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 - jagan.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
(Eg: C2H5–Br - Bromo ethane) Compounds
containing Csp2 – X
Poly Halo compounds bond
(Eg: CCl3–CH2–CH3
Trichloro propane) Vinylic Halides
(Eg: CH2 = CHI Vinyl Iodide)

Compounds
Aryl halides (or) Halo arenes
containing Csp3 – X
(Eg: C6H5 – Cl Chlorobenzene)
bond
Alkyl halides (or) Haloalkanes
(Eg: CH3 – I – lodomethane)

Allylic halides
(Eg: CH2 = CH – CH2 – Cl – Allyl chloride)
Benzylic halides
(Eg: C6H5CH2 Br - Benzyl bromide)
Alicyclic halides
(Eg:  - 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
(1o Haloalkane)
H
Bromoethane

Secondary haloalkane

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

Tertiary haloalkane

CH 3

CH3 C CH3
(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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 S.No Structural formula Common name IUPAC name

1 CH3I methyl iodide Iodomethane

2 CH3CH2Br ethyl bromide Bromoethane

3 CH3CH2CH2F n-propyl fluoride 1-Fluoropropane

CH3 - CH - CH3
4 isopropyl fluoride 2- Fluoropropane
F

5 CH3 - CH2 - CH2 - CH2 - Cl n- butyl chloride 1-Chlorobutane

CH3 - CH - CH2 - Cl 1- Chloro-2-methyl

6 isobutyl chloride
CH3 p
­ ropane

CH3 - CH - CH2 - CH3

7 sec-butyl chloride 2-Chlorobutane
Cl

CH3
2- Chloro -2- methyl
8 CH3 - C- CH3 tert-butyl chloride
propane
Cl

CH3
1-Bromo-2,
9 CH3 - C - CH2 Br neo-pentyl ­bromide
2- ­dimethylpropane
CH3

10 CH2 = CH - Cl vinyl chloride Chloroethene

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

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 S.No Structural formula Common name IUPAC name

Poly halogen Compounds:

The common and IUPAC name of polyhalogen compounds are give below

CH2Cl Ethylene chloride (or) 1,2- Dichloroethane

12 Ethylene dichloride
CH2Cl

CHCl 2 Ethylidene chloride 1,1- Dichloroethane

13 CH 3
(or)
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
move 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
alkanes 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 + NaBr
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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 14.3.4 Physical Properties
1. Pure haloalkanes are colourless.
Bromo and iodo alkanes are coloured in
the presence of light.
2. Haloalkanes having one, two or
three carbon atoms are in the gaseous
state at normal temperature. Haloalkanes
having more than three carbon atoms are
liquids or solids.
3. Boiling point and Melting point
i) Haloalkanes have higher boiling
point and melting point than the
parent alkanes having the same
number of carbons because the
intermolecular forces of attraction
(dipole – dipole interaction and
vander Waals forces) are stronger
in haloalkane.
ii) The boiling point and melting
point of haloalkanes decreases
with respect to the helogen in the
following order.
Example
CH3I > CH3Br > CH3Cl > CH3F
iii) The boiling points of chloro,
bromo and iodo alkanes increase
with the increase in the number of
halogen atoms.
For Example:
CCl4 > CHCl3 > CH2Cl2 > CH3Cl
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iv) The boiling point and melting
point of mono haloalkane increase
with the increase in the number of
carbon atoms.
Example
CH3CH2CH2Cl > CH3CH2Cl > CH3Cl
v) Among isomeric alkyl halides the
boiling point decreases with the
increase in branching in the alkyl
group; with increase in branching,
the molecule attains spherical
shape with less surface area. As a
result the inter molecular forces
become weak, resulting in lower
boiling points.
Example
CH3CH2CH2CH2Cl > CH3CH2CHCH3 >
(351.5K) (341K) Cl
CH3
CH3 C CH3
Cl
(324K)
4. Solubility
Haloalkanes are polar covalent
compounds soluble in organic
solvents, but insoluble in water
because they cannot form hydrogen
bonds with water molecules
4/14/2020 6:21:41 PM
 5. Density Example

The density of liquid alkyl halides are CH3 - CH2 - Br + KOH (aq)
higher than these of hydrocarbons of Bromoethane boil
comparable molecular weight.
CH3 - CH2 - OH + KBr
Evaluate Yourself ? Ethyl alcohol
CH 3 - CH 2 - Br + AgOH
3) Write all possible chain isomers with
Bromoethane Moist silver
molecular formula C5H11Cl oxide
boil
14.3.5 Chemical properties
CH 3 - CH 2 - OH + AgBr
Haloalkanes are one of the most Ethanol
reactive classes of organic compounds.
Their reactivity is due to the presence i) Reaction with alcoholic ammonia
of polar carbon – halogen bond in their (Ammonolysis)
molecules. The reactions of haloalkane Haloalkanes react with alcoholic
may be divided into the following types ammonia solution to form alkyl amines.
Example
i) Nucleophilic substitution reactions
CH3 – CH2 – Br + H – NH2
ii) Elimination reactions Bromo ethane ammonia
iii) Reaction with metals
CH3 – CH2 – NH2 + HBr
iv) Reduction Ethyl amine
1) Nucleophilic substitution reactions However, with excess of halo alkane,
secondary and tertiary amines along with
We know that the Cδ+ - Xδ- present
quartenary ammonium salts are obtained
in halo alkane is polar and hence the
nucleophilic reagents are attracted by CH3CH2NH2 CH3CH2Br (CH 3CH2)2NH
partially positively charged carbon atoms Ethyl amine -HBr
Diethyl amine
resulting in substitution reactions. (1) (2)
CH3CH2Br
Reaction with aqueous alkali or moist -HBr
silver oxide.(Hydrolysis) (CH 3CH2)3N
Triethyl amine
Haloalkane reacts with aqueous (3)
CH3CH2Br
solution of KOH or moist silver oxide -HBr
(Ag2O/H2O) to form alcohols. (CH 3CH2)4N+Br -
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 of the nucleophile
are called ambident nucleophiles. These Bromo ethane Nitro ethane
nucleophiles can attack with either of the
vi) Reaction with sodium or potassi-
two sides depending upon the reaction
um hydrogen sulphide
conditions 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

Nucleophilic 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.
(c) (+) 2 – Octanol (product)
This reaction involves the formation
of a transition state in which both the SN1 Mechanism
reactant molecules are partially bonded
to each other. The attack of nucleophile SN1 stands for unimolecular
occurs from the back side (i.e opposite to nucleophilic substitution
the side in which the halogen is attacked).
The carbon at which substitution occurs has ‘S’ stands for substitution
inverted configuration during the course of ‘N’ stands for nucleophilic
reaction just as an umbrella has tendency ‘1’ stands for unimolecular (one
to invert in a wind storm. This inversion of molecule is involved in the rate determining
configuration is called Walden inversion; step)
after paul walden who first discovered the
inversion of configuration of a compound in The rate of the following SN1 reaction
SN2 reaction. depends upon the concentration of alkyl
halide (RX) and is independent of the
SN2 reaction of an optically active concentration of the nucleophile (OH−).
haloalkane is always accompanied by
inversion of configuration at the asymmetric Hence Rate of the reaction = k[alkyl
centre. Let us consider the following example 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 CH3 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

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

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 haloalkane 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 which the abstraction of the proton from
alkane. This reaction is called β elimination the β carbon and expulsion of halide from
reaction. (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-Bromobutane undergoes elimination reaction by this
CH 2 = 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.
Dry ether
CH3 CH3 CH3 CH2 Br + 2Li
Cl Ethyl bromide CH CH Li + LiBr
C 3 2
Ethyl Lithium
CH 3
4CH3 CH2 Br + 4Na-Pb
Step - 2 Elimination of a proton from the Ethyl bromide Sodium - lead alloy
β - carbon to produce an alkene Dry ether

HO : (CH3CH2)4Pb + 4NaBr + 3Pb

Tetra ethyl lead (TEL)
CH3 CH2 H fast 4) Reduction reactions
C
Haloalkanes are reduced to alkanes
CH3 CH2 by treating with H2 in the presence of
CH3
C H 2O metal catalyst like nickel, palladium etc or
Carbocation with hydroiodic acid in the presence of red
CH 3 phosphorous.
Ni(or)Pd
2 - methyl propene CH 3CH2 Br+H2 523 K
CH3-CH3+HBr
Bromo ethane Ethane

3) Reaction with metals

CH3 CH2 I + HI Red P CH3 - CH3 +I2
Haloalkane reacts with metals, to Iodo ethane Ethane
form a compound containing carbon - metal
bond known as organometallic compounds. 14.3.6 Uses of haloalkane
Chloroform:
a) Grignard reaction
1. is used as a solvent in pharmaceutical
When a solution of halo alkane in industry
ether is treated with magnesium, we get 2. is used for producing pesticides and
alkyl magnesium halide known as Grignard drugs
reagent.
3. is used as an anaesthetic.
Example 4. used as a preservative for anatomical
specimens.
CH3CH2 Br+Mg Dry ether CH3CH2MgBr
Iodoform:
Ethyl bromide Ethyl magnesium bromide
1. is used as an antiseptic for dressing
wounds.

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 Carbon tetrachloride: converted to various organic compounds
1. is used as dry cleaning agent like alcohols, carboxylic acids, aldehydes
2. is used as a solvent for oils, fats and waxes and ketones. The alkyl group being electron
rich acts as a carbanion or a nucleophile.
3. As the vapour of CCl4 is non –
They would attack polarized molecules at a
combustible, it is used under the name
point of low electron density. The following
pyrene for extinguishing the fire in oil or
reactions illustrate the synthetic uses of
petrol.
Grignard reagent.
14.4 Organo metallic Compounds
(1) Preparation of primary alcohol
Organo metallic compounds are
Formaldehyde reacts with Grignard
organic compounds in which there is a
reagent to give addition products which on
direct carbon –metal bond. For Example
hydrolysis yields primary alcohol.
CH3Mg I - Methyl magnesium iodide
O
CH3CH2MgBr - Ethyl magnesium bromide
The Carbon - Magnesium bond in H C H + CH 3 MgI
Grignard reagent is covalent but highly polar. Formaldehyde
The carbon atom is more electro negative OH I
OMgI
than magnesium. Hence, the carbon atom has
partial negative charge and the magnesium H C H H C H + Mg
OH
atom has partial positive charge CH 3 CH3
Ethylalcohol (1o )
δ- δ+
R ----- MgX
14.4.1. Preparation
When a solution of alkyl halide 2) Preparation of secondary alcohol
in ether is allowed to stand over pieces of Aldehydes other than formaldehyde,
magnesium metal, the metal gradually react with Grignard reagent to give addition
dissolves and alkyl magnesium halide product which on hydrolysis yields
(Grignard reagent) is formed. All the secondary alcohol.
reagents used should be pure and dry O OMgI
H
Example CH3 C H + CH3MgI CH3 C H

CH3 I Mg
dry ether Acetaldehyde CH3
CH3MgI
Iodomethane Methyl magnesium iodide
OH I
2O /H+
Evaluate Yourself CH3 C H + Mg
? OH
CH3
5) Why Grignard reagent should be
Isopropylalcohol ( 2o)
prepared in anhydrous condition?
3) Preparation of Tertiary alcohol
14.4.2. Uses of Grignard reagent
Ketone reacts with Grignard reagent
Grignard reagents are synthetically
to give an addition product which on
very useful compounds. These reagents are hydrolysis yields tertiary alcohols.

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 Example For Example
O OMgI
O
CH3 C CH3 CH3MgI CH3 C CH3
O=C=O + CH3MgI CH3 C OMgI
Acetone CH3
OH
I
I H+/H2O
H2O/H +
CH3 C OH+ Mg
CH3 C CH3 Mg
OH
OH O
CH3
Acetic acid
Tert - Butylalcohol( 3o)

(4) Preparation of aldehyde 7) Preparation of esters

Ethyl formate reacts with Grignard
Ethylchloroformate reacts with
reagent to form aldehyde. However,
Grignard reagent to form esters.
with excess of Grignard reagent it forms
secondary alcohol. Example
Example O OMgI
O OMgI C2H 5O C Cl + CH3MgI C2H 5O C Cl
H C OC 2H5 + CH3MgI H C OC2H5 Ethylchloroformate CH3
Ethylformate CH3 I
O CH3 C OC2H5+ Mg
I
H2O/H+ Cl
H C CH3 + Mg
O
Acetaldehyde OC2H5
Ethylacet
ate

(5) Preparation of ketone
8) Preparation of higher ethers
Acid chloride reacts with Grignard
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
CH3 O CH2Cl + CH 3MgI
OMgI
Chloro dimethyl ether
CH3 C Cl + CH3MgI CH3 C Cl
I
Acetyl chloride CH3
CH3 O CH2CH3 + Mg
O I
H2O/H+
Ethyl methyl ether Cl
CH3 C CH 3 + Mg
Acetone Cl

9) Preparation of alkyl cyanide

6) Preparation of carboxylic acids
Grignard reagent reacts with
Solid carbon dioxide reacts with cyanogen chloride to from alkyl cyanide
Grignard reagent to form addition product Example
which on hydrolysis yields carboxylic acids.
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 Cl Compound IUPAC NAME
CH3 Mg I + CNCl CH3CN + Mg Cl
Cyanogen chloride Methyl cyanide I 1 Cl 1, 2 -
Dichlorobenzene

10) Preparation of Alkanes Br

1, 3-
2 Dibromobenzene
Br
Compounds like water, alcohols and amines
which contain active hydrogen atom react Br

3 1,3,5-tri
with Grignard reagents to form alkanes. Br bromobenzene
Br

Example F

4 1- Bromo - 4- fluoro
CH3MgI + HO H CH4+ MgI (OH) -2- iodobenzene
I
Br

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

Ethyl alcohol methane Cl
5 1- Bromo -2- chloro-4-
14.5 Haloarenes iodobenzene
I

Haloarenes are the compounds X

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.
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
are arranged in alphabetic order.
Nomenclature can be well understood from
the following examples.
14.5.2 Nature of C- X bond in haloarenes
In halo arenes the carbon atom is sp2
hybridised. The sp2 hybridised orbitals are
shorter and holds the electron pair of bond
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:
+
X:
: X:

Due to this double bond character of

C- X bond in haloarenes ,the C-X bond is
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 shorter in length and stronger than in halo
alkanes.
Example
Cl
1.70A o
sp 2
Chloro benzene
H
1.77A o
sp3
H C
hybridisation
H KI solution.
Chloro methane
14.5.3 Methods of preparation
1) Direct halogenation
Chlorobenzene is prepared by
the direct chlorination of benzene in the
presence of lewis acid catalyst like FeCl3
Cl
FeCl3
+ Cl 2
Benzene Chloro benzene
2) From benzene diazonium chloride
Chloro benzene is prepared by
Sandmeyer reaction or Gattermann reaction
using benzene diazonium chloride.
(i) Sandmeyer reaction
When aqueous solution of benzene
diazonium chloride is warmed with Cu2Cl2
in HCl gives chloro benzene
Unit 14 - jagan.indd 242
N= N- Cl
Cu 2Cl 2 / HCl (Sandmeyer reaction)
or
Cu/ HCl (Gattermann reaction)
Benzene dizonium chloride Cl
+ N2
Chlorobenzene
3) Preparation of iodobenzene
Iodobenzene is prepared by warming
Cl benzene diazonium chloride with aqueous
C6H5N2Cl+KI warm C6H5I+N2+KCl
Benzene diazonium Iodo benzene
chloride
4) Preparation of fluorobenzene
Fluoro benzene is prepared by
treating benzenediazonium chloride with
fluoro boric acid. This reaction produces
diazonium fluoroborate which on heating
produces fluorobenzene. This reaction is
+ HCl called Balz – schiemann reaction.
heat
C6H5N2Cl + HBF 4 C6H5N2 BF4
- HCl
Benzene diazonium chloride
C6H 5F + BF3 + N2
Fluorobenzene
5) Commercial preparation of chloro
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
process.
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4/14/2020 6:21:59 PM
 CuCl 2 3. Density
+ HCl + 1/2 O 2
525K
Benzene Cl
Halo arenes are all heavier than water
and their densities follow the order.
+ H 2O
Iodo benzene > Bromo benzene >
Chloro benzene Chloro benzene

14.5.4 Physical properties 14.5.5 Chemical properties

1. Melting and boiling points A. Reactions invoving halogen atom

The boiling points of monohalo 1. Aromatic nucleophilic substitution

benzene which are all liquids follow the
order
Iodo > Bromo > Chloro
The boiling points of isomeric
dihalobenzene are nearly the same
reaction
Halo arenes do not undergo
nucleophilic substitution reaction readily.
This is due to C–X bond in aryl halide is
short and strong and also the aromatic ring
is a centre of high electron density.

The melting point of para isomer The halogen of haloarenes can be

is generally higher than the melting substituted by OH– , NH2–, or CN– with
points of ortho and meta isomers. The appropriate nucleophilic reagents at high
higher melting point of p-isomer is due temperature and pressure.
to its symmetry which leads to more close
packing of its molecules in the crystal lattice For Example
and consequently strong intermolecular
350 oC
attractive force which requires more energy C6H5Cl + NaOH C H OH +NaCl
300 atm 6 5
Chlorobenzene Pheno1
for melting

p –Dihalo benzene > o- Dichloro This reaction is known as Dow’s Process

benzene > m-Dichloro benzene
250 0C
C6H5Cl + 2NH3 50 atm C6H5NH2 +NH4Cl
2. Solubility Aniline
Chlorobenzene

Haloarenes are insoluble in water

because they cannot form hydrogen bonds 2500 C
C6H5Cl+CuCN Pyridine
C6H5CN+CuCl
with water ,but are soluble in organic Chlorobenzene Phenyl cyanide
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 Chloro benzene
(Minor) p-Dichloro benzene
(Major)

alkanes when heated with sodium in (Nitration)

Cl Cl

H2SO4 /HNO3 NO2

ether solution to form alkyl benzene. This +

reaction is called Wurtz Fittig reaction. o-chloro nitro benzene

NO2
(Minor)
p-chloro nitro benzene
(Major)
Ether C6H5 C2H5 +2NaCl
(Sulphonation)
C6H5Cl +2Na + ClC 2 H5 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
Crafts alklation) (Major)
Haloarenes react with sodium metal Anhydrous
Cl Cl

CH 3
in dry ether, two aryl groups combine AlCl3/CH3Cl
+

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

CH 3
(Minor)
called Fittig reaction p-chloro Toluene
(Major)

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

Chlorobenzene Biphenyl
Toluene
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. Ni-Al
C6H5Cl+2(H) C6H6 + HCl
The rate of eleclophilic substitution of Chloro benzene
NaOH
Benzene
halobenzene is lower than that of benzene.
halogen is deactivating due to - I effect
5) Formation of Grignard reagent
of halogen. The lone pair of electrons on
the chlorine involves in resonance with Haloarenes reacts with magnesium to
the ring. It increases the electron density form Grignard reagent in tetra hydrofuran
at ortho and para position (refer figure no (THF).
14.1). The halogen attached to the benzine THF
C6H5Cl + Mg C6H5MgCl
ring with draw electron and thereby and
Chloro benzene Phenyl magnesium
hence the halogen which is attached to the
chloride
benzene directs the incoming, electrophile
either to ortho or to para position in 14.5.6 Uses of Chloro benzene
electrophilie 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 + POCl3
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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 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 3) Reaction with Alcoholic KOH

CH3 CHCl2 [CH 3CH(OH) 2]
-2KCl unstable ­(Dehydrohalogenation)
Ethylidene dichloride
-H2O
gem- Dihalides and vic- Dihalides on
treatment with alcoholic KOH give alkynes.
CH3CHO
Acetaldehyde
H Cl
Ethanol
CH2 CH2 2KOH H C C H + 2KOH
(aq)
Cl Cl H Cl
Ethylene dichloride Ethylidene dichloride
CH2 CH2 + 2KCl
HC CH + 2KCl + 2H 2O
OH OH Acetylene
Ethylene glycol
Cl H
This reaction can be used to distinguish the Ethanol
H C C H + 2KOH
gem- Dihalides and vic- Dihalides.
H Cl
2) Reaction with Zinc (Dehalogenation) Ethylene dichloride

Gem- Dihalides and vic- Dihalides HC CH + 2KCl + 2H 2O

on treatment with zinc dust in methanol Acetylene
give alkenes.
Methylene chloride (Di chloromethane)
Preparation
Methylene chloride is prepared by
the following methods

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 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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 Properties
CHCl 3 + HNO 3 CCl 3NO2 + H2O
Physical properties Chloroform Chloropicrin

(i) Chloroform is a colourless liquid with It used as an insecticide and soil sterilising
peculiar sickly smell and a burning taste agent.

(ii) The vapours of chloroform when 4) Carbylamine reaction

inhaled it causes unconsciousness
(depress the central nervous system)
and hence it is used as an anaesthetic.
Chemical properties
Chloroform reacts with aliphatic
or aromatic primary amine and alcoholic
caustic potash, to give foul smelling alkyl
isocyanide (carbylamines)

1) Oxidation CH3NH2+ CHCl3 + 3KOH

Methylamine Chloroform
Chloroform undergoes oxidation
in the presence of light and air to form
phosgene (carbonyl chloride) CH3NC+3KCl+3H 2O
Methylisocyanide
1 air
CHCl 3 + O2 COCl 2+ HCl This reaction is used to test primary amine.
2 light
Chloroform Phosgene
Evaluate Yourself ?
Since phosgene is very poisonous, its 7) Chloroform is kept with a little ethyl
presence makes chloroform unfit for use as alcohol in a dark coloured bottle why?
anaesthetic.
14.6.3 Tetra haloalkane
2) Reduction
Carbon tetrachloride is a good
Chloroform undergoes reduction example for tetra haloalkane
with zinc and HCl in the presence of ethyl
alcohol to form methylene chloride. Carbon tetrachloride

Zn Preparation
CHCl 3 + 2[H] CH2Cl 2 + HCl
HCl
Methylene chloride
1. Chlorination of methane
Chloroform
The reaction of methane with excess
of chlorine in the presence of sunlight will
3) Nitration give carbon tetrachloride as the major
product.
Chloroform reacts with nitric acid
hγ
to form chloropicrin.(Trichloro nitro CH4 + 4Cl2 → CCl4 + 4HCl
methane)
Methane Carbon tetrachloride
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 2. Action of carbondisulphide with Nomenclature
chlorine gas Freon is represented as Freon-cba
Where c = number of carbon atoms – 1
Carbon disulphide reacts with
chlorine gas in the presence of anhydrous b = number of hydrogen atoms + 1
AlCl3 as catalyst giving carbon tetrachloride
a = total number of fluorine atoms
anhydrous Example
CS 2 + 3Cl2 CCl 4+ S2Cl2
AlCl 3
carbon disulphide carbon tetrachloride
Formula C–1 H+1 F Name
CFCl3 1–1=0 0+1=1 1 Freon–11
Physical properties CF2Cl2 1–1=0 0+1=1 2 Freon–12
(i) Carbon tetrachloride is a colourless Freon–
liquid with its specific smell C2F2Cl4 2–1=1 0+1=1 2
112
Freon-
(ii) It is insoluble in water and soluble in C2F3Cl3 2–1=1 0+1=1 3
113
organic solvents
Freon – 12 is prepared by the
Chemical properties action of hydrogen fluoride on carbon
(i) Hydrolysis tetrachloride in the presence of catalylic
Carbon tetrachloride reacts with hot amount of antimony pentachloride. This is
water or with hot water vapour producing called swartz reaction.
the poisonous gas, phosgene.
Sbcl5
CCl 4 + 2HF 2HCl+ CCl2F2
CCl 4 + H2O(g) COCl 2 + 2HCl Carbon Freon - 12
carbon tetrachloride Phosgene tetrachloride

Physical properties
(ii) Reduction
Freons are highly stable, unreactive,
Carbon tetrachloride is reduced by non corrosive, non toxic, easily liquefiable
iron powder in dilute HCl medium to form gases.
chloroform
Uses:
Fe/HCl (i) Freons are a used as refrigerants in
CCl 4 + 2(H) CHCl 3 + HCl refrigerators and air conditioners.
carbon tetrachloride chloroform
(ii) It is used as a propellant for aerosols
and foams
14.6.4 Freons (CFC)
The chloro fluoro derivatives of (iii) It is used as propellant for foams to
methane and ethane are called freons. spray out deodorants, shaving creams,
and insecticides.

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 14.6.5 DDT (p,p’-dichloro diphenyl tri-
chloro ethane)
DDT, the first chlorinated organic
pesticide was prepared in 1873, and in 1939
Paul Muller discovered the effectiveness
of DDT as an insecticide. He was awarded
Noble prize in medicine and physiology in
1948 for this discovery.
DDT can be prepared by heating
a mixture of chlorobenzene with chloral
(Trichloro acetaldehyde) in the presence of
Conc.H2SO4.
H Cl
H
CCl3 - C = O
Chloral H Cl
Chloro benzene
H Cl
con.H2SO4
CCl3 - C
Cl
DDT
Evaluate Yourself ? product formed exhibits inversion of
8) What is the IUPAC name of the
insecticide DDT? Why is their use
banned in most of the countries?
Uses:
i) DDT is used to control certain insects
which carries diseases like malaria and
yellow fever
ii) It is used in farms to control some
agricultural pests
iii) It is used in building construction as
pest control
iv) It is used to kill various insects like
housefly and mosquitoes due to its high
and specific toxicity.
Unit 14 - jagan.indd 250
SUMMARY
• The compounds obtained by the
substitution of hydrogen atom of alkanes
by halogen atom are called haloalkane,
while the compounds obtained by the
substitution of hydrogen atoms of arenes
by halogen atom are called haloarenes.
• Modern classification of halo
compounds is based on the halogen with
carbon possessing sp3 hybridisation. In
these compounds the electronegativity
of halogen is more than that of carbon,
hence Cδ+ – Xδ- bond becomes polar.
• Haloalkane
• Haloalkanes are prepared from alkanes,
alkenes or alcohols. The boiling points
of haloalkane are higher than that of
H2O corresponding hydrocarbons.
• Haloalkane undergoes nucleophilic
substitution and elimination reactions.
Primary alkyl halides undergo SN2
mechanism. If the reactant is chiral, the
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
250
4/14/2020 6:22:11 PM
 • Haloarenes are prepared from arenes
or by decomposition of benzene Evaluation
diazonium chloride. Haloarenes are I. Choose the best answer.
more stable than haloalkane. C – X H 3C H
bond in halo arenes is short and strong. 1. The IUPAC name of H
H
Br is
H 3C

• Under normal conditions halo a) 2-Bromo pent – 3 – ene

arenes do not undergo nucleophilic b) 4-Bromo pent – 2 – ene
substitution but takes part in c) 2-Bromo pent – 4 – ene
electrophilic substitution. Electron
d) 4-Bromo pent – 1 – ene
withdrawing inductive effect of
halogen atom deactivates the benzene 2. Of the following compounds, which
ring whereas resonating structure has the highest boiling point?
control o, p directing nature of halo a) n-Butyl chloride
arenes.
b) Isobutyl chloride
• Poly halogen compounds c) t-Butyl chloride
d) n-propyl chloride
• Organic compounds having two or
more halogen atoms are called poly 3. Arrange the following compounds in
halogen compounds. These compounds increasing order of their density
are useful in our day to day life but pose A) CCl4 B) CHCl3
environmental threat.
C) CH2Cl2 D) CH3Cl
• Chloroform is used as an anasthetic, a) D < C < B < A b) C > B > A > D
but because of its toxic nature it has c) A < B < C < D d) C > A > B > D
been replaced by less toxic and safer
4. With respect to the position
anaesthetic like ethers.
of – Cl in the compound
CH3 – CH = CH – CH2 – Cl, it is
• Iodoform is used as an antiseptic, due to
classified as
the liberation of free iodine. But it has been
replaced by other formulation containing a) Vinyl b) Allyl
iodine, due to its objectional smell. c) Secondary d) Aralkyl

• Carbon tetrachloride is used in fire 5. What should be the correct IUPAC

extinguishers. Freons are used as name of diethyl chloromethane?
refrigerant. But both these compounds a) 3 – Chloro pentane
lead to adverse environmental effect.
b) 1-Chloropentane
• DDT is used an effective insecticide. c) 1-Chloro-1, 1, diethyl methane
Now a days it is banned because of it's
d) 1 –Chloro-1-ethyl propane
long term toxic effect.

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 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

12. Which of the following reagent is

8. Which of the following compounds helpful to differentiate ethylene
will give racemic mixture on dichloride and ethylidene chