+ 2Na + CH3-Cl + 2NaCl
Example: 

Chlorobenzene Chloro methane Methyl benzene

(Methyl chloride) (Toluene)
CH3-CH-CH 3
Cl

CH3-CH-CH 3 Dry ether

+ 2Na + + 2NaCl
Example: I 
Cl
Chlorobenzene 2-Chloro propane Isopropyl benzene

(Isoproplyl chloride) (Cumene)

b) Fittig reaction:
When aryl halides or haloarenes are heated with sodium metal in presence of dry ether
diphenyl is obtained. This reaction is called Fittig reaction.

Cl

Dry ether
+ 2Na + 2NaCl
Example: 2 

Chlorobenzene Diphenyl

SKCH COMP. PU COLLEGE 27 DEPARTMENT OF CHEMISTRY

2) Nucleophilic reactions:
Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to
the following reasons:

(i) Resonance effect: In haloarenes, the lone pair of electrons on halogen atom are in
conjugation with -electrons of the ring and the following resonating structures are
possible.

..
:Cl: Cl
+
Cl
+
Cl
+
Cl

As a result C-Cl bond acquires a partial double bond character due to resonance.
As a result, the bond cleavage in haloarene is difficult than haloalkane and therefore,
they are less reactive towards nucleophilic substitution reaction.

(ii) Difference in hybridisation of carbon atom in C—X bond: In haloalkane, the carbon
atom attached to halogen is sp3 hybridised while in case of haloarene, the carbon atom
attached to halogen is sp2-hybridised. The sp2 hybridised carbon with a greater s-
character is more electronegative and can hold the electron pair of C—X bond more
tightly than sp3-hybridised carbon in haloalkane with less s-chararcter. Thus, C—Cl
bond length in haloalkane is 177pm while in haloarene is 169 pm. Since it is difficult to
break a shorter bond than a longer bond, therefore, haloarenes are less reactive than
haloalkanes towards nucleophilic substitution reaction.

X
X

2
sp hybridised
3
sp hybridised
Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as a result of
self-ionisation will not be stabilized by resonance and therefore, SN1 mechanism is ruled out.

(iii) Because of the possible repulsion, it is less likely for the electron rich nucleophile to
approach electron rich arenes.

Example:

1) Replacement by hydroxyl group (formation of phenol): Dow’s process

On heating aryl halides (Chlorobenzene) with aqueous solution sodium hydroxide at a
temperature of 623K under a pressure of 300 atmospheres the halogen atom is replaced by
an hydroxyl group leading to the formation of phenol.

SKCH COMP. PU COLLEGE 28 DEPARTMENT OF CHEMISTRY

 ONa OH
Cl

623K, 300atm
+ NaOH + HCl + NaCl

Sodium phenate Phenol
Chlorobenzene

The presence of an electron withdrawing group (-NO2) at ortho- and para-positions

increases the reactivity of haloarenes.
ONa OH
Cl

443K
+ NaOH + HCl + NaCl


NO 2 NO 2
NO 2
4-Nitrophenol
4-Nitrochlorobenzene

ONa OH
Cl
NO 2 NO 2
NO 2
368K
+ NaOH + HCl + NaCl


NO 2 NO 2
NO 2
2,4-Dinitrophenol
2,4-Dinitrochlorobenzene
The effect is pronounced when (-NO2) group is introduced at ortho and para- positions.
However, no effect on reactivity of haloarenes is observed by the presence of electron
withdrawing group at meta-position.

Mechanism of the reaction is as depicted:

SKCH COMP. PU COLLEGE 29 DEPARTMENT OF CHEMISTRY

 3) Electrophilic reactions:
Haloarenes undergo the usual electrophilic substitution reactions of the benzene ring such
as halogenation, nitration, sulphonation and Friedel-Crafts reactions. Halogen atom besides
being slightly deactivating is o, p directing; therefore, further substitution occurs at ortho- and
para positions with respect to the halogen atom.
The o, p-directing influence of halogen atom can be easily understood if we consider the
resonating structures of halobenzene as shown:

Due to resonance, the electron density increases more at ortho- and para-positions than at
meta-positions. Further, the halogen atom exhibits -I effect as a result some electron cloud is
withdrawn from the benzene ring. As a result, the ring gets deactivated when compared to
benzene and hence the electrophilic substitution reactions in haloarenes occur slowly and
require more drastic conditions as compared to those in benzene.

i. Halogenation:
When haloarenes are treated with halogens in the presence of a lewis acid catalyst
which also acts as a halogen carrier such as ferric salts, halogenation takes place
leading to the formation of a mixture of o- dihalobenzene and p- dihalobenzene.
Cl
Cl
Cl
Cl
anhy.FeCl 3
2 + 2 Cl 2 + + 2HCl

Cl
Chlorobenzene 1,2-Dichlorobenzene 1,4-Dichlorobenzene

(o-Dichlorobenzene) (p-Dichlorobenzene)

ii. Nitration
When haloarenes are heated with conc. Nitric acid in presence of conc.H2SO4 a mixture
of o-nitrohalobenzene and p-nitrohalobenzene are obtained.
Cl
Cl
Cl
NO 2
conc.H 2SO4
2 +2 HNO 3 + + 2H2O

NO 2
Chlorobenzene 1-chloro,2-nitrobenzene 1-chloro,4-nitrobenzene

(o-nitrochlorobenzene) (p-nitrochlorobenzene)

iii. Sulphonation
When haloarenes are heated with conc.H2SO4 a mixture of o-Chlorosulphonicacid and p-
Chlorosulphonicacid are obtained.

SKCH COMP. PU COLLEGE 30 DEPARTMENT OF CHEMISTRY

 Cl
Cl Cl
SO3H
conc.H 2SO4
2 + 2 H2SO4 + + 2H2O

SO3H
Chlorobenzene 2-chlorobenzene sulphonic acid 4-chlorobenzene sulphonic acid

iv. Friedel-Crafts alkylation

When haloarenes are heated with Alkyl halides such as methyl chloride in presence of
anhydrous aluminium chloride catalyst a mixture of o-Chlorotoluene and p-
Chlorotoluene are obtained.
Cl
Cl Cl
CH3
Anhy.AlCl 3
2 + 2 CH3Cl + + 2HCl

CH3
Chlorobenzene 1-chloro-2-methylbenzene 1-chloro-4-methylbenzene

v. Friedel-Crafts acylation
When haloarenes are heated with Acyl halides such as ethonyl chloride or acetyl
chloride in presence of anhydrous aluminium chloride catalyst a mixture of o-
Chloroacetophenone and p- Chloroacetophenone are obtained.
Cl
Cl Cl O
O

Anhy.AlCl 3 CH3
2 + 2 H3C Cl + + 2HCl


Chlorobenzene Acetylchloride
H3C O
2-chloroacetophenone 4-chloroacetophenone

Polyhalogen Compounds:
Carbon compounds containing two or more halogen atoms are usually referred to as
polyhalogen compounds. These compounds are useful in industry and agriculture.
Some commercially important polyhalogen compounds are:

1) Dichloromethane (Methylene chloride), CH2Cl2:

Uses:
Dichloromethane is widely used.
1. As a solvent for paint remover, metal cleaning, finishing solvent and in the in the
manufacture of drugs.
2. As a propellant in aerosols,

SKCH COMP. PU COLLEGE 31 DEPARTMENT OF CHEMISTRY

Harm full effects:
1. Methylene chloride harms the human central nervous system. Exposure to lower levels
of methylene chloride in air can lead to slightly impaired hearing and vision.
2. Higher levels of methylene chloride in air cause dizziness, nausea, tingling and
numbness in the fingers and toes.
3. In humans, direct skin contact with methylene chloride causes intense burning and mild
redness of the skin. Direct contact with the eyes can burn the cornea.

2) Trichloromethane (Chloroform), CHCl3:

Uses:
1. In industry, chloroform is used as a solvent for fats, alkaloids, iodine and other
substances.
2. It is used the production of the Freon refrigerant R-22.
3. It is used as general anesthetics in surgery. But has been replaced by less toxic, safer
anesthetics, such as ether.

Harm full effects:

1. Chronic chloroform exposure may cause damage to the liver (where chloroform is
metabolised to phosgene) and to the kidneys, and some people develop sores when the
skin is immersed in chloroform.
2. Chloroform is slowly oxidised by air in the presence of light and release extremely
poisonous gas i.e carbonyl chloride, also known as phosgene (COCl2). (Therefore it is
stored in closed dark coloured bottles completely filled so that air is kept out).
2CHCl3 +O2 2COCl2+2HCl
Note: Chloroform was used as a general anesthetic in surgery. This is because inhaling
chloroform vapours depresses the central nervous system. Breathing about 900 parts of
chloroform per million parts of air (900 parts per million) for a short time can cause
dizziness, fatigue, and headache.

