Unit 14 Haloalkanes and
Haloarenes
Francois Auguste Victor
Grignard
He a French chemist
was awarded the noble
prize for chemistry in 1912.
He prepared and realised
the usefulness of organo
magnesium compounds.
He took maths degree and
eventually switched over
organic chemistry while
attempting to find the
catalyst for the process of
Methylation.
Unit 14.indd 225
Learning Objectives
After learning this unit, students will be able to
• classify the various organic halo compounds.
• name the organic halo compounds according to
IUPAC system.
• recognise the nature of C-X bond.
• describe the general methods of preparation of
haloalkanes and haloarenes
• explain the physical and chemical properties of
haloalkanes and haloarenes.
• describe the mechanism of nucleophilic
substitution and elimination reactions of halo
organics
• explain the preparation and synthetic uses of
grignard reagent.
• highlight the uses of poly halogen compounds.
• comprehend the environmental effect of poly
halogen compounds.
14.1 INTRODUCTION
In the previous unit we learnt about the
chemistry of hydrocarbons. In this unit us learn about
organic compounds containing halogens. When one
or more hydrogen atoms of aliphatic or aromatic
hydrocarbons are replaced by the corresponding
number of halogens like fluorine, chlorine, bromine
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 or iodine, the resultant compounds are called either haloalkanes or halo arenes. They
serve as starting materials for many organic synthesis.

Halogen substituted organic compounds are widely spread in nature and

find application in our day to day life as well as in industry. Certain compounds like
chloramphenicol produced by soil microbes are used in the treatment of typhoid;
chloroquine is used in the treatment of malaria, halothane is used as an anesthetic, and
halogenated solvents like trichloroethylene are used for cleaning electronic equipments.

14.2 Classification of organic halogen compounds

Organic Halogen Compounds

Based on the Hybridisation of

Carbon attached with halogen,

Based on number
of Halogens

Mono Halo compounds

(C2H5 Br - Bromo ethane Compounds
containing Csp2 – X
Poly Halo compounds bond
CCl3–CH2 - CH3
Trichloro propane. Vinylic Halides CH2 = CHI
Vinyl Iodide
Compounds Aryl halides (or Halo arenes)
containing Csp3 – X C6H5 Cl Chlorobenzene
bond

Alkyl halides (or) Haloalkanes

CH3 I lodomethane

Allylic halides CH2 = CH – CH2 – Cl – Allyl chloride

Benzylic halides C6H5CH2 Br Benzyl bromide

Alicyclic halides Br Bromo cyclobutane

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 14.3 Haloalkanes

Mono halogen derivatives of alkanes are called haloalkanes. Haloalkanes are

represented by general formula R – X, Where, R is an alkyl group (CnH2n+1) – and X is a
halogen atom (X=F, Cl, Br or I). Haloalkanes are further classified into primary, secondary,
tertiary haloalkane on the basis of type of carbon atom to which the halogen is attached.

Primary haloalkane

Examples:
H
CH3 C Br
(a 1o Haloalkane)
H
Bromoethane

Secondary haloalkane

H
CH 3 C CH3
Cl
(a 2o Haloalkane)
2- Chloro propane
(Iso propylchloride)

Tertiary haloalkane

CH 3

CH3 C CH3
(a 3o Haloalkane)
I
2- Iodo - 2- methyl propane
(tert- Butyl iodide)

14.3.1 Nomenclature
Common system
In the common system, haloalkanes are named as alkyl halides. It is derived by
naming the alkyl group followed by the halide.
IUPAC system
Let us write the IUPAC name for the below mentioned haloalkanes by applying the
general rules of nomeclature that are already discussed in Unit no : 11

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 Common
S.No Structural formula IUPAC name
name
1 CH3I methyl iodide Iodomethane

2 CH3CH2Br ethyl bromide Bromoethane

n-propyl fluo-
3 CH3CH2CH2F 1-Fluoropropane
ride

CH3 - CH - CH3
iso - propyl flu-
4 2- Fluoropropane
F oride

CH3 - CH2 - CH2 - CH2 - Cl n- butyl chlo-

5 1-Chlorobutane
ride

CH3 - CH - CH2 - Cl iso butyl chlo- 1- Chloro-2-methyl pro-

6
CH3 ride pane

CH3 - CH - CH2 - CH3 sec-butyl chlo-

7 2-Chlorobutane
Cl ride

CH3
tert-butyl chlo- 2- Chloro -2- methyl
8 CH3 - C- CH3
ride propane
Cl

CH3
neo-pentyl bro- 1-Bromo-2, 2- dimethyl-
9 CH3 - C - CH2 Br
mide propane
CH3

10 CH2 = CH - Cl vinyl chloride Chloroethene

11 CH2 = CH - CH2 - Br allyl bromide 3-Bromopropene

Poly halogen Compounds:

The common and IUPAC name of polyhalogen compounds are give below

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 Common
S.No Structural formula IUPAC name
name
CH2Cl Ethylene 1,2- Dichloroethane
chloride (or)
12 CH2Cl
Ethylene
dichloride

CHCl 2 Ethylidene 1,1- Dichloroethane

CH 3
chloride (or)
13
Ethylidene
dichloride

CH2 CH CH2CH3 – 1- Bromo-2, 3-dichloro

14. butane
Br Cl Cl

Br – 2-Bromo -3- Chloro -2, 4-

dimethyl pentane
15 CH 3 - C - CH - CH - CH3
CH 3Cl CH 3

Evaluate Yourself ?
1) Write the IUPAC name of the following

i) ii) H3C CH3 iii) H3C H

CH3 C=C H
H CH - I H F
CH2 = C - CH2 - Cl
CH3 CH3

Evaluate Yourself ?
2) Write the structure of the following compounds

i) 1-Bromo-4-ethyl cyclohexane ii) 1,4 – Dichlorobut – 2 – ene

iii) 2- Chloro – 3- methyl pentane

14.3.2 Nature of C – X bond in haloalkane

Carbon halogen bond is a polar bond as halogens are more electro negative than
carbon. The carbon atom exhibits a partial positive charge (б+) and halogen atom a partial
negative charge (б-)

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 a)Reaction with hydrogen halide
δ+ δ− Anhydrous
ZnCl2
C X CH3CH2OH+HCl CH3CH2Cl+H2O
Ethanol Chloroethane

Mixture of con.HCl and anhydrous ZnCl2

The C –X bond is formed by is called Lucas reagent.
overlap of sp3 orbital of carbon atom with
CH3
half filled p-orbital of the halogen atom.
The atomic size of halogen increases CH3 C OH + HI
from fluorine to iodine, which increases CH3 KI
the C – X bond length. Larger the size, H3PO 4
tert - Butyl alcohol
greater is the bond length, and weaker is
the bond formed. The bond strength of C
CH3
– X decreases from C – F to C – I in CH3X.
The changes in the value of bond length, CH3 C I + H 2O
bond enthalpy and bond polarity, as we CH3
more from C –F to C –I, is given in the tert - Butyl iodide
table.
The order of reactivity of halo acids
Table showing carbon – halogen bond
with alcohol is in the order HI > HBr >
length, bond enthalpy and polarity of
HCl. The order of reactivity of alcohols
bond.
with halo acid is tertiary > secondary >
primary.
Polarity of bond

dipole moment
Bond Enthalpy
Bond length

in terms of
(kJmol-1)

b)Reaction with phosphorous halides

(Debye)
Bond

(pm)

Alcohols react with PX5 or PX3 to

form haloalkane. PBr3 and PI3 are usually
generated in situ (produced in the reaction
CH3 – F 139 452 1.847
mixture) by the reaction of red phosphorus
CH3 – Cl 178 351 1.860 with bromine and iodine, respectively.
CH3 – Br 193 293 1.830
Example
CH3 – I 214 234 1.636
CH3CH2OH + PCl 5
14.3.3 Methods of preparation Ethanol
Haloalkanes are prepared by the following CH3CH2Cl + POCl 3 + HCl
methods
Chloro ethane
1) From alcohols 3CH 3CH2OH + PCl 3
Ethanol
Alcohols can be converted into halo
alkenes by reacting it with any one of the 3CH 3CH2Cl + H 3PO 3
following reagent 1. hydrogen halide 2. Chloro ethane
Phosphorous halides 3. Thionyl chloride

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 c) Reaction with thionyl chloride 4) Halogen exchange reactions
(Sulphonyl chloride) a) Finkelstein reaction
Example Chloro or bromoalkane on heating
with a concentrated solution of sodium
CH3CH2OH + SOCl2
iodide in dry acetone gives iodo alkanes.
Ethanol Pyridine This reaction is called Finkelstein reaction,
CH3CH2Cl+SO2↑+HCl↑ (SN2 reaction).
Chloroethane
CH3CH2Br + Nal
This reaction is known as Darzen's Bromoethane Acetone
halogenation ∆
CH3CH2I + NaI
2) From alkenes Iodoethane
Alkenes react with halogen acids
b) Swarts reaction
(HCl, HBr, HI) to give haloalkane. The
mode of addition follows Markovnikov’s Chloro or bromo alkanes on heating
rule. with metallic fluorides like AgF, SbF3 or
3) From alkanes Hg2F2 gives fluoro alkanes. This reactions
is called Swarts reaction.
Alkanes react with halogens (Cl2
or Br2) in the presence of ultra violet light Example
to form haloalkane. This reaction is a free
radical substitution reaction and gives a CH 3CH 2Br + AgF
mixture of mono, di or poly substituted Bromo ethane
haloalkane.

Example CH 3CH 2F + AgBr

Fluoro ethane
Chlorination of methane gives
different products which have differences
5) From silver salts of fatty acids
in the boiling points. Hence, these can be
(Hunsdiccker reaction)
separated by fractional distillation.

CH 4
Cl / light
2
CH 3 Cl
Silver salts of fatty acids when refluxed
- HCl
Methane Chloromethane with bromine in CCl4 gives bromo alkane
Cl 2
- HCl
CH3CH2COOAg + Br2
CH 2 Cl 2 Silver propionate CCl 4
Dichloromethane reflux
Cl 2
- HCl
CH3CH2Br + CO2 + AgBr
Cl 2 Bromo ethane
CHCl 3 CCl 4
- HCl
Trichloro methane Tetrachloro methane

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 For Example:
CH3CH2COOAg + Br2
Silver propionate CCl 4
reflux CCl4 > CHCl3 > CH2Cl2 > CH3Cl
CH3CH2Br + CO2 + AgBr
Bromo ethane iv) The boiling point and melting
point of mono haloalkane increase
14.3.4 Physical Properties with the increase in the number of
carbon atoms.
1. Pure haloalkanes are colourless.
Example
Bromo and iodo alkanes are coloured in
the presence of light.
CH3CH2CH2Cl > CH3CH2Cl > CH3Cl
2. Haloalkanes having one, two or
three carbon atoms are in the gaseous v) Among isomeric alkyl halides the
state at normal temperature. Haloalkanes boiling point decreases with the
having more than three carbon atoms are increase in branching in the alkyl
liquids or solids. group; with increase in branching,
the molecule attains spherical
3). Boiling point and Melting point shape with less surface area. As a
result the inter molecular forces
i) Haloalkanes have higher boiling become weak, resulting in lower
point and melting point than the boiling points.
parent alkanes having the same
number of carbons because the Example
intermolecular forces of attraction
(dipole – dipole interaction and CH3CH2CH2CH2Cl > CH3CH2CHCH3 >
vander Waals forces) are stronger
in haloalkane. (351.5K) (341K) Cl
CH3
ii) The boiling point and melting
point of haloalkanes decreases CH3 C CH3
with respect to the helogen in the
following order. Cl
(324K)
Example

CH3I > CH3Br > CH3Cl > CH3F 4. Solubility

Haloalkanes are polar covalent

iii) The boiling points of chloro,
compounds soluble in organic
bromo and iodo alkanes increase
solvents, but insoluble in water
with the increase in the number of
because they cannot form hydrogen
halogen atoms.
bonds with water molecules

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 5. Density CH3 - CH2 - Br + KOH (aq)
Bromoethane boil
The density of liquid alkyl halides are
higher than these of hydrocarbons of
CH3 - CH2 - OH + KBr
comparable molecular weight.
Ethyl alcohol
CH 3 - CH 2 - Br + AgOH
Evaluate Yourself ?
Bromoethane Moist silver
3) Write all possible chain isomers with oxide
molecular formula C5H11Cl
boil

14.3.5 Chemical properties CH 3 - CH 2 - OH + AgBr

Haloalkanes are one of the most
reactive classes of organic compounds.
Their reactivity is due to the presence
of polar carbon – halogen bond in their
molecules. The reactions of haloalkane
may be divided into the following types
Ethanol
i) Reaction with alcoholic ammonia
(Ammonolysis)
Haloalkanes react with alcoholic
ammonia solution to form alkyl amines.

i) Nucleophilic substitution reactions Example

ii) Elimination reactions CH3 – CH2 – Br + H – NH2

Bromo ethane ammonia
iii) Reaction with metals

iv) Reduction CH3 – CH2 – NH2 + HBr

Ethyl amine
1) Nucleophilic substitution reactions
However, with excess of halo alkane,
We know that the Cδ+ - Xδ- present secondary and tertiary amines along with
in halo alkane is polar and hence the quartenary ammonium salts are obtained
nucleophilic reagents are attracted by
partially positively charged carbon atoms CH3CH2NH2 CH3CH2Br (CH 3CH2)2NH
Ethyl amine -HBr
resulting in substitution reactions. Diethyl amine
(1) (2)
Reaction with aqueous alkali or moist CH3CH2Br
-HBr
silver oxide.(Hydrolysis)
(CH 3CH2)3N
Triethyl amine
Haloalkane reacts with aqueous (3)
solution of KOH or moist silver oxide CH3CH2Br
-HBr
(Ag2O/H2O) to form alcohols.
(CH 3CH2)4N+Br -
Example Tetra ethyl ammonium
bromide

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 Ambident Nucleophiles solution of AgNO2 to form nitro alkanes.

Nucleophiles such as cyanide and Example

nitrite ion which can attack nucleophilic CH3CH2Br+AgNO2→CH3CH2NO2+ AgBr
centre from two sides are called ambident
nucleophiles. These nucleophiles can Bromo ethane Nitro ethane
attack with either of the two sides
vi) Reaction with sodium or potassi-
depending upon the reaction conditions
um hydrogen sulphide
and the reagent used.
Haloalkanes react with sodium or
ii) Reaction with alcoholic KCN potassium hydrogen sulphide to form thio
alcohols.
Haloalkanes react with alcoholic
KCN solution to form alkyl cyanides. Example
Example alcohol/
H2O
CH3CH2Br+NaSH CH3CH2SH+NaBr
∆
CH3–CH2–Br+KCN→ CH –CH –CN+KBr
Bromoethane
3 2 Bromo ethane Ethane thiol
Ethyl cyanide

vii) Williamson ether synthesis

iii) Reaction with alcoholic AgCN
Haloalkane, when boiled with
Haloalkanes react with alcoholic sodium alkoxide gives corresponding ethers.
AgCN solution to form alkyl isocyanide.
Example
Example
This method can be used to prepare mixed
CH3CH2Br + AgCN CH3CH2NC+AgBr
Bromoethane Ethyl isocyanide (unsymmetrical) ethers also.

CH3CH2Br+NaOCH2CH3
iv) Reaction with sodium or potassi-
Bromo ethane Sodium ethoxide
um nitrite
Haloalkanes react with alcoholic CH3CH2OCH2CH3+NaBr
solution of NaNO2 or KNO2 to form alkyl diethyl ether
nitrites.

Example Mechanism of Nucleophilic substitu-

tion reaction
CH3CH2Br + KNO2→CH3CH2–O–N=O+KBr
The mechanism of nucleophilic
Bromoethane Ethyl nitrite
substitution reaction is classified as

v) Reaction with silver nitrite a) Bimolecular Nucleophilic

Haloalkanes react with alcoholic substitution reaction (SN2)

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 b) Unimolecular Nucleophilic – 2 – Bromo octane is heated with sodium
substitution reaction (SN1) hydroxide (+) – 2 – Octanol is formed
in which – OH group occupies a position
SN2 Mechanism opposite to what bromine had occupied,

Substitution H3C
Bimolecular H
HO-
SN2 C Br HO Br

Nucleophilc H H nC6H13
nC6H13 (b)
(a) CH3
The rate of SN2 reaction depends upon
the concentration of both alkyl halide HO C
H
and the nucleophile.
nC6H13 (c)

Rate of reaction = k2 [alkylhalide]

[nucleophile] (a) (-) 2 – Bromo octane

It follows second order kinetics and (b) Transition State

occurs in one step.
This reaction involves the formation
of a transition state in which both the
reactant molecules are partially bonded
to each other. The attack of nucleophile
occurs from the back side (i.e opposite to
the side in which the halogen is attacked).
The carbon at which substitution occurs has
inverted configuration during the course of
reaction just as an umbrella has tendency
to invert in a wind storm. This inversion of
configuration is called Walden inversion;
after paul walden who first discovered the
inversion of configuration of a compound in
SN2 reaction.
SN2 reaction of an optically active
haloalkane is always accompanied by
inversion of configuration at the asymmetric
centre. Let us consider the following example
(c) (+) 2 – Octanol (product)
SN1 Mechanism
SN1 stands for unimolecular
nucleophilic substitution
‘S’ stands for substitution
‘N’ stands for nucleophilic
‘1’ stands for unimolecular (one
molecule is involved in the rate determining
step)
The rate of the following SN1 reaction
depends upon the concentration of alkyl
halide (RX) and is independent of the
concentration of the nucleophile (OH−).
Hence Rate of the reaction = k[alkyl
halide]

When 2 - Bromooctane is heated R−Cl + OH− R – OH + Cl−

with sodium hydroxide, 2 – octanol is This SN1 reaction follows first order
formed with invesion of configuration. (-) kinetics and occurs in two steps.
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 We understand SN1 reaction As shown above, the nucleophilic
mechanism by taking a reaction between reagent OH- can attack carbocation from
tertiary butyl bromide with aqueous KOH. both the sides.

CH3 CH3 In the above example the substrate

OH (aq)
-
tert-butyl bromide is not optically active,
CH3 C Br CH 3 C OH
-Br- hence the obtained product is optically
CH3 CH 3 inactive. If halo alkane substrate is optically
Tert-Butyl bromide Tert-Butyl alcohol
active then, the product obtained will
be optically inactive racemic mixture.
This reaction takes place in two steps
As nucleophilic reagent OH- can attack
as shown below
carbocation from both the sides, to form
Step - 1 Formation of carbocation equal proportion of dextro and levorotatory
optically active isomers which results in
The polar C - Br bond breaks forming optically inactive racemic mixture.
a carbocation and bromide ion. This step is
slow and hence it is the rate determining Example
step.
Hydrolysis of optically active 2 -
CH3 bromo butane gives racemic mixture of ±
CH3 butan-2-ol
Slow + Br-
CH3 C Br C+

CH3 The order of reactivity of haloalkanes

H3C CH3
towards SN1 and SN2 reaction is given below.
t butyl bromide
SN2 reaction

The carbocation has 2 equivalent lobes SN2

of the vacant 2p orbital, so it can react
Tertiary, Secondary, Primary, CH3X
equally rapidly from either face
SN1
Step - 2
The nucleophile immediately reacts Evaluate Yourself ?
with the carbocation. This step is fast and
4) neo-pentyl bromide undergoes
hence does not affect the rate of the reactions.
nucleophilic substitution reactions very
CH3
CH3 slowly - justify.
+ OH - fast
C CH3 C OH +

CH3
CH3 2) Elimination reactions
CH3
tertiary butyl alcohol

CH3 When a haloalkene containing a

C CH3
hydrogen on β carbon is treated with an
HO
ethanolic solution of potassium hydroxide,
CH3
tertiary butyl alcohol
an alkene is formed. In this reaction a double
bond between α and β carbon is formed by

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 releasing a halogen attached to a α carbon alcoholic KOH. It is a one step process in
and a hydrogen to a β carbon of halo alkane. which the abstraction of the proton from
This reaction is called β elimination reaction. the β carbon and expulsion of halide from
(dehydrohalogenation). the ∝ carbon occur simultaneously. The
mechanism is shown below.
CH 3 CH2 Br+KOHethanol CH2=CH2+KBr+H2O
Ethylene
HO - H
Some haloalkanes yield a mixture of alcoholic
CH3 CH CH2 Cl
olefins in different amounts. It is explained KOH
1-chloro propane
by Saytzeff ’s Rule, which states that ‘In
a dehydrohalogenation reaction, the CH3 CH = CH2 + H2O + KCl
preferred product is that alkene which has Propene
more number of alkyl groups attached to the
doubly bonded carbon (more substituted
E1 reaction mechanism
double bond is formed)
Elimination
Example E1 Unimolecular
CH3 CH CH2 CH3
Br Generally, tertiary alkyl halide which
2-Bromopropane undergoes elimination reaction by this
CH2 = CH - CH2 - CH3 mechanism in the presence of alcoholic
alcoholic 1-Butene KOH. It follows first order kinetics. Let us
KOH (Minor product)
CH3 - CH = CH - CH3 consider the following elimination reaction.
2-Butene
(Major product) CH3
alcoholic
CH3 C Cl
Elimination reactions may proceed through KOH
two different mechanisms namely E1 and E2 CH3
tert-butyl chloride
E2 reaction mechanism
CH3
Elimination
E2 CH3 C CH2 KCl H 2O
bimolecular
(Second order) Iso butylene
(2-Methyl propene)
The rate of E2 reaction depends on the
concentration of alkyl halide and base Step - 1 Heterolytic fission to yield a carbo-
cation
Rate = k [alkyl halide] [base]

It is therefore, a second order

reaction. Generally primary alkyl halide
undergoes this reaction in the presence of

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 CH3 b) Reaction with active metals like so-
Slow dium, lead etc
CH3 C Cl Haloalkane reacts with active metals
like sodium, lead etc in the presence of dry
CH3
ether to form organo metallic compounds.

CH3 CH3 Dry ether

Cl CH3 CH2 Br + 2Li
C Ethyl bromide CH CH Li + LiBr
3 2
Ethyl Lithium
CH 3

Step - 2 Elimination of a proton from the 4CH3 CH2 Br + 4Na/Pb

β - carbon to produce an alkene Ethyl bromide Sodium - lead alloy
HO : (CH3CH2)4Pb + 4NaBr + 3Pb
Tetra ethyl lead (TEL)
CH3 CH2 H fast
C 4) Reduction reactions
CH3 CH2
CH3 Haloalkanes are reduced to alkanes
C H 2O by treating with H2 in the presence of
Carbocation
metal catalyst like nickel, palladium etc or
CH 3 with hydroiodic acid in the presence of red
phosphorous.
2 - methyl propene
Ni(or)Pd
CH 3CH2 Br+H2 523 K
CH3-CH3+HBr
3) Reaction with metals Bromo ethane Ethane
Haloalkane reacts with metals, to
form a compound containing carbon - metal CH3 CH2 I + HI Red P CH3 - CH3 +I2
bond known as organometallic compounds. Iodo ethane Ethane
a) Grignard reaction
The chemistry of haloalkane can be well
When a solution of halo alkane in understood by the following flowchart.
ether is treated with magnesium, we get
alkyl magnesium halide known as Grignard 14.3.6 Uses of haloalkane
reagent. Chloroform: As a solvent in pharmaceutical
Example industry and for producing pesticides and
drugs As an anaesthetic.
CH3CH2 Br+Mg Dry ether CH3CH2MgBr
As a preservative for anatomical specimens.
Ethyl bromide Ethyl magnesium bromide
Iodoform: Iodoform is used as an antiseptic
for dressing wounds.

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 Carbon tetrachloride: Carbon tetrachloride 14.4.2. Uses of Grignard reagent
is used as dry cleaning agent Grignard reagents are synthetically
It is used as a solvent for oils, fats and waxes very useful compounds. These reagents are
As the vapour of CCl4 is non – combustible, converted to various organic compounds
it is used under the name pyrene for like alcohols, carboxylic acids, aldehydes
extinguishing the fire in oil or petrol. and ketones. The alkyl group being electron
rich acts as a carbanion or a nucleophile.
14.4 Organo metallic Compounds
They would attack polarized molecules at a
point of low electron density. The following
Organo metallic compounds are
reactions illustrate the synthetic uses of
organic compounds in which there is a
Grignard reagent.
direct carbon –metal bond
(1) Preparation of primary alcohol
Example
Formaldehyde reacts with Grignard
CH3 Mg I - Methyl magnesium
reagent to give addition products which on
iodide
hydrolysis yields primary alcohol.
CH3 CH2 Mg Br - Ethyl magnesium
O
bromide
The carbon - magnesium bond in H C H + CH 3 MgI
Grignard reagent is covalent but highly Formaldehyde
polar. The carbon atom is more electro OH I
OMgI
negative than magnesium. Hence, the
carbon atom has partial negative charge and H C H H C H + Mg
OH
the magnesium atom has partial positive CH 3 CH3
charge Ethylalcohol ( o1 )
δ- δ+ R ----- MgX
14.4.1. Preparation 2) Preparation of secondary alcohol
When a solution of alkyl halide Aldehydes other than formaldehyde,
in ether is allowed to stand over pieces of react with Grignard reagent to give addition
product which on hydrolysis yields
magnesium metal, the metal gradually
secondary alcohol.
dissolves and alkyl magnesium halide
O OMgI
(Grignard reagent) is formed. All the H
reagents used should be pure and dry CH3 C H + CH3MgI CH3 C H
Acetaldehyde CH3
Example
dry ether OH I
CH3 I Mg CH3MgI
Iodomethane 2O /H+
Methyl magnesium iodide CH3 C H + Mg
OH
Evaluate Yourself CH3
?
Isopropylalcohol ( 2o)
5) Why Grignard reagent should be
prepared in anhydrous condition?

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 3) Preparation of Tertiary alcohol 6) Preparation of carboxylic acids

Ketone reacts with Grignard reagent Solid carbon dioxide reacts with
to give an addition product which on Grignard reagent to form addition product
hydrolysis yields tertiary alcohols. which on hydrolysis yields carboxylic acids.
Example
O
For Example
OMgI
H2
CH3 C CH3 CH3MgI CH3 C H O
Acetone CH3 O=C=O + CH3MgI CH3 C OMgI
OH
O/H
I I
CH3 C CH3 Mg H+/H2O
CH3 C OH+ Mg
CH3 OH OH
O
Tert - Butylalcohol( 3o) Acetic acid

(4) Preparation of aldehyde

7) Preparation of esters
Ethyl formate reacts with Grignard
reagent to form aldehyde. However, Ethylchloroformate reacts with
with excess of Grignard reagent it forms Grignard reagent to form esters.
secondary alcohol.
Example
Example
O O OMgI
OMgI
H2 C2H 5O C Cl + CH3MgI C2H 5O C Cl
H C OC2H5 + CH3MgI H C OC2H5
Ethylformate Ethylchloroformate CH 3
CH3
O I I
O /H+ CH3 C OC2H5+ Mg
H C CH3 + Mg
OC 2H5 Cl
Acetaldehyde O
Ethylacet
ate
(5) Preparation of ketone
Acid chloride reacts with Grignard 8) Preparation of higher ethers
reagent to form ketones. However, with
Lower halogenated ether reacts with
excess of Grignard reagent it forms tertiary
Grignard reagent to form higher ethers.
alcohol.
Example Example

O OMgI CH3 O CH2Cl + CH 3MgI

H2
H C OC2H5 + CH3MgI H C OC2H5 Chloro dimethyl ether
Ethylformate CH3 I
O I CH3 O CH2CH3 + Mg
O /H+
H C CH3 + Mg Ethyl methyl ether Cl
Acetaldehyde OC 2H5

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 9) Preparation of alkyl cyanide the following examples.
Grignard reagent reacts with Compound IUPAC NAME
cyanogen chloride to from alkyl cyanide 1 Cl
Cl 1, 2 -
Example Dichlorobenzene

Cl
2 Br
1, 3-
CH3 Mg I + CNCl CH3CN + Mg Dibromobenzene
Br
Cyanogen chloride Methyl cyanide I
3 Br
1,3,5-tri
10) Preparation of Alkanes Br Br
bromobenzene

Compounds like water, alcohols and amines 4 F

1- Bromo - 4- fluoro
which contain active hydrogen atom react -2- iodobenzene
I
with Grignard reagents to form alkanes. Br

5 Br
Example Cl
1- Bromo -2- chloro-4-
CH3MgI + HO H CH4+ MgI (OH) iodobenzene
I

CH3MgI + C 2 H 5 OH CH4 + MgI (OC 2H5)

Ethyl alcohol methane
14.5 Haloarenes
Haloarenes are the compounds X shorter and holds the electron pair of bond
in which the halogen is directly
attached to the benzene ring.
14.5.1. Nomenclature of haloarenes
In the IUPAC nomenclature, the halo
arenes are named by adding prefix halo before
the name of the aromatic hydrocarbon. For
naming disubstituted arenes, the relative
position of the substituent 1,2; 1,3 and 1,4
are indicated by the prefixes ortho, meta and
para, respectively.
14.5.2 Nature of C- X bond in haloarenes
In halo arenes the carbon atom is sp2
hybridised. The sp2 hybridised orbitals are
more tightly.
Halogen atom contains P-orbital
with lone pair of electrons which interacts
with π-orbitals of benzene ring to form
extended conjugated system of π- orbitals.
The delocalisation of these electrons give
double bond character to C – X bond. The
resonance structure of halobenzene is given
as
:X: + X: + X:

For poly haloarenes the numbering

should be done in such a way that the lowest
possible number should be given to the
substituents and the name of the halogens +
X:
: X:
are arranged in alphabetic order.
Nomenclature can be well understood from

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 Due to this double bond character of in HCl gives chloro benzene
C- X bond in haloarenes ,the C-X bond is
shorter in length and stronger than in halo N= N- Cl

alkanes.
Cu 2Cl 2 / HCl (Sandmeyer reaction)
or
Example Cu/ HCl (Gattermann reaction)

Benzene dizonium chloride Cl

Cl
1.70A o
sp 2 + N2

Chlorobenzene
Chloro benzene

3) Preparation of iodobenzene
H
1.77A o Iodobenzene is prepared by warming
sp3
H C Cl benzene diazonium chloride with aqueous
hybridisation
KI solution.
H
Chloro methane
C6H5N2Cl+KI warm C6H5I+N2+KCl
Benzene diazonium Iodo benzene
14.5.3 Methods of preparation chloride

1) Direct halogenation 4) Preparation of fluorobenzene

Chlorobenzene is prepared by Fluoro benzene is prepared by
the direct chlorination of benzene in the treating benzenediazonium chloride with
presence of lewis acid catalyst like FeCl3 fluoro boric acid. This reaction produces
diazonium fluoroborate which on heating
Cl
produces fluorobenzene. This reaction is
+ Cl 2
FeCl3
+ HCl
called Balz – schiemann reaction.

