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CHAPTER – 10: HALOALKANES AND HALOARENES

Organo halogen compounds are those compounds in which one or more
hydrogen atoms of the hydrocarbon chain are replaced by halogen atoms.
Applications:
 as solvents, refrigerants medicines, polymers, insecticides, pesticides .
Some halogenated organic compounds are
 chloramphenicol an antibiotic used for the treatment of typhoid.
 thyroxine a hormone containing iodine.
 Chloroquine an antimalarial drug.
 chlorotetracycline an antibiotic
 Perfluorodecalin used as artificial blood product for carrying oxygen
 Halothane CF3 –CHClBr is used as an anaesthetic.

Classification of organo halogen compounds based on the number of halogen

atoms:
Monohalogen compounds

Organo halogen compounds Dihalogen compounds

Polyhalogen compounds

Mono halides: compounds containing one halogen atom

Eg: methyl chloride, chlorobenzene etc.

Di halides: compounds containing two halogen atoms.

Eg: dichloromethane, o–dichlorobenzene, m–dichlorobenzene,
p–dichlorobenzene, etc.
If the carbon chain is aliphatic then they are further classified into,

Vicinal dihalides
Dihalides Geminal dihalides
Terminal dihalides

Vicinal di halides (Vic – dihalides):

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Dihalides in which the two halogen atoms are bonded to two adjacent or
neighbouring carbon atoms.
They are called as alkylenedihalides (in trivial system) and 1,2 – dihalides (in
IUPAC system).
Eg: 1,2 – dichloroethane.

Geminal di halides( Gem – dihalides):

Dihalides in which the two halogen atoms are bonded to same carbon atoms.
They are called alkylidene halides (in trivial system) and 1,1 – dihalides
(in IUPAC system).
Eg: 1,1 – dichloroethane.
Terminal di halides:
Dihalides in which the halogen atoms are bonded to the terminal carbon
atoms.
They are called polymethylene dihalides in the trivial system.
Eg: 1,3 – dichloropropane.

Poly halides: Compounds containing many halogen atoms.

Eg: trichloromethane, BHC etc.

Perhalo compounds: Halo compounds containing only carbon and halogen

atoms are called perhalo compounds. Eg: CCl4 (carbon tetrachloride or
tetrachloromethane or pyrene).

Based on the type of hybridisation of carbon atom to which halogen atom is

bonded

Mono halogen
compounds

Compounds having Compounds having Compounds having

sp3 -C-X bond sp2 -C-X bond sp -C-X bond

I] compounds having sp3 hybridised Carbon – halogen bond:

This is further classified as follows:

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Compounds having
sp3 -C-X bond

Alkargyl halides

Alkyl halides Allylic halides Benzylic halides

 Alkyl halides or monohaloalkanes :

Mono halogen derivatives of alkanes obtained by replacing one hydrogen
atom of alkane by halogen atom.
Here, all the C atoms are sp3 hybridised. (All C atoms are saturated).

Their general formula is CnH2n+1 X , X- -F ,-Cl,-Br, -I

These are further classified into

Primary alkyl halide (1O):
Alkyl halide in which the Halogen atom bonded to a primary C- atom. (Primary
carbon atom is that carbon bonded to two hydrogen atoms and one C atom.)

Secondary alkyl halide (2O):

Alkyl halides in which the halogen atom bonded to a secondary C atom.
(secondary C atom is that carbon bonded to two C atoms and a H atom.)

Tertiary alkyl halide (3O):

Alkyl halides in which the halogen atom is bonded to a tertiary C atom.
(Tertiary carbon atom is the carbon atom bonded to three C atoms and no H
atom. )

 Allylic halides:
Allylic halides are the mono halogen compounds in which the halogen atom
is bonded to sp3 hybridised carbon atom which is next to the sp2 hybridised
carbon of the C –C double bond.
Eg: CH2= CH –CH2-Cl ie allyl chloride or 3 –chloro propene

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Allyl halides are further classified as

a) Primary allylic halides (1O)
b) Secondary allylic halides(2O)
c) Tertiary allylic halides (3O)

 Benzylic halides :
Monohalogen compounds in which the halogen atom is bonded to the sp3
hybridised C atom which is next to the sp2 hybridised carbon of aromatic
ring, are called Benzylic halides .

Eg:
They are further classified into
a) Primary benzylic halides (1O)
b) Secondary benzylic halides (2O)
c) Tertiary benzylic halides (3O)
d)
Alkargyl halides:
They are the mono halogen compounds in which the halogen atom is bonded
to the sp3 hybridised C- atom is which is next to an sp hybridised C atom of C -
C triple bond.
Eg: propargyl chloride

II] Compounds having sp2 carbon- halogen bond:

These are further classified into two types

Vinylic halides
Compounds having sp2 C-X bond
Aryl halides

Vinylic halides ( Alkenyl halides) :

Monhalogen compounds in which the halogen atom is bonded to an sp2
hybridised C atom of a C=C double bond are called vinylic halides.
Eg: H2C= CH-Cl vinyl chloride

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Aryl halides or mono halo arenes:

Monohalogen compounds in which the halogen atom is bonded to an sp2
hybridised C atom of an aromatic ring are called aryl halides.
Eg: chloro benzene, bromo benzene

III] Compounds having sp carbon- halogen bond atom bond:

Monohaloalkynes or Alkynyl halide:
Monohalogen compounds in which halogen atom is bonded to sp hybridised
carbon atom of a C-C triple bond are called monohaloalkynes.

Eg:
chloro propyne

Nomenclature of organo halogen compounds:

For haloalkanes:
In trivial system, haloalkanes are named as alkyl halide.
First the name of the alkyl group is written and then the name of the halogen
as halide. Prefixes like n –, iso –, sec –, tert –,neo – etc are used.
In IUPAC system, they are named as haloalkane.

Vicinal di haloalkanes, in the trivial system are named as alkylenedihalides

In the IUPAC system, they are named as 1,2 – dihaloalkanes .
Geminal dihalides, in trivial system, are named as alkylidenehalides.
In IUPAC system, it is called 1,1 – dihaloalkanes.
Terminal dihalo alkanes, in trivial system, are named as poly methylene
dihalides.
For haloalkenes: In case of halogenated alkenes, double bonded C atoms are
given higher priority than the halogen.

Haloarenes are named by writing the name of the halogen first and then the
name of the aromatic ring.

The following table gives the structure, trivial and IUPAC names of some
halogenated compounds:

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Structure/formula Trivial name IUPAC name

CH3F Methyl fluoride Fluoromethane
CH3CH2Cl Ethyl chloride Chloroethane
CH3CH2CH2Br n–propyl bromide 1–bromopropane
CH3CHBrCH3 iso–propyl bromide 2–bromopropane
CH3CH2CH2CH2I n–butyl iodide 1 – iododbutane

sec–butyl iodide 2–iodobutane

iso–butyl iodide 1–iodo–2–methylpropane

tert–butyl iodide 2–iodo–methylpropane

CH3CH2CH2CH2CH2Cl n–pentyl chloride 1–chloropentane
sec–pentyl chloride 2–chloropentane

sec–pentyl chloride 3–chloropentane

iso–pentyl chloride 1–chloro–3–methylbutane

sec–iso–pentyl chloride 2–chloro–3–methylbutane

tert–pentyl chloride 2–chloro–methylbutane

neo – pentyl chloride 1–chloro–2,2–dimethylpropane

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ethylenedichloride 1,2 – dichloroethane

ethylidene chloride 1,1 – dichloroethane

CH2 = CHCl vinyl chloride Chloroethene

CH2 = CH – CH2Cl
allyl chloride 3–chloroprop–1–ene

CH2Cl2 methylene chloride dichloromethane

CHCl3
chloroform trichloromethane

BrCH2 – CH2Cl bromochloroethane 1–bromo–2–chloroethane

benzyl chloride (Chloromethyl)benzene

chlorobenzene Chlorobenzene

o – dichlorobenzene 1,2 – dichlorobenzene

m – dichlorobenzene 1,3 – dichlorobenzene

p – dichlorobenzene 1,4 – dichlorobenzene

p – chloro toluene 4 – methylchlorobenzene

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Isomerism in alkyl halides:

Alkyl halides exhibit two types of isomerism.
1) Structural Isomerism
2) Stereo isomerism
Haloalkanes exhibit structural isomerism of two types
I.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.
Ex: CH3 CH2CH2CH2-Cl CH3CH( CH3) CH2- Cl CH3)3 C –Cl

ll.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 CHI- CH3

STEREO ISOMERISM:

Two or more compounds having 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:

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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 optical isomerism.

It will be further discussed later.

Methods of preparation of haloalkanes:

Haloalkanes can be prepared by the following methods:
1) From alkanes (by substitution reaction)
2) From alkenes (by addition reaction)
3) From alcohols (by substitution reaction)
4) From haloalkanes (by halogen exchange reaction)

From alkanes:
Haloalkanes can be prepared from alkanes by halogenation (chlorination,
bromination) in the presence of diffused sunlight. The reaction follows free
radical mechanism. Diffused sunlight initiates the formation of free radicals.
h
Cn H 2n 2  X 2   Cn H 2n1 X  HX

h
Ex: CH 4  Cl2   CH 3Cl  HCl
But, chlorination further continues to give CH2Cl2 ,CHCl3 and CCl4.
It is difficult to get the mono substituted productby this method
because,chlorination and bromination of alkanes leads to the formation of
complex mixture of poly halogen and isomeric monohalogen compounds.
Eg : CH3 CH2CH3 + Br2 ----> CH3 CHBrCH3 + CH3 CH2CH2Br
Major minor
This depends on the nature of Hydrogen atom to be substituted and nature of
halogen.
ie, it is dependent on the stability of the alkyl free radicals formed. For
example, when propane is chlorinated, we get n – propyl chloride and iso –
propyl chloride, latter being the major product as secondary free radical is
more stable than primary free radical.

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[ Note:
1) Chlorination in the presence of direct sunlight, leads to explosive
reaction leading to the formation of carbon and hydrogen chloride
2) Fluorination reaction is highly explosive as the F – F bond is very weak,
and the reaction is highly exothermic. Energy released is greater than
the energy required to break the F – F and C – C bond. But the reaction
can be carried out by diluting F2 in inert atmosphere like N2 or Ar.
However, alternative methods which are more effective are available.
3) Iodination reaction is reversible due to reducing nature of HI. Therefore,
it has to be carried out in the presence of oxidising agents like HIO3 or
HNO3 etc. Again, like alkyl fluorides, other effective methods are
available.]

From alkenes:
i) By reaction with halogen:
Alkenes react with Br2 in inert solvent like CCl4 to give vic–dibromides in
this the brown colour of bromine is discharged. Hence this bromine
water test is used as a test for unsaturation.

ii) By reaction with hydrogen halides:

Alkenes undergo addition reaction. Addition of hydrogen halides to
alkenes leads to formation of haloalkanes. The relative order of reactivity
for different hydrogen halides is HI > HBr > HCl > HF
This is due to the bond dissociation enthalpies are of the order
HI<HBr < HCl <HF

If the alkene is symmetrical like ethylene, 2 – butene, etc, then we get only one
type of haloalkane.
Eg: CH2 =CH2 + HCl -----> H3C –CH2Cl

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If the alkene is unsymmetric, then different products are obtained in the

presence or absence of organic peroxides.

In the absence of peroxides:

In the absence of organic peroxides, when alkenes are treated with hydrogen
halides, we get products according to Markownikov’s rule. It follows
electrophilic addition reaction mechanism.

Ex:
Markovnikov’s rule (Markovnikoff’s rule):
When an asymmetric molecule is added to an asymmetric alkene, the
positive part of the molecule is added to the carbon atom involved in the
double bond containing more number of hydrogen.
Such an addition reaction is called Markownikov addition.
Note:
Markovnikov’s addition is possible for the addition of HCl,HBr and HI

In the presence of peroxides:

Unsymmetrical alkenes and HBr (not HCl or HI) react in the presence of organic
peroxides like benzoyl peroxide ( C6H5 -CO-O-O-CO- C6H5 ) to give a product
which is against Markownikov’s rule. This takes place due to free radical
addition reaction.
Such an addition in presence of the peroxide is called Anti Markovnikov
addition or peroxide effect or Kharasch effect.

Ex:
Note:
Anti Markownikov addition is only for the addition of HBr but not HCl and HI.
This is because, the bond dissociation enthalpy for HCl is very high and cannot
undergo homolysis. HI bond enthalpy is low, so can undergo homolysis to give

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Iodine free radical. But it is unstable and combines to form I2 molecule.

Starting from Alcohols:

Starting from alcohols, haloalkanes can be prepared by reaction with
I;hydrogen halides (HX),
ii. Phosphorus halides [both phosphorus tri halides (PX3) and phosphorus
pentachloride (PCl5)]
iii. thionylchloride (SOCl2).
1. From alcohols by reaction with hydrogen halides:
From alcohols by reaction with hydrogen halides alkyl halide and water as the
by product are obtained. It is a nucleophilic substitution reaction.
Water also acts as a nucleophile and gives back alcohol ie, the reaction is
reversible in nature.Hence the reaction has to be performed in the presence of
a suitable dehydrating agent.
R  OH  HX 
 R  X  H 2O

Note:
i.Order of reactivity of alcohols for this reaction is 30 > 20 > 10 > CH3OH.
ii. Order of reactivity of halogen acids for this reaction is HI > HBr > HCl

a. For alkyl chlorides or chloroalkanes:

primary and secondary chloroalkanes can be prepared by passing dry hydrogen
chloride gas or conc HCl, through the alcohol in the presence of anhydrous zinc
chloride. This reaction is called Grove’s process.
R-OH + HCl(g) 
anhydrous ZnCl2
R-Cl + H 2O
Ex: CH3CH 2 -OH + HCl (g) 
anhydrous ZnCl 2
CH 3CH 2 -Cl + H 2O

Turbidity

Note:
 The mixture of anhydrous ZnCl2 and conc.HCl is called Lucas reagent.
 This test can be used to distinguish between 10 20 and 30 alcohols
 As the product alkyl chloride is insoluble in water, there is a formation of
turbidity.