3) Triiodomethane (Iodoform),CHI3:
Uses:
1. It was earlier used as an antiseptic but the antiseptic properties are due to the
liberation of free iodine and not due to Iodoform itself. Due to its unpleasant smell, it
has been replaced by other formulations containing iodine.
2. It is used in the manufacture of pharmaceuticals.

4) Tetrachloromethane (Carbontetrachloride),CCl4:

Uses:
1. It is produced in large quantities for use in the manufacture of refrigerants and
propellants for aerosol cans.
2. It is also used as feedstock in the synthesis of chlorofluorocarbons and other
chemicals, pharmaceutical manufacturing, and general solvent use.
3. Until the mid 1960’s it was widely used as a cleaning fluid, both in industry, as a
degreasing agent, and in the home, as a spot remover and as fire extinguisher.

SKCH COMP. PU COLLEGE 32 DEPARTMENT OF CHEMISTRY

 Harm full effects:
1. There is some evidence that exposure to carbon tetrachloride causes liver cancer in
humans. The most common effects are dizziness, light headedness, nausea and
vomiting, which can cause permanent damage to nerve cells. In severe cases, these
effects can lead rapidly to stupor, coma, unconsciousness or death. Exposure to
CCl4 can make the heart beat irregularly or stop. The chemical may irritate the eyes
on contact.
2. When carbon tetrachloride is released into the air, it rises to the atmosphere and
depletes the ozone layer. Depletion of the ozone layer is believed to increase human
exposure to ultraviolet rays, leading to increased skin cancer, eye diseases and
disorders, and possible disruption of the immune system.
5) Freons:
Definition: The chlorofluorocarbon compounds of methane and ethane are collectively
known as freons.
Example: Freon 12 (CCl2F2). (It is one of the most common freons in industrial use)

Preparation: Freon 12 is manufactured by the action of antimony fluoride on

tetrachloromethane in the presence of antimony pentachloride by Swarts reaction.
Physical properties: They are extremely stable, unreactive, non-toxic, non-corrosive
and easily liquefiable gases.

Uses of Freon 12 (CCl2F2):

1. These are usually produced for aerosol propellants, refrigeration and air conditioning
purposes.

Harm full effects:

1. Freon are used in refrigeration, eventually makes its way into the atmosphere where it
diffuses unchanged into the stratosphere. In stratosphere, freon is able to initiate radical
chain reactions that can upset the natural ozone balance.
2. By 1974, total freon production in the world was about 2 billion pounds annually.

6) p,p’-Dichlorodiphenyltrichloroethane(DDT):
DDT is the first chlorinated organic insecticides.

Uses:
1. The use of DDT increased enormously on a worldwide basis after World War II,
primarily because of its effectiveness against the mosquito that spreads malaria and
lice that carry typhus.

Harm full effects:

However, problems related to extensive use of DDT began to appear in the late 1940s.
Many species of insects developed resistance to DDT, and it was also discovered to have a
high toxicity towards fish. The chemical stability of DDT and its fat solubility compounded the
problem. DDT is not metabolised very rapidly by animals; instead, it is deposited and stored
in the fatty tissues. If ingestion continues at a steady rate, DDT builds up within the animal
over time.

SKCH COMP. PU COLLEGE 33 DEPARTMENT OF CHEMISTRY

Structure of DDT:
Cl

Cl
Cl Cl

Cl H
DDT
Note:
1. DDT was first prepared in 1873, but it was not until 1939 that Paul Muller of Geigy
Pharmaceuticals in Switzerland discovered the effectiveness of DDT as an
insecticide. Paul Muller was awarded the Nobel Prize in Medicine and Physiology in
1948 for this discovery.
2. IUPAC name for DDT is 2, 2-bis (p-chlorophenyl)-1,1,1-trichloroethane.
3. The use of DDT was banned in the United States in 1973, although it is still in use in
some other parts of the world.

Preparation of DDT:
Cl

Cl
Cl
Conc. H2 SO4
CCl 3CHO + 2  Cl C C Cl

Cl H
Chloral Chlorobenzene DDT

*********

SKCH COMP. PU COLLEGE 34 DEPARTMENT OF CHEMISTRY