Benzene Chloro benzene C6H5N2Cl + HBF 4 C6H5N2 BF heat

- HCl
Benzene diazonium chloride
C6H 5F + BF3 + N2
2) From benzene diazonium chloride Fluorobenzene

Chloro benzene is prepared by 5) Commercial preparation of chloro

Sandmeyer reaction or Gattermann reaction
using benzene diazonium chloride.
(i) Sandmeyer reaction
When aqueous solution of benzene
diazonium chloride is warmed with Cu2Cl2
benzene (Raschig process)
Chloro benzene is commercially
prepared by passing a mixture of benzene
vapour, air and HCl over heated cupric
chloride .This reaction is called Raschig

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Unit 14.indd 242 27-08-2018 17:55:56

 process. 3. Density

+ HCl + 1/2 O 2
CuCl 2 Halo arenes are all heavier than water
525K and their densities follow the order.
Benzene Cl
Iodo benzene > Bromo benzene >
+ H 2O Chloro benzene
Chloro benzene
14.5.5 Chemical properties

14.5.4 Physical properties A. Reactions invoving halogen atom

1. Melting and boiling points 1. Aromatic nucleophilic substitution

reaction
The boiling points of monohalo
benzene which are all liquids follow the Halo arenes do not undergo
order nucleophilic substitution reaction readily.
This is due to C–X bond in aryl halide is
Iodo > Bromo > Chloro short and strong and also the aromatic ring
is a centre of high electron density.
The boiling points of isomeric
dihalobenzene are nearly the same The halogen of haloarenes can be
substituted by OH– , NH2–, or CN– with
The melting point of para isomer appropriate nucleophilic reagents at high
is generally higher than the melting temperature and pressure.
points of ortho and meta isomers. The
higher melting point of p-isomer is due For Example
to its symmetry which leads to more close
packing of its molecules in the crystal lattice C6H5Cl + NaOH
350 oC
C H OH +NaCl
300 atm 6 5
and consequently strong intermolecular Chlorobenzene Pheno1
attractive force which requires more energy
for melting
This reaction is known as Dow’s Process
p –Dihalo benzene > o- Dichloro
250 0C
benzene > m-Dichloro benzene C6H5Cl + 2NH3 50 atm C6H5NH2 +NH4Cl
Chlorobenzene Aniline

2. Solubility
2500 C
C6H5Cl+CuCN C6H5CN+CuCl
Haloarenes are insoluble in water Pyridine
Phenyl cyanide
Chlorobenzene
because they cannot form hydrogen bonds
with water ,but are soluble in organic
solvents

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 2. Reaction with metals Cl
Cl
(Halogenation)
Cl Cl
a) Wurtz Fittig reaction
FeCl 3 /Cl 2 +
dark

o-Dichlorobenzene Cl
Halo arenes reacts with halo alkanes Chloro benzene
(Minor) p-Dichloro benzene
(Major)

when heated with sodium in ether solution (Nitration)

Cl Cl

H2SO4 /HNO3 NO2

to form alkyl benzene. This reaction is called +

wurtz fittig reaction. o-chloro nitro benzene

NO2
(Minor)
p-chloro nitro benzene
(Major)
Ether (Sulphonation)
C6H5Cl +2Na + ClC 2 H5 C6H5 C2H5 +2NaBr Cl Cl
fuming
Chlorobenzene chloroethane ethyl benzene H 2SO 4
SO 3H
+

o-chloro benzene
SO 3H
b) Fittig reaction sulphonic acid
(Minor) p-chloro benzene
(Friedel - sulphonic acid
(Major)
Haloarenes react with sodium metal Crafts alklation) Cl Cl
Anhydrous CH 3
in dry ether, two aryl groups combine to AlCl3/CH3Cl
+

give biaryl products. This reaction is called o-chloro Toluene

CH 3
(Minor)
fittig reaction p-chloro Toluene
(Major)

C6H5Cl+2Na+Cl-C6H5 Ether C6H5 C6H5 +2NaCl

Chlorobenzene Biphenyl
Toluenes.
4) Reduction
B) Reaction involving aromatic ring
Haloarenes on reduction with Ni-
3. Electrophilic substitution reaction Al alloy in the presence of NaOH gives
Haloarenes undergo aromatic corresponding arenes.
electrophilic substitution reactions. The rate Ni-Al
C6H5Cl+2(H) C6H6 + HCl
of eleclophilic substitution of halobenzene Chloro benzene
NaOH
Benzene
is lower than that of benzene. halogen is
deactivating due to - I effect of halogen.
5) Formation of Grignard reagent
The lone pair of electrons on the chlorine
involves in resonance with the ring. It Haloarenes reacts with magnesium to
increases the electron density at ortho and form Grignard reagent in tetra hydrofuran
para position (refer figure no 14.1). The (THF).
halogen attached to the benzine ring with THF
C6H5Cl + Mg C6H5MgCl
draw electron and thereby and hence the
Chloro benzene Phenyl magnesium
halogen which is attached to the benzene
chloride
directs the incoming, electrophile either to
ortho or to para position in electrophilie 14.5.6 Uses of Chloro benzene
substitution reaction
i) Chloro benzene is used in the
manufacture of pesticides like DDT
ii) It is used as high boiling solvent in
organic synthesis.

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 iii) It is used as fibre - swelling agent in 14.6.1 Preparation
textile processing.
a) gem- Dihalides
Evaluate Yourself ?
Ethylidene dichloride (1, 1 - Dichloro
6) Haloalkanes undergo nucleophilic ethane) is prepared by
substitution reaction whereas haloarenes
undergo electrophilic substitution (i) Treating acetaldehyde with PCl5
reaction. comment.
CH3CHO + PCl 5 CH3CHCl 2 + POCl
14.6 Poly halogen compounds Acetaldehyde Ethylidene dichloride

Carbon compounds containing more (ii) Adding hydrogen chloride to

than one halogen atoms are called poly acetylene
halogen compounds. Some of the important HCl
HC CH + HCl CH2 CH
poly halogen compounds are described
Acetylene
below. Cl
Vinylchloride
They are classified as
CH3 CHCl2
a) gem – dihalides Ethylidene dichloride

CH3CHCl 2 b) vic- Dihalides

Ethylidene chloride
1,1 - Dichloro ethane Ethylene dichloride (1, 2 - Dichloro
ethane) is prepared by the following
CH3
methods.
CH3 -C - Cl
Cl i) Addition of chlorine to ethylene
Isopropylidene chloride (or) CH2 = CH2 + Cl2 → CH2– CH2
Isopropylidene dichloride
Ethylene
2,2-Dichloropropane Cl Cl
Ethylene dichloride
b) vic - dihalides
ii) Action of PCl5 (or HCl) on ethylene
For Example glycol
CH2 CH2 CH2 CH2+ 2POCl 3 +2HCl
CH 2 CH2 + 2PCl 5
Cl Cl OH OH Cl Cl
Ethylene glycol Ethylene dichloride
Ethylene dichloride (or) Ethylene chloride
1, 2 -Dichloro ethane
Properties
CH3

CH3 C CH2 Br Physical Properties

Br i) They are sweet smelling, colourless

Isobutylene dibromide (or) Isobutylene bromide
liquids having relatively high boiling points.
1, 2-Dibromo-2-methyl propane

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Unit 14.indd 245 27-08-2018 17:55:57

 ii) The boiling point of ethylidene CH3 CHCl2 + Zn Methanol
chloride is less than that of ethylene
Ethylidene dichloride
dichloride.
CH2 CH2 + ZnCl2
Chemical properties Ethylene

1) Hydrolysis with aqueous NaOH or

CH2 CH2 + Zn Methanol
KOH
Cl Cl
gem-Dihalides, on hydrolysis with Ethylene dichloride
aqueous KOH give an aldehyde or a ketone
vic-Dihalides, on hydrolysis with aqueous CH2 CH2 + ZnCl 2
KOH gives glycols. Ethylene

2KOH
CH3 CHCl2 [CH 3CH(OH) 2] 3) Reaction with Alcoholic KOH
-2KCl
Ethylene dichloride unstable ­(Dehydrohalogenation)
CH3CHO
-H2O Acetaldehyde gem- Dihalides and vic- Dihalides on
treatment with alcoholic KOH give alkynes.

CH2 CH2 2KOH

H Cl
(aq)
Ethanol
Cl Cl H C C H + 2KOH
Ethylene dichloride H Cl
CH2 CH2 + 2KCl Ethylidene dichloride

OH OH HC CH + 2KCl + H 2O
Ethylene glycol Acetylene

Cl H
This reaction can be used to distinguish the H C C H + 2KOH
Ethanol
gem- Dihalides and vic- Dihalides.
H Cl
2) Reaction with Zinc (Dehalogenation) Ethylene dichloride

HC CH + 2KCl + H 2O
gem- Dihalides and vic- Dihalides on Acetylene
treatment with zinc dust in methanol give
alkenes.
Methylene chloride (Di chloromethane)

Preparation

Methylene chloride is prepared by

the following methods

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Unit 14.indd 246 27-08-2018 17:55:57

 1) Reduction of chloroform Example

a) Reduction of chloroform in the CHCl3 CHI3

presence of Zn + HCl gives methylene
chloride. Chloroform Iodoform

1) Chloroform
Zn+HCl
CHCl 3 CH2Cl 2 + HCl
chloro form 2(H) methylene chloride Chloroform is an important
trihaloalkane. Dumas named CHCl3 as
chloroform as it gives formic acid on
b) Reduction of chloroform using H2/Ni hydrolysis.
H2
CHCl 3 CH2Cl 2 + HCl Preparation:
Ni methylene chloride
chloro form
Chloroform is prepared in the
2) Chlorination of methane laboratory by the reaction between ethyl
alcohol with bleaching powderfollowed by
Chlorination of methane gives the distillation of the product chloroform.
methylene chloride Bleaching powder act as a source of chlorine
and calcium hydroxide. This reaction is
Cl 2/hυ called haloform reaction. The reaction
CH4 CH 3Cl
-HCl proceeds in three steps as shown below.
Methane Methyl chloride

Cl 2/hυ Step – 1: Oxidation

CH2Cl 2
-HCl
Methylene chloride CH3CH2OH + Cl2 → CH3CHO + 2HCl

Ethyl alcohol Acetaldehyde

Uses of methylene chloride
Step – 2: Chlorination
Methylene chloride is used as
1) aerosol spray propellant CH3CHO + 3Cl2 → CCl3CHO + 3HCl

2) solvent in paint remover Acetaldehyde Trichloro acetaldehyde

3) process solvent in the manufacture of Step – 3: Hydrolysis
drugs
2CCl3CHO + Ca(OH)2 → 2CHCl3 + (HCOO)2 Ca
4) a metal cleaning solvent
Chloral   chloroform
14.6.2 Trihaloalkane

Trihaloalkanes are compounds

obtained by replacing three hydrogen atoms
of a hydrocarbon by three halogen atoms.
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Unit 14.indd 247 27-08-2018 17:55:58

 Properties Chloroform reacts with nitric acid
to form chloropicrin.(Trichloro nitro
Physical properties methane)

(i) Chloroform is a colourless liquid with

CHCl 3 + HNO 3 CCl 3NO2 + H2O
peculiar sickly smell and a burning taste
Chloroform Chloropicrin
(ii) The vapours of chloroform when
inhaled cause unconsciousness (depress It used as an insecticide and soil sterilising
the central nervous system) and hence agent.
it is used as an anaesthetic.
4) Carbylamine reaction
Chemical properties
Chloroform reacts with aliphatic
1) Oxidation or aromatic primary amine and alcoholic
caustic potash, to give foul smelling alkyl
Chloroform undergoes oxidation isocyanide (carbylamines)
in the presence of light and air to form CH3NH2+ CHCl3 + 3KOH
phosgene (carbonyl chloride) Methylamine Chloroform

1 air
CHCl 3 + O2 COCl 2+ HCl
2 light CH3NC+3KCl+3H 2O
Chloroform Phosgene
Methylisocyanide

Since phosgene is very poisonous, its This reaction is used to test primary amine.
presence makes chloroform unfit for use as
anaesthetic. Evaluate Yourself ?
7) Chloroform is kept with a little ethyl
2) Reduction alcohol in a dark coloured bottle why?
Chloroform undergoes reduction
with zinc and HCl in the presence of ethyl 14.6.3 Tetra haloalkane
alcohol to form methylene chloride.
Carbon tetrachloride is a good
example for tetra haloalkane
Zn
CHCl 3 + 2(H) CH2Cl 2 + HCl
HCl
Chloroform Methylene chloride Carbon tetrachloride

Preparation
Zn
CHCl 3 + 2(H) CH2Cl 2 + HCl
HCl 1. Chlorination of methane
Chloroform Methylene chloride

The reaction of methane with excess

3) Nitration of chlorine in the presence of sunlight will

248

Unit 14.indd 248 27-08-2018 17:55:58

 give carbon tetrachloride as the major Fe/HCl
product. CCl 4 + 2(H) CHCl 3 + HCl
carbon tetrachloride chloroform
hγ
CH4 + 4Cl2 → CCl4 + 4HCl
Methane Carbon tetrachloride 14.6.4 Freons (CFC)
2. Action of carbondisulphide with
chlorine gas The chloro fluoro derivatives of
methane and ethane are called freons.
Carbon disulphide reacts with Nomenclature
chlorine gas in the presence of anhydrous
AlCl3 as catalyst giving carbon tetrachloride Freon is represented as Freon-cba
Where c = number of carbon atoms – 1
anhydrous
CS 2 + 3Cl2 CCl 4+ S2Cl2
AlCl 3 b = number of hydrogen atoms + 1
carbon disulphide carbon tetrachloride
a = total number of fluorine atoms
Physical properties Example

(i) Carbon tetrachloride is a colourless Formula C–1 H+1 F Name

liquid with its specific smell CFCl3 1–1=0 0+1=1 1 Freon–11
CF2Cl2 1–1=0 0+1=1 2 Freon–12
(ii) It is insoluble in water and soluble in
Freon–
organic solvents C2F2Cl4 2–1=1 0+1=1 2
112
Freon-
Chemical properties C2F3Cl3 2–1=1 0+1=1 3
113

(i) Oxidation Freon – 12 is prepared by the action

of hydrogen fluoride on carbon tetrachloride
Carbon tetrachloride reacts with hot
in the presence of catalylic amount of
water or with hot water vapour producing
antimony patachloride. This is called swartz
the poisonous gas, phosgene.
reaCTION

CCl 4 + H2O(g) COCl 2 + 2H2O Sbcl5

carbon tetrachloride Phosgene CCl 4 + 2HF 2HCl+ CCl2F2
Carbon Freon - 12
tetrachloride
(ii) Reduction
Physical properties
Carbon tetrachloride is reduced by
iron powder in dilute HCl medium to form Freons are highly stable, unreactive,
chloroform non corrosive, non toxic, easily liquefiable
gases.

249

Unit 14.indd 249 27-08-2018 17:55:59

 Uses:
Evaluate Yourself ?
(i) Freons are a used as refrigerants in 8) What is the IUPAC name of the
refrigerators and air conditioners. insecticide DDT? Why is their use
banned in most of the countries?
(ii) It is used as a propellant for aerosols
and foams
Uses:
(iii) It is used as propellant for foams to
i) DDT is used to control certain insects
spray out deodorants, shaving creams,
which carries diseases like malaria and
and insecticides.
yellow fever
14.6.5 DDT (p,p’-dichloro diphenyl tri-
ii) It is used in farms to control some
chloro ethane)
agricultural pests
DDT, the first chlorinated organic
iii) It is used in building construction as
pesticide was prepared in 1873, and in 1939
pest control
Paul Muller discovered the effectiveness
of DDT as an insecticide. He was awarded iv) It is used to kill various insects like
Noble prize in medicine and physiology in housefly and mosquitoes due to its high
1948 for this discovery. and specific toxicity.

DDT can be prepared by heating SUMMARY

a mixture of chlorobenzene with chloral
(Trichloro acetaldehyde) in the presence of • The compounds obtained by the
con.H2SO4. substitution of hydrogen atom of alkanes
by halogen atom are called haloalkane,
H while the compounds obtained by the
H Cl
substitution of hydrogen atoms of arenes
CCl3 - C = O by halogen atom are called haloarenes.
Chloral H Cl
• Modern classification of halo
Chloro benzene compounds is based on the halogen with
H Cl carbon possessing sp3 hybridisation. In
con.H2SO4 H2O these compounds the electronegativity
CCl3 - C
of halogen is more than that of carbon,
Cl
hence Cδ+ – Xδ- bond becomes polar.
DDT
• Haloalkane

• Haloalkanes are prepared from alkanes,

alkenes or alcohols. The boiling points
of haloalkane are higher than that of
corresponding hydrocarbons.

250

Unit 14.indd 250 27-08-2018 17:55:59

 • Haloalkane undergoes nucleophilic
substitution and elimination reactions.
Primary alkyl halides undergo SN2
mechanism. If the reactant is chiral, the
product formed exhibits inversion of
stereo chemical configuration Tertiary
alkyl halide undergoes SN1 mechanism,
via carbonium ion formation. If the
reactant is chiral, the product formed is
optically inactive due to racemisation.
• Organo metallic compound
• Haloalkane reacts with metal to
form organometallic compounds like
Grignard reagent. It is represented as
Rδ- - Mgδ+X. Grignard reagent reacts
with variety of substances to give almost
all class of organic compounds like
alcohols, aldehydes, ketones, acids etc.
• Haloarenes
• Haloarenes are prepared from arenes
or by decomposition of benzene
diazonium chloride. Haloarenes are
more stable than haloalkane. C – X
bond in halo arenes is short and strong.
• Under normal conditions halo
arenes do not undergo nucleophilic
substitution but takes part in
electrophilic substitution. Electron
withdrawing inductive effect of
halogen atom deactivates the benzene
ring whereas resonating structure
control o, p directing nature of halo
arenes.
• Poly halogen compounds
• Organic compounds having two or
more halogen atoms are called poly
251
Unit 14.indd 251
halogen compounds. These compounds
are useful in our day to day life but pose
environmental threat.
• Chloroform is used as an anasthetic,
but because of its toxic nature it has
been replaced by less toxic and safer
anaesthetic like ethers.
• Iodoform is used as an antiseptic, due to
the liberation of free iodine. But it has been
replaced by other formulation containing
iodine, due to its objectional smell.
• Carbon tetrachloride is used in fire
extinguishers. Freons are used as
refrigerant. But both these compounds
lead to adverse environmental effect.
• DDT is used an effective insecticide.
Now a days it is banned because of it's
long term toxic effect.
Evaluation
I. Objective type questions (MCQ)
H 3C H
1. The IUPAC name of H
H
Br is
H3C
a) 2-Bromo pent – 3 – ene
b) 4-Bromo pent – 2 – ene
c) 2-Bromo pent – 4 – ene
d) 4-Bromo pent – 1 – ene
2. Of the following compounds, which
has the highest boiling point?
a) n-Butyl chloride
b) Isobutyl chloride
c) t-Butyl chloride
d) n-propyl chloride
27-08-2018 17:55:59
 3. Arrange the following compounds in 8. Which of the following compounds
increasing order of their density will give racemic mixture on
A) CCl4 B) CHCl3 nucleophilic substitution by OH- ion?
C) CH2Cl2 D) CH3Cl CH3 - CH - CH2Br
i)
a) D < C < B < A b) C > B > A > D C2H 5
c) A < B < C < D d) C > A > B > D
CH3
4. With respect to the position
of – Cl in the compound ii) H3C C C 2H 5
CH3 – CH = CH – CH2 – Cl, it is
classified as Br
H
a) Vinyl b) Allyl
c) Secondary d) Aralkyl iii) CH3 - C - C2H5
Cl
5. What should be the correct IUPAC
name of diethyl chloromethane? a) (i) b) (ii) and (iii)
c) (iii) d) (i) and (ii)
a) 3 – Chloro pentane
b) 1-Chloropentane 9. The treatment of ethyl formate with
excess of RMgX gives
c) 1-Chloro-1, 1, diethyl methane - -
R CH R
d) 1 –Chloro-1-ethyl propane a) R- C - R b)
O OH

6. C -X bond is strongest in c) R- CHO d) R- O – R

a) Chloromethane
10. Benzene reacts with Cl2 in the presence
b) Iodomethane of FeCl3 and in absence of sunlight to
c) Bromomethane form
d) Fluoromethane a) Chlorobenzene
7. In the reaction N= N-Cl b) Benzyl chloride
Cu c) Benzal chloride
HCl X+N2.
X is _________ d) Benzene hexachloride
Cl
11. The name of C2F4Cl2 is ___________
a) b)
a) Freon – 112
b) Freon – 113
Cl Cl
Cl c) Freon – 114
c) d)
d) Freon – 115
Cl Cl

252

Unit 14.indd 252 27-08-2018 17:56:00

 12. Which of the following reagent is (iii) If assertion is true but reason is false.
helpful to differentiate ethylene (iv) If both assertion and reason are false.
dichloride and ethylidene chloride?
a) Zn / methanol 15. Consider the reaction,
b) KOH / ethanol CH3CH2CH2Br + NaCN →
CH3CH2CH2CN + NaBr
c) aqueous KOH
This reaction will be the fastest in
d) ZnCl2 / Con HCl
a) ethanol b) methanol
13. Match the compounds given in c) DMF (N, N' – dimethyl formanide)
Column I with suitable items given in
Column II d) water
16. Freon-12 is manufactured from
Column
tetrachloro methane by
I (Com- Column II (Uses)
pound) a) Wurtz reaction
A Iodoform 1 Fire extinguisher b) Swarts reaction
B Carbon 2 Insecticide
c) Haloform reaction
tetra
chloride d) Gattermann reaction
C CFC 3 Antiseptic 17. The most easily hydrolysed molecule
D DDT 4 Refrigerants under SN1 condition is
Code a) allyl chloride
a) A → 2 B → 4 C →1 D →3 b) ethyl chloride
b) A → 3 B → 2 C →4 D →1 c) ispropylchloride
c) A → 1 B → 2 C →3 D →4 d) benzyl chloride
d) A → 3 B → 1 C →4 D →2 18. The carbo cation formed in SN1
14. Assertion: In mono haloarenes, reaction of al kyl halide in the slow
electrophilic substitution occurs at step is
ortho and para positions. a) sp3 hybridised b) sp2 hybridised
Reason: Halogen atom is a ring c) sp hybridised d) none of these
deactivator 19. The major products obtained when
(i) If both assertion and reason are true chlorobenzene is nitrated with HNO3
and reason is the correct explanation and con H2SO4
of assertion. a) 1-chloro-4-nitrobenzene
(ii) If both assertion and reason are b) 1-chloro-2-nitrobenzene
true but reason is not the correct
explanation of assertion. c) 1-chloro-3-nitrobenzene
d) 1-chloro-1-nitrobenzene

253

Unit 14.indd 253 27-08-2018 17:56:00

 20. Which one of the following is 25. Silverpropionate when refluxed with
most reactive towards nucleophilic Bromine in carbontetrachloride gives
substitution reaction ? a) propionic acid
a) O Cl
b) chloro ethane
c) bromo ethane
b) Cl d) chloro propane

c) Cl 26. Classify the following compounds

in the form of alkyl, allylic, vinyl,
benzylic halides
d) Cl a) CH3 – CH = CH – Cl
(ii) C6H5CH2I
21. Ethylidene chloride on treatment with
aqueous KOH gives (iii) CH3 - CH - CH3

a) acetaldehyde Br

b) ehtyleneglycol (iv) CH2 = CH – Cl

c) formaldehyde 27. Why chlorination of methane is not

d) glycoxal possible in dark?
22. The raw material for Rasching process 28. How will you prepare n propyl iodide
from n-propyl bromide?
a) chloro benzene b) phenol
29. Which alkyl halide from the following
c) benzene d) anisole
pair is i) chiral ii) undergoes faster
23. Chloroform reacts with nitric acid to SN2 reaction?
produce
a) nitro toluene
Br Cl
b) nitro glycerine
30. How does chlorobenzene react with
c) chloropicrin
sodium in the presence of ether?
d) chloropicric acid What is the name of the reaction?
i) CH3MgI 31. Give reasons for polarity of C-X bond
24. acetone X, X is
ii) H2O / H–1 in halo alkane.
32. Why is it necessary to avoid even
a) 2-propanol traces of moisture during the use of
b) 2-methyl-2-propanol Grignard reagent?
c) 1-propanol 33. What happens when acetyl chloride is
d) acetonol treated with excess of CH3MgI?

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 34. Arrange the following alkyl halide in
increasing order of bond enthalpy of
RX
CH3Br, CH3F, CH3Cl, CH3I
35. What happens when chloroform
reacts with oxygen in the presence of
sunlight?
(ii) p-dichloro benzene has higher
melting point than those of o-and
m-dichloro benzene.
42. In an experiment ethyliodide in ether
is allowed to stand over magnesium
pieces. Magnesium dissolves and
product is formed

36. Write down the possible isomers of a) Name the product and write the
C5H11Br and give their IUPAC and equation for the reaction.
common names. b) Why all the reagents used in the
37. Mention any three methods of reaction should be dry? Explain
preparation of haloalkanes from c) How is acetone prepared from the
alcohols. product obtained in the experiment.
38. Compare SN1 and SN 2 reaction 43. Write a chemical reaction useful to
mechanisms. prepare the following:
39. Reagents and the conditions used i) Freon-12 from Carbon tetrachloride
in the reactions are given below. ii) Carbon tetrachloride from carbon
Complete the table by writing down disulphide
the product and the name of the
reaction. 44. What are Freons? Discuss their uses
and environmental effects
Name of
45. Predict the products when
Reaction Product the reac-
bromoethane is treated with the
tion
following
CH3CH2OH + -------- --------
pyridine i) KNO2
SOCl2 ? ii) AgNO2
CH3CH2Br + -------- -------- 46. Explain the mechanism of SN1 reaction
AgF ?
by highlighting the stereochemistry
C6H5Cl + Na -------- -------- behind it
ether
? 47. Write short notes on the the following
40. Discuss the aromatic nucleophilic i) Raschig process
substitutions reaction of
ii) Dows Process
chlorobenzene.
iii) Darzens process
41. Account for the following
(i) t-butyl chloride reacts with
aqueous KOH by SN1 mechanism
while n-butyl chloride reacts with SN2
mechanism.

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 48. Starting from CH3MgI, How will you 51. An organic compound (A) with
prepare the following? molecular formula C2H5Cl reacts with
i) Acetic acid KOH gives compounds (B) and with
alcoholic KOH gives compound (C).
ii) Acetone Identify (A),(B), and (C)
iii) Ethyl acetate 52. Simplest alkene (A) reacts with HCl
iv) Iso propyl alcohol to form compound (B).Compound
v) Methyl cyanide (B) reacts with ammonia to form
49. Complete the following reactions compound (C) of molecular formula
C2H7N.Compound (C) undergoes
carbylamine test. Identify (A), (B),
Peroxide
i) CH 3 - CH = CH2 + HBr and (C).
alcohol 53. A hydrocarbon C3H6 (A) reacts
ii) CH3 - CH2 - Br + NaSH
H 2O with HBr to form compound (B).
Compound (B) reacts with aqueous
THF potassium hydroxide to give (C) of
iii) C6H5Cl + Mg molecular formula C3H6O.what are
(A) (B) and (C). Explain the reactions.
iv) CHCl 3 + HNO3 54. Two isomers (A) and (B) have the
same molecular formula C2H4Cl2.
v) CCl 4 + H2O Compound (A) reacts with aqueous
KOH gives compound (C) of molecular
50. Explain the preparation of the formula C2H4O. Compound (B) reacts
following compounds with aqueous KOH gives compound
(D) of molecular formula C2H6O2.
i) DDT ii) Chloroform
Identify (A),(B),(C) and (D).
iii) Biphenyl
iv) Chloropicrin
v) Freon-12

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 FLOW CHART

Haloalkane

Method of Preparation Chemical Properties

Aq KOH R - OH
HX
R - OH NH3 R - NH2

PX 3 or PX 5 KCN R - CN
R - OH
AgCN
R - NC

R - CH = CH 2 HX KNO 2 R O N=O

AgNO 2 R - NO2
Alkyl halide
X2 hu R- X
R H
NaSH R - SH
Na I / Acetone
R X RONa R O R
Finkel stein reaction
X= Cl, Br
AgF / Alc KOH Alkene
R X swarts reaction
X = Cl, Br Mg / Ether R Mg X
Br 2 / CCl4
R- COOAg
Hunsdiecker reaction HI
R H
Red P

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 FLOW CHART

Synethetic uses of Grignard reagent

O O
R- OH C O
o-
H C H R - COOH
1 alcohol H 2O Carboxylic acid
H H 2O H
O O
R CH R O
OH RC H R O C Cl
o R C OR
2 - alcohol H H 2O H H 2O
Ester
R O
R C R R C R R MgX
Grignard R O CH2 X R O CH2 R
OH H H2O Reagent
Higher eter
3o - alcohol
O
R CHO H C OR CNCl R CN
Aldehyde H H 2O Alkyl cyanide

O
R C R R C Cl HO H R H
O H 2O Alkane
H
Ketone
R OH R H
Alkane

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