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 Depending on the time required to develop the turbidity, the different

types of alcohols can be distinguished.
 30 alcohols develop turbidity with Lucas reagent immediately.
 20 alcohols develop turbidity after 5 -10 min
 10 alcohols don’t develop turbidity at room temperature and develop
turbidity only after heating.
 Tertiary alcohols, however, react readily with Conc. HCl even in the
absence of zinc chloride.

b.For alkyl bromides or bromoalkanes:

Alkyl bromides are obtained by refluxing alcohols with constant boiling
hydrobromic acid (48%) in the presence of little conc. H2SO4.
HBr is can be generated in situ by the action of Conc. H2SO4 on KBr or NaBr.
R-OH + HBr 
conc H2SO4
 R-Br + H2O
CH3CH2 -OH + HBr 
conc H2SO4
 CH3CH 2 -Br + H 2O
CH3CH2OH + NaBr + H2SO4 ------ > CH3CH2Br + NaHSO4 + H2O
c.For alkyl iodides or iodoalkanes:
These are prepared by refluxing a suitable alcohol with constant boiling
hydroiodic acid (57%). HI may also be generated in situ by the action of 95%
phosphoric acid on KI.
R-OH + HI 
Reflux
 R-I + H 2O
CH3CH2 -OH + HI 
Reflux
 CH3CH2 -I + H 2O
CH3CH2OH + KI + H3PO4 ------ > CH3CH2I + KH2PO4 + H2O
Note:
H2SO4 cannot be used here, because, it oxidises HI into I2.

2.From alcohols by the reaction with phosphorus tri halides (PX3):

Alcohols react with PX3 to form the corresponding haloalkanes.
3R-OH + PX3 
 3R-X + H3PO3 ; X  Cl, Br , I
3CH3CH2 -OH + PCl3 
 3CH3CH 2 -Cl + H3PO3
3CH3 -OH + PBr3 
 3CH3 -Br + H3PO3
3CH3 -OH + PI3 
 3CH3 -I + H3PO3

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Note: The compounds PBr3 and PI3 are less stable and they are prepared in situ
by the action of red P on bromine and iodine respectively

From alcohols by the action on PCl5:

Alkyl chlorides can also be prepared by the action of phosphorus
pentachloride.
R-OH + PCl5 
 R-Cl + HCl + POCl3
CH3CH2 -OH + PCl5 
 CH3CH2 -Cl + HCl + POCl3
Note:
PBr5 and PI5 are unstable and don’t exist.

From alcohols by the action of SOCl2 (Darzen’s method):

Alkyl chlorides are best prepared by the action of alcohols with thionyl
chloride in the presence of pyridine (base). In this reaction the by-products SO2
and HCl are gases and the product is left in pure state.
R-OH +SOCl2 
pyridine
 R-Cl + HCl +SO2
CH3CH2 -OH +SOCl2 
pyridine
 CH3CH 2 -Cl + HCl +SO2
Note:
 Only alkyl chloride can be prepared by Darzen’s method, because,
SOBr2 and SOI2 are unstable and don’t exist.
 As discussed above, Alkyl chlorides can be prepared by alcohols.
 But aryl halides can not be prepared by phenols because, DUE TO
RESONANCE, C-OH BOND DEVELOPS PARTIAL DOUBLE BOND
CHARACTER. Hence, it is difficult to break the C-OH bond.

From haloalkanes by halogen exchange reaction:

Fluoroalkanes and iodoalkanes are best prepared by halogen exchange
reaction.
Swart’s reaction:
Fluoroalkanes are prepared by the action of inorganic fluorides like AsF3, SbF3,
CoF2, AgF, Hg2F2, etc. on chloroalkanes or bromoalkanes.
Ex: CH3Br + AgF 
 CH3 - F+ AgBr
Finkelstein’s reaction:

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Iodoalkanes are prepared by the action of sodium iodide in dry acetone on the
action of chloroalkanes or bromoalkanes.
This reaction is based on the Le Chatelier’s principle.
NaI is more covalent and soluble in dry acetone while NaBr and NaCl are more
ionic and insoluble in dry acetone, hence, NaBr and NaCl get
precipitated.Therefore, the reaction shifts in the forward direction.
CH3Br + NaI 
dryacetoneΔ
CH3 - I + NaBr

Nature of C–X bond in haloalkanes:

The carbon – halogen bond in haloalkanes are polar in nature due to greater
electronegativity of halogen. The halogen atom showing –I effect develops a
partial negative charge on it. The alkyl group shows +I effect the C- atom
develops a partial positive charge. Hence the C – X bond has a permanent
dipole moment.

Bond length and bond energies:

The C–X bond length increases from fluoroalkane to iodoalkane as the atomic
radius increases from fluorine to iodine. As the bond length increases bond
energies decreases.

Dipole moments:
Dipole moments of a bond depends on
i.the bond length
ii. bond polarity
because, dipole moment = charge x distance between the charges.
Bond polarity depends on the electronegativities and also, it depends on the
shape of the molecule.
In haloalkanes, the dipole moments first increases, from fluorides to chlorides
and then decreases till iodides.
This is because fluorine atom is so small that the product of the charge
separation and bond length in alkyl fluorides decreases than that in alkyl

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chlorides. But in other halides (i.e. in bromides and iodides) the bond polarity
predominates the bond length.

Bond Bond length in pm Bond energy in kJ mol–1 Dipole moment in D

CH3–F 139 452 1.847
CH3–Cl 178 351 1.860
CH3–Br 193 293 1.830
CH3–I 214 234 1.636

Physical properties of haloalkanes:

Physical state:
Methyl chloride, methyl bromide, ethyl chloride and few
chlorofluoromethanes are gases at room temperature. Higher members are
liquids and crystalline solids.
Colour:
Pure alkyl halides are colourless. However, alkyl bromides and alkyl iodides
develop colour on exposure to light.
Odour:
Many volatile halogen derivatives have sweet smell.
Melting and boiling points:
Haloalkanes have higher melting and boiling points than the parent alkane due
to polarity in the C–X bond due to which the intermolecular forces in
haloalkanes have dipole – dipole interactions which are stronger compared to
the London forces present between the molecules in alkanes. As the
intermolecular forces increase, the melting and boiling points increases.

Among the different homologues of a given haloalkane, the melting and boiling
points increase with increase in the carbon chain length due to increase in
molecular mass and molecular size which increases the Vander–Waal’s forces.

For a given alkyl group, the melting and boiling points vary in the order
R–I > R–Br > R–Cl > R–F. This is due to increase in the molecular size and
molecular mass from fluorides to iodides which increases the Vander Waal’s
forces.

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For isomeric haloalkanes, boiling point decreases with branching. This is

because, as the branching increases, the molecule develops spherical shape
and the surface area decreases which decreases the Vander Waal’s forces.
CH3 CH2CH2CH2-Cl < CH3CH( CH3) CH2- Cl < CH3)3 C -Cl

Density:
Chloroalkanes are lighter than water. Bromo and iodo alkanes are heavier than
water. Relative densities follow the order R–I > R–Br > R–Cl
For a given haloalkane (a halogen) density increases with increase in molecular
mass.
Solubility:
They are very slightly soluble in water and soluble in organic solvents. This is
because, water molecules are held by strong hydrogen bonds. While
haloalkanes by weaker dipole – dipole forces. The energy released due to new
interactions on mixing is not sufficient to break the hydrogen bonds of water.
Haloalkanes do not form hydrogen bonds due to lack of electropositive
hydrogen atoms. The magnitude of interactions is identical with organic
solvents. Hence soluble in organic solvents.

Chemical properties:
The chemical reactions of hahoalkanes are
1) Reaction with metals
2) Elimination reaction
3) Nucleophilic substitution reaction

1) Reaction with metals:

a) Reaction with sodium:
i) Wurtz reaction:
Alkyl halides react with sodium metal in the presence of dry ether to form
higher alkanes.

Ex:
Note:
1.If Wurtz reaction is carried out with two different haloalkane, we get mixture

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of three alkanes.

Ex: CH3–Cl + 2Na + C2H5–Cl  C2H6 + C3H8 + C4H10 + 2NaCl

2. Tertiary haloalkanes generally fails to undergo Wurtz reaction. Due to basic
conditions, they prefer to undergo elimination reaction.

ii) Wurtz – Fittig’s reaction:

Haloalkanes react with haloarenes and sodium in presence of dry ether to give
alkyl arenes.

Ex:
Methyl chloride toluene
b) Reaction with magnesium:
Alkyl halides react with magnesium in dry ether to form alkyl magnesium
halide. These class of compounds are called Grignard’s reagent.
Grignard reagent is discovered by Victor Grignard in the year 1900, it is called
an organo metallic compound.
Dry ether is used as a solvent medium and is an inert solvent. Grignard’s
reagents are very sensitive reagentsand are hghly reactive. Hence an inert
medium like dry ether has to be used.
R - X + Mg 
dry ether
R-Mg -X
Ex: CH3 - I + Mg  CH3 -Mg -I
dry ether

These class of compounds have C –Mg covalent bond and Mg – X ionic bond.
Grignard reagent is highly reactive, hence, any traces of water or moisture
should be avoided in its preparation.In presence of water, it forms
corresponding hydrocarbon.
R-Mg-X + H2O ----- > R-H + Mg( OH ) X

2) Elimination reactions (Dehydrohalogenation) elimination)

Removal of hydrogen halide from haloalkane to form alkene by heating with
the alcoholic KOH is named as dehydrohalogenation. Here the Hydrogen atom
on the  carbon atom i.e. the hydrogen atom bonded to the C atom adjacent
to the C atom bonded to the halogen is removed, it is called  elimination

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reaction.  H atom is acidic in nature due to the –I effect of the halogen.

Alcoholic KOH is basic in nature and abstracts a proton from the  C atom.

Ex: CH3CH2Br + alc. KOH  CH2=CH2 + KBr + H2O

If the haloalkane is symmetric we get only one type of product.

If the haloalkane is asymmetric the product gives two products according to
Zaitsev’s (Saytzeff’s) rule.

Zaitsev’s (Saytzeff’s) rule:

Proposed by Alexander Zaitsev (Saytzeff) in the year 1875.
Duing the dehydrohalogenation of asymmetric alkyl halide to form an
alkene, the preferred product is that alkene with more alkyl groups attached
to the double bonded carbon atoms.
Or
Duing the dehydrohalogenation of asymmetric alkyl halide to form an
alkene, hydrogen atom is preferably removed from that  carbon atom
having lesser number of hydrogen atoms. 

Nucleophilic substitution reaction:

In haloalkanes the halogen atom has partial negative charge. When it is treated
with electron rich species which has affinity to positive charges (nucleophile),
we get substituted product. A nucleophile replaces a halogen atom. This type
of reaction is called nucleophilic substitution reaction.

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Nucleophiles can be classified into negative nucleophiles and neutral

nucleophiles. Negative nucleophiles behave as nucleophiles as they possess a
negative charge. Neutral nucleophiles behave as nucleophiles due to lone pair
of electrons.
Eg for negative nucleophiles: OH–, CN–, R–O–, NO2–, H–, R–, RCOO–, X–, etc.
Eg for neutral nucleophiles: H2O, NH3, ROH, etc.
The atom which possess negative charge or lone pair of electrons in a
nucleophile is called the nucleophilic centre. There might be more than one
nucleophilic centre.
Ambident nucleophiles :
Nucleophiles having two nucleophilic center, But at a given time only one
atom acts as the nucleophilic centre are called ambident nucleophiles.
Eg: CN–, NO2–. Such nucleophiles depending the reagent and the condition,
give different substituted products.

a) Reaction with aqueous KOH or NaOH:

Haloalkanes on heating with aqueous KOH or NaOH, to form the
corresponding alcohols.
R - X +aq KOH 
 R -OH + KX
Ex: CH3 -Cl + aq KOH 
 CH3 -OH + KCl
C2 H5 - Br + aq KOH 
 C2 H5 -OH + KBr

b) Reaction with water:

Haloalkanes react with water, to form alcohols
R - X + H2O 
 R -OH + HX
Ex: (CH3 )3C- Br + H 2O 
 (CH3 )3C-OH + HBr
Ex: tertiary butyl bromide reacts with water to give tertiary butyl alcohol

c) Reaction with alcoholic ammonia (Hoffmann’s ammonolysis):

Ammonia reacts with haloalkane to produce primary amine.
If haloalkane is in excess, the primary amine further reacts with it to produce
secondary amine, tertiary amine and quaternary ammonium salts in different
steps.

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Note:
In every step, the nitrogen atom has the lone pair of electrons and it tends to
behave as a nucleophile as long as the nitrogen atom has the lone pair of
electrons

Ex: methyl iodide reacts with alcoholic ammonia to give methyl amine,
dimethyl amine, trimethyl amine and tetramethyl ammonium iodide

d)Reaction with alcoholic sodium alkoxide ( Williamson’s ether synthesis):

Haloalkanes react with alcoholic sodium alkoxide to form ethers.
Ex: ethyl bromide reacts with sodium ethoxide to give diethyl ether.

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Ex:
e)Reaction with silver carboxylate or silver salt of carboxylic acid:
Alkyl halides react with alcoholic silver carboxylate to give esters. Ex: ethyl
bromide reacts with alcoholic silver acetate to give ethyl acetate.

Ex:

f) Reaction with lithium aluminium hydride(Reduction):

Haloalkanes react with lithium aluminium hydride to give alkanes. Ex: methyl
iodide reacts with lithium aluminium hydride to give methane.
4R – X + LiAlH4  4R –H + LiX + AlX3
4CH3Cl + LiAlH4  4CH4 + LiCl + AlCl3

g) Reaction with R’–M+:

Haloalkanes react with alkyl metallic compounds to give higher alkanes.
R – X + +M – R’  R – R’ + MX.

h) Reaction with alcoholic potassium cyanide (KCN) and alcoholic silver

cyanide (AgCN):
Since CN– is an ambident nucleophile we get different products. Haloalkanes
react with alcoholic potassium cyanide and alcoholic silver cyanide to give
alkanenitrile (or alkyl cyanide) and alkyl isocyanide respectively.

Ex: C2H5Br + alc. KCN  C2H5CN + KBr

C2H5Br + alc AgCN C2H5NC + AgBr

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KCN being strong electrolyte and ionic in nature undergoes complete

ionisation, and C – C is preferably formed as it is stronger than C – N bond.

When AgCN reacts, it does not undergo complete ionisation as it is a weak

electrolyte and it is covalent in nature.
Hence, the lone pair of electrons attack the alkyl group followed by the
cleavage of Ag – C bond to form alkyl isocyanide.

j) Reaction with alcoholic potassium nitrite (KNO2) and alcoholic silver nitrite
(AgNO2):
Similarly, haloalkanes react with KNO2 and AgNO2 to form two different
products, namely alkyl nitrite and nitro alkanes respectively.

Reason:
KNO2 is a strong electrolyte and undergoes complete dissociation and O- atom
acts as the nucleophilic centre.
While AgNO2 is a weak electrolyte and undergoes incomplete dissociation and
first the lone pair of electrons on nitrogen atom acts as a nucleophilic centre
and attacks the carbon atom and then the bond between Ag and O cleaves.
Ex: Ethyl bromide reacts with alcoholic KNO2 and alcoholic AgNO2 to give ethyl
nitrite and nitro ethane respectively

Ex: C2H5Br + alc. KNO2  C2H5ONO + KBr

C2H5Br + alc AgNO2 C2H5NO2 + AgBr

k) Reaction with lithium aluminium hydride LiAlH4;:

When alkyl halides react with LiAlH4., corresponding hydrocarbons are
obtained.
4 R-X + LiAlH4 -------- > 4R-H + AlX3 + LiX
Eg: 4 CH3-Cl + LiAlH4 -------- > 4CH4 + AlCl3 + LiCl

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Mechanism of nucleophilic substitution reaction:

Nucleophilic substitution reactions proceed through two types of mechanisms
1. SN2 (Substitution nucleophilic bimolecular) mechanism
2. SN1 (Substitution nucleophilic unimolecular)mechanism
SN2 mechanism:
It was proposed by Edward Davies Hughes and Christopher Ingold in the year
1937.
Eg: the reaction between methyl bromide and aq. KOH.
CH3 Br + aq. KOH  CH3OH + KBr
Mechanism:

The nucleophile OH- approaches the molecule of the methyl bromide.from the
opposite side of the halogen atom to avoid repulsion. and it leads to the
formation of an intermediate transition state, where, carbon and the three
hydrogen atoms are in the same plane and carbon is partially bonded to OH
group and the bromine atom.Here, the carbon aom is simultaneously bonded
to five atoms.
The formation of the transition state is the slow and the rate determining
step.As the C-OH bond becomes stronger, C_Br bond becomes weaker and
C-Br bond breaks. Both bond formation and bond breaking takes place
simultaneously.
Note:
1. As the slowest step involves both the substrate and the nucleophile,
r = k [CH3Br]1[OH–]1.
2. Hence the order is 1 + 1 = 2.
3. It is a bimolecular reaction following second order kinetics
4. The order of reactivity for different haloalkanes is 1O > 2O > 3O.
5. The product obtained has inversion in the configuration.

SN1 mechanism:
Eg: hyrdolysis of tert – butyl bromide.

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(CH3)3C – Br + aq. KOH  (CH3)3C – OH + KBr

Step 1:
Slow dissociation of tert –butyl bromide to give stable tertiary butyl
carbocation. It is a slow step and rate determining step.

Step 2:
tert – butyl carbocation combines with hydroxide ion to form tert – butyl
alcohol and it is a fast sep.

Since the step 1 is. Rate of the reaction depends on the step one and the
concentration of tert–butyl bromide alone as that is the only reacting species
in the rate determining step. Rate is independent of the concentration of
nucleophile.
Note:
 As the slowest step involves only the substrate alkyl halide,
r = k[(CH3)3C–Br]1[OH–]0.
 Therefore order of the reaction is 1 + 0 = 1.
 Hence it is a bimolecular reaction following first order kinetics.
 Order of reactivity among different haloalkanes towards sN1 mechanism
is 3O > 2O > 1O.
 Allylic halides and benzylic halides also undergo reaction by SN1
mechanism as the carbocation formed is stable due to resonance.

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 If the alkyl halide is opticaly active, the product obtained dis a racemic
mixture.

Note:
Factors affecting whether the compound undergoes SN1 or SN2 reaction
are
i) Nature of substrate (Haloalkane),
ii) Nature of nucleophile
iii) Nature of solvent and
iv) Nature of leaving group.
Substrates in which stable carbocation is formed, undergo SN1 and those
having less bulky groups, undergo SN2 mechanism.
Weaker nucleophiles undergo SN1 mechanism and stronger nucleophile
undergo SN2 mechanism.
Polar protic solvents help SN1 and polar aprotic solvents favour SN2
mechanism

SN1 reaction SN2 reaction

1) Two step reaction 1) One step reaction

2)Unimolecular reaction following first 2) Bimolecular reaction following

order kinetics Second order kinetics
3) rate is dependent on the 3) the rate is dependent on
concentration of the substrate concentration of both the substrate
alone. and nucleophile

3) Order of reactivity among the 3) Order of reactivity among the

different types of haloalkanes is different types of haloalkanes is
O O O
3 > 2 > 1 > methyl halides. methyl halides > 1O > 2O > 3O.

4) Proceeds through carbocation 4) Proceeds by the formation of the

formation. transition state.

5) Polar protic solvents like H2O, acetic 5) Polar aprotic solvents like
acid, etc favour this mechanism. DMF(Dimethyl formamide) ,
DMSO(Dimethyl sulphoxide) favour

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this mechanism.

6) Proceeds to racemisation of 6) Proceeds to inversion of

configuration of products. configuration of products.

Fundamentals of optical isomerism

Plane polarised light and optical activity:

Normal light contains light waves vibrating in different planes . Such a light is
called unpolarised light.
When it is passed through a polariser like nicol prism, the vibrations of light
waves get confined to one plane. This is called plane polarised light.
and the plane in which, it vibrates, is called plane of polarisation.
Nicol prism is made up of calcite (crystalline calcium carbonate) or Iceland spar
which is also called polariser.

Oplically active compounds:

When the plane polarised light is passed through a solution of certain organic
compounds, the plane of polarisation is rotated by certain angle to right or left
side.
Such substances are said to be optically active.
Eg: lactic acid, sucrose, oil of turpentine etc
Dextro and laevo compounds:
Compounds which can rotate the plane of polarisation to the right or
clockwise are called dextro rotatory compounds .
(latin; dexter = right) denoted as (d) or (+)
Ex: (d) – lactic acid.

Those which can rotate the plane polarised light to the left or antclockwise are
called laevo rotatory compounds.
(laevus = left) denoted as (l) or ( – )
Ex: (l) – lactic acid.

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Racemic mixture or Racemic modification:

Equimolar mixture of dextro and laevo rotatory isomers of the same
compound without showing optical activity is called racemic mixture.
Or
Racemic mixture is an equimolar mixture of enantiomers is called racemic
mixture.
Or
A mixture containing two enantiomers in equal proportions which has zero
optical rotation is called racemic mixture.

Eg: lactic acid

Racemic mixture is optically inactive because, the clockwise rotation produced
by (+) isomer is cancelled by anti clockwise rotation by (-) isomer.Hence , the
racemic mixture is optically inactive due to external compensation.

Optical activity of a substance can be expressed in terms of specific rotation.

This optical activity can be attributed to molecular dissymmetry. It was Louis
Pasteur who studied about molecular asymmetry and its close relation to the
optical isomerism in the year 1848.

Chiral carbon/ Assymmetric carbon/ chirality centre/ stereo centre:

Carbon atom to which four different atoms or groups are bonded is called
chiral carbon atom.
Eg:

Bromo chloro iodo methane lactic acid

 Such compounds having one chiral carbon are always optically active.
 Compounds having one chiral carbon atom always exhibit optical
isomerism.
 Such compounds are nonsuperimposable on their mirror images.

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Both of these are optically active and one of these will be dextro rotatory
isomer and another will be laevorotatory isomer.They are together called
enantiomers.
Enantiomers:
A pair of optically active isomers which are non superimposable mirror
images of each other.
Eg: (+) bromobhloro fluoroiodo methane and
(-) bromobhloro fluoroiodo methane

Properties of enantiomers:
 Enantiomers have identical physical properties like melting point, boiling
point, refactive index, .etc.
 Their chemical properties are also similar.
 However, their optical properties and biological properties are different.

Optical isomerism:
Compounds having same molecular formula and and structural formula, but
differ in the direction od rotation of plane polarise light and also differ in the
spacial arrangement of atoms or groups are called optical isomers and the
pheomenon is calle optical isomerism.

Stereo chemical aspects of Nucleophilic substitution reaction:

During any nucleophilic substitution reaction, with regard to stereochemical
aspect, three possibilities occur.
(I) Retention of configuration
(II) Inversion of configuration
(lll) racemisation
Configuration:
Three dimensional arrangement of atoms or groups with respect to the chiral
carbon atom is called configuration.

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Retention of configuration:
The preservation of special arrangement of bonds to an asymmetric centre is
called retention of configuration.
If the absolute configuration of the compound will remain the same even after
the reaction, then it is called retention of configuration.
In a reaction, if the reactant and the product both have same configuration,
then it is called retention in configuration.
This generally happens when the nucleophilic substitution reaction takes place
at a C atom next to the asymmetric carbon atom. When the leaving group is
not bonded to the chiral carbon and the bond between the chiral carbon and
the leaving group is not broken.That is the asymmetric carbon atom is
unaffected.

Ex: Consider the reaction between 2–methylbutan–2–ol and conc. HCl to give
2–chloro–2–methylbutane. Nucleophilic substitution reaction takes place at a
C atom adjacent to chiral carbon atom. Therefore, the configuration remains
the same.

In the above reaction, the absolute configuration remains the same. But the
optical activity has changed since optical activity and absolute configuration
has no relation. Since the absolute configuration is same, it is an example for
retention of configuration.
Note :

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(I) If the bond between the chiral carbon and the leaving group is
broken, then configuration of the product can change.
(II) If the substitution takes place by SN1 mechanism, then racemisation
takes place
(III) By SN2 mechanism, inversion takes place.

Inversion of configuration:
If the absolute configuration of the reactant and product are different, then it
is called inversion of configuration.
When configuration of the product with respect to the chiral carbon is
opposite to that of the reactant , then it is called inversion of configuration. It
is called Walden inversion.

This happens in SN2 reaction as the nucleophile attacks from the back side, the
remaining three groups are pushed to the other side. Therefore, in SN2
reaction inversion of configuration takes place.

Ex:

Racemisation :
Obtaining a racemic mixture using either dextro rotatory or laevorotatory
isomer is called racemiation
Or
The reaction involving 50% inversion and 50% retention of configuration is
called racemisation.
In SN1 reaction, since the reaction proceeds through the formation of a
carbocation by slow dissociation of the optically active alkyl halide, the carbon

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atom of carbocation is sp2 hybridised, it attains planar structure. During this,

the nucleophile can attack from either side of the plane, and we get 50%
inversion and 50% retention of configuration. This results in racemic mixture of
the product. Hence racemisation takes place in SN1 reaction.
Ex: Consider 2–bromobutane undergoing nucleophilic substitution reaction by
SN1 mechanism.
Step 1:

Step 2:

Competition between elimination and substitution:

When an alkyl halide having  – hydrogen atoms is treated with a base or a
nucleophile, it can undergo two competing reactions, namely, substitution (SN1
and SN2) and elimination.
Which reaction will occur predominantly will depend up on the following
factors:
(i) Nature of the alkyl halide,
(ii) strength and size of the base/nucleophile and
(iii) reaction conditions.

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If the nucleophile is bulkier like tert – butoxide ion, prefer to abstract a proton
to give elimination product rather giving a substitution product.
For example, 2 – bromopropane when treated with potassium tert – butoxide
we get propene than substitution product. If 2 – bromopropane is reacted with
aq. KOH we get propan – 2 – ol.

In terms of the strength of the base, stronger base will abstract a proton,
therefore leads to elimination. If the base is weak, then substitution will be
predominant.
Ex. 2 – bromopropane when treated with sodium ethoxide, and sodium
acetate separately, sodium ethoxide leads to elimination and sodium acetate
leads to substitution to give propene and isopropyl acetate respectively. This is
because acetate ion is a weak base and ethoxide ion is strong base.

Primary haloalkanes prefer to undergo substitution reaction by SN2

mechanism in the presence of aq. KOH or aq. NaOH at about 373 K to form
alcohols.
Primary haloalkanes undergo elimination by using stronger base than NaOH
and KOH, and less polar solvent such as alcohol rather than water and high
temperature. For example, ethyl bromide, undergoes substitution with aq.
KOH at 373 K to give ethyl alcohol. While, with ethanolic KOH where a
stronger base like ethoxide ion, at 473 to 573 K undergoes elimination to form
ethene.
Elimination reaction require higher temperature than substitution as more
number of bonds have to undergo cleavage. Energy of activation for
elimination reactions are higher than that of substitution.

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Tertiary alkyl halides preferentially undergo elimination reactions. For

example, tert – butyl bromide on heating with ethoxide ion in ethanol mainly
undergoes elimination to form 2–methylpropene.
If however, it is treated with a weak nucleophile such as pure ethanol both
substitution and elimination occur in which substitution product being
predominant.

Methods of preparation of haloarenes:

1) By electrophilic substitution reaction of benzene:
Chlorobenzene and bromobenzene can be prepared by the direct chlorination
and bromination of benzene in the presence of FeCl3 or FeBr3 respectively.
Fluorobenzene and iodobenzene cannot be prepared by this method.

Similarly, toluene on halogenation gives ortho and para halotoluene. They can
be easily separated as they have large difference in melting point.

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Note:
 Iodo benzene cannot be prepared by this method because, the reaction
is reversible in nature and requires an oxidising agent like HNO3 or HIO4
to oxidise HI formed during oxidation.
 Due to high reactivity of fluorine, reaction is very fast and exothermic,
hence, fluoro benzene can not be prepared by this method.

2) By Sandmeyer’s reaction:
When benzene diazonium salts like benzene diazonium chloride (BDC) are
reacted with HCl and HBr in the presence of Cu2Cl2 and CuBr we get
chlorobenzene and bromobenzene respectively.

Diazotisation:
When aromatic primary amine like aniline is treated with the mixture of NaNO2
HCl at 0- 50C, benzene diazonium chloride is formed.
C6H5NH2 + NaNO2 + 2HCl ---> C6H5N2+Cl- + NaCl + 2H2O

Iodobenzene can be prepared by the action of aq.KI on benzene diazonium

chloride.

Fluorobenzene is obtained by heating benzene diazonium chloride with

fluoroboric acid to give benzene diazonium fluoroborate which on strong
heating gives fluorobenzene. This reaction is called Balz –Schiemann reaction.

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Nature of Carbon – halogen bonds in haloarenes:

In halo arenes , C-X bond develops partial double bond character due to
resonance.
Note: vinylic halides similar to haloarenes, undergo resonance due to which
the carbon halogen bonds have partial single double bond characteristics.

Physical properties of haloarenes:

1. Melting and boiling points of haloarenes are nearly same as those of
haloalkanes of same number of carbon atoms.
2. Melting and boiling points increase, with the increase in the size of halogen
atom. Iodobenzene > Bromobenzene > Chlorobenzene > fluorobenzene.
3. Boiling points of isomeric dihaloarenes are almost same. Melting points are
higher for para isomer than the ortho and meta isomers. Para isomers have
greater symmetry in the molecule and helps to have closed packed structure
in crystal lattice.

4. They are heavier than water.

5. They are insoluble in water and soluble in organic solvents.

Chemical properties of haloarenes:

Haloarenes show the following type of chemical reactions.
1) Nucleophilic substitution reactions
2) Electrophilic substitution reactions.
3) reaction with metals.

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Nucleophilic substitution reactions:

Unlike haloalkanes, haloarenes cannot undergo nucleophilic substitution
reaction easily. Haloarenes undergo nucleophilic substitution reaction under
drastic conditions like high temperature and high pressure.
Reason:
(i) Resonance:
The halogen atom of halobenzene has three lone pair of electrons
and has +R effect when bonded to the benzene ring.Due to
resonance, the C-X bond develops partial doublebond character and
it is difficult to break the C-X bond.

(ii) Sp2 hybridisation of the carbon :

The carbin atom bonded to the halogen atom is sp2 hybridised in a
haloarene. sp2 hybridisedCarbon is more electronegative hence ,
bond polarity of C-X bond decreases and it is difficult to break the C-X
bond.
(iii) Instability of the phenyl carbocation:
If the haloarene undergoes substitution by SN1mechanism, then it
results in the formation of phenyl carbocation which can not be
stabilised by resonance.
(iv) Due to the possible repulsion between the pi electrons of the
benzene ring and the incoming nucleophile, the nucleophilic
substitution is not possible easily.
Ex: Reaction with aq.NaOH:
Chlorobenzene when heated with an aqueous solution of NaOH at 623 K and
300 atm pressure, gives sodium phenate which upon acidification, gives
phenol. This reaction is called Dow’s process.

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However, the nucleophilic substitution reaction of haloarenes can be made

easier, by introducing electron withdrawing group like –NO2, –CN, etc. at ortho
or para positions but not meta positions with respect to the halogen.
Such electron withdrawing groups greatly activates the halogen towards
nucleophilic substitution . Further greater the number of such groups at o– and
p– positions with respect to the halogen, more reactive is the haloarene.

Mechanism and explanation:

The presence of –NO2 group at o– and p– positions withdraws electrons
from benzene ring due to -R effect also due to –I effect. The carbanion
thus formed is stabilised by resonance. In these structures, structure II of
p – chlorobenzene, and V of o – chlorobenzene, carry a negative charge

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on the carbon atom bonded to the nitro group. These carbanions are
stabilised by the –M effect of the –NO2 group and as well as the 
electrons of the benzene ring.
In m – chlorobenzene, such structures are not possible. Hence it is not
stabilised. Therefore, –NO2 group on meta position only acts as electron
withdrawing group due to –I effect. Hence, does not facilitate the
reaction.

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Electrophilic substitution reaction:

Since chlorobenzene has aromatic ring, the hydrogen atom of benzene ring can
be replaced by electron deficient species like Cl+, NO2+, SO3, R+, RCO+ to give
substituted chlorobenzenes. The chlorine atom of chlorobenzene, shows +M /
+R effect. Therefore, it directs the incoming electrophile to ortho and para
position. Hence it is ortho – para director. We get ortho and para substituted
chlorobenzenes with respect to chlorine atom. Para products being more
stable due to steric reasons.
But Cl atom also has –I effect, hence withdraws electron from benzene ring .
Therefore , deactivates benzene ring towards electrophilic substitution.Hence
electrophilic substitution takes place slowly in chloro benzene.

Chloro benzene undergoes

1. Chlorination
2. Nitration
3. Sulphonation

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4. Friedel-Crafts alkylation
5. Friedel- Crafts acylation
In all cases, para product is the major product.

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Reaction with metals:

1) Reaction with sodium:
a) Wurtz – Fittig’s reaction: (refer to reaction of haloalkanes).
b) Fittig’s reaction:
Halobenzene react with sodium metal in dry ether to give diphenyl or biphenyl.
This is called Fittig’s reaction.

Note: Similar to haloalkanes, haloarenes also give phenyl magnesium halide

that is Grignard’s reaction, with magnesium but in the presence of tetra hydro
furan (THF)
Polyholgen compounds:
Organic compounds having more than one same of different halogen atoms
are called as polyhalogen compounds.
1. Dichloromethane (or methylene chloride) CH2Cl2:
 It is used as a solvent for paint removal
 As a propellant in aerosols
 As a process solvent in the manufacture of drugs.
 As a solvent in metal cleaning and finishing.
Harmful effects:
 It harms human central nervous system.
 Exposure to lower levels in air leads to slight impairment in
hearing and vision.
 Higher levels in air cause dizziness, nausea, tingling and
numbness in fingers and toes.
 Direct contact on skin causes intense burning and redness.
 Direct contact on eyes can cause burning of cornea.
2. Trichloromethane (or chloroform) CHCl3:
 It is used as a solvent for fats, alkaloids, iodine etc.
 Used in the production of Freon refrigerant R – 22.
 Previously used as anaesthetic in surgery. Replaced by ethers now
a days due to its toxicity.

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Harmful effects:
 Inhaling vapours depresses the central nervous system.
 Breathing 900 ppm of it causes dizziness, fatigue and headache.
 Chronic exposure causes damage to the liver and kidneys.
 When skin is immersed in it, it causes sores.
 It is slowly oxidised by air in the presence of light to form a
highly poisonous gas, carbonyl chloride also known as phosgene.
Hence it is stored in dark coloured bottles.
2CHCl3 + O2  2COCl2 + 2HCl
3. Tetrachloromethane (or carbon tetrachloride or pyrene) CCl4:
 Used in the manufacture of refrigerants and propellants in the
aerosol cans.
 Used as feed stock in the synthesis of chlorofluorocarbons,
manufacture of pharmaceutical and general solvent.
 Previously it was used as cleaning fluid, degreasing agent, spot
remover and as fire extinguisher.
Harmful effects:
 Exposure to it may cause liver cancer in humans.
 Prolonged exposure causes dizziness, light headedness, nausea,
vomiting etc. ultimately leading to damage of nerve cells.
 In severe cases it can lead rapidly to stupor, coma, and death.
 Causes irregularity in heartbeat.
 Causes irritation in eyes.
 When released into the air, it rises to atmosphere and depletes
the ozone layer.
4. Freons (chlorofluorocarbons) or CFC’s
Chloro fluorocarbon compounds of methane and ethane are
collectively called as freons.
Properties:
 Gases at room temperature.
 Extremely stable and unreactive.
 Non – toxic.
 Easily liquefiable.
 Important members are dichlorodifluoromethane (Freon 12),

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 CCl 2F2 dichlorodifluoromethane (Freon 12),is prepared using Ccl4

by Swarts reaction.
Trichlorofluoromethane (Freon 11), chlorodifluoromethane
(Freon 22), dichlorotetrafluoroethane (Freon 114),
trichlorotrifluoroethane (Freon 113)…are other examples of
freons.
 They are used in aerosol propellants, refrigeration and
airconditioning purpose.
Harmful effects: Most of the freons, including the one used for
refrigerators enter into atmosphere and initiate radical chain reaction
in the stratosphere. These reactions upset the natural ozone balance.
5. DDT:
Trivial name: p,p’ – dichlorodiphenyltrichloroethane.
IUPAC name: 1,1,1 – trichloro – 2,2 – bis(chlorophenyl)ethane:

First chlorinated organic insecticide prepared in 1873. Its effectiveness

as insecticide was discovered by Paul Muller of Geigy pharmaceuticals in
Switzerland who received Nobel Prize for this discovery in 1948.
 Used as insecticide enormously after world war – II.
 Banned in US in 1973.
 It is proved effective insecticide against the mosquito that spreads
malaria (Female anopheles) and lice that carry typhus.
Harmful effects:
 Many species of insects developed resistance to DDT.
 It has high toxicity towards fish.
 It is chemically stable and not metabolised by the animals. Instead
it is deposited in the fatty tissues due to solubility.
6. Triiodomethane (or iodoform):
It was used earlier as an antiseptic but the antiseptic properties are due
to the liberation of free iodine and not due to iodoform itself. Due to its
objectionable smell, it has been replaced by other formulations
containing iodine.

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1 Mark questions:

1) Mention any two halogenated hydrocarbons used as insecticide

2) What are freons?
3) What are alkyl halides?
4) Write the general formula of alkyl halides.
5) What are allylic halides?
6) What are benzylic halides?
7) What are vinylic halides?
8) What are aryl halides?
9) What is the hybridisation of carbon atom in C–X bond of alkyl halides?
10) What is the hybridisation of carbon atom in C–X bond of allylic halides?
11) What is the hybridisation of carbon atom in C–X bond of benzylic halides?
12) What is the hybridisation of carbon atom in C–X bond of vinylic halides?
13) What is the hybridisation of carbon atom in C–X bond of aryl halides?
14) Why the dipole moment of CH3F is greater than that of CH3Cl even though
the electronegativity of F is greater than Cl?
A) Fluorine atom is so small that the product of the charge separation and
bond length between carbon and fluorine atom in methyl fluoride
decreases than that in methyl chloride.
15) Why haloalkanes are insoluble in water?
A) Haloalkanes can neither form hydrogen bonds with water nor break the
hydrogen bonds of water. Hence insoluble in water. (1M)
OR
Haloalkanes are less soluble in water even though they are polar in nature.
Why?
For a haloalkane to dissolve in water, energy is required to overcome and
break the hydrogen bond between water molecules. Less energy is
released when new attractions are set up between the haloalkane and
water molecules as these are not as strong as the original hydrogen bonds
in water. Hence, they are less soluble. (2M)
16) Why the order of boiling points is in the order 1O > 2O > 3O for alkyl
halides?
A) Tertiary alkyl halides are more branched and attain spherical shape and less
surface area which decreases the Vander–Waal’s forces.

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17) What type of substitution reactions do alkyl halides undergo?

A) Nucleophilic substitution reaction.
18) Why haloalkanes undergo nucleophilic substitution reaction?
19) Name the reagent used for dehydrohalogenation?
A) Alcoholic KOH.
20) Why haloarenes are less reactive towards nucleophilic substitution
reaction?
21) What are Grignard’s reagents?
A) alkyl magnesium halides (R–Mg–X) are called Grignard’s reagents.
22) H3C–Br + AgF  H3C–F + AgBr. Name the reaction.
A) Swarts reaction..
23) R  X  NaI 
dry acetone
 R  I  NaX . Name the reaction.
A) Finkelstein’s reaction.
24) Name the gas liberated when 2–bromopropane is heated with alcoholic
potash.
A) Propene.
25) What is chirality?
A) The property by which a molecule forms non–superimposable mirror
image is called chirality.

26) Write the IUPAC name of

A) 1–Chloro– 2–methyl benzene (or) 2–chlorotoluene.

27) What is the name of the following reaction?

A) Fittig’s reaction.

28) Name the major product obtained when tertiary butyl bromide is heated
with alcoholic potash.
A) isobutene (or) 2–methylpropene.

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29) In aryl halides, what is the hybridisation of the carbon atom bonded to
halogen atom?
A) sp2
30) Write the general equation for Wurtz reaction.
A) 2R  X  2 Na 
dry ether
 R  R  2 NaX where R is an alkyl group
31) Name the major product obtained when 2–bromopentane is heated with
alcoholic potassium hydroxide solution.
A) 2–pentene (or) pent–2–ene.
32) Complete the following equations:
i) C2H5OH + SOCl2  _________ A) C2H5Cl + SO2↑ + HCl↑

ii) ___________ A)
33) Mention the major product of the following reactions:
i) C6 H 5 Br  Mg 
dry ether
 ____ A) C6H5MgBr
alc. KOH.
ii) 2  bromopentane   ____ A) CH3–CH=CH–CH2–CH2 + KCl + H2O
iii) CH 3Cl  NaI  ____ A) CH3I + NaCl
dry acetone

34) What is the reagent used in the conversion of alkyl halide into alkene?
A) Alcoholic KOH.
35) Complete the reaction CH3–CH2–Br + AgCN(alc)  ___ A) CH3–CH2–NC + AgBr
36) What are enantiomers?
A) A pair of optically active isomers which are non – superimposable mirror
images of each other.
37) What is racemic mixture?
38) Write the general formula of Grignard’s reagent. A) R – Mg – X
37) Write the general equation for the reaction of primary alcohol with SOCl2.
A) R–CH2–OH + SOCl2  R–CH2–Cl + SO2 + HCl
38) p–dichlorobenzene has higher melting point than those of ortho and
meta isomers. Give reason.
A) p–dichlorobenzene molecule is symmetrical and the molecule can fit into
the ccystal lattice more easily and has close packing structure in solid state
than ortho and meta isomers.

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39) What is asymmetric carbon?

40) Name the product formed for the reaction of isopropyl iodide on
alcoholic KOH.
A) propene.
41) What is the condition to be satisfied for a compound to be chiral?
A) The molecule of the compound should not possess plane of symmetry (OR)
The molecule and its mirror should be non–superimposable.
42) What is racemic mixture?
A) Equimolar mixture of enantiomers (dextro and laevo isomers) which is
optically inactive is called racemic mixture.
43) Complete the following equations:
i) CH3–CH=CH2 + HI  A) CH3CHICH3

ii) A)

TWO-mark questions:

1) What are ambident nucleophiles? Give example

2) Explain the Grove’s method of preparation of chloroalkane with an
example
3) Explain the reaction of magnesium with alkyl halide. (OR) Explain the
formation of Grignard’s reagent with an example.
4) Explain Wurtz reaction with an example.
5) Explain Wurtz – Fittig’s reaction with an example.
6) Explain Fittig’s reaction with an example.
7) Explain Sandmayer’s reaction for preparation of chlorobenzene
8) Distinguish between SN1 and SN2 reaction.
9) Explain the conversion of chlorobenzene to phenol.
10) Write the equations for the steps in SN1 mechanism of the conversion of
tert. butyl bromide into tert. butyl alcohol.
11) Explain the SN2 mechism.
12) Explain Fittig’s reaction with equation

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13) Explain the mechanism of SN1 reaction taking

2–bromo–2–methylpropane (t–butyl bromide)
14) Aryl halides are extremely less reactive towards nucleophilic substitution
reactions. Give any two reasons.
15) Explain Friedel – Craft’s alkylation for chlorobenzene. Give equation.
16) State and explain Saytzeff rule with an example.

THREE–mark questions:

3) Identify the products A, B and C in the following equation.

CH 3OH 
Red P
Cl2
 A  NaI
dry acetone
 B C6 H 5 I
Na in dry ether
C
A) A = methyl chloride (CH3Cl), B = methyl iodide (CH3I), C = toluene (C6H5CH3)

4) Explain SN1 mechanism with example.

__________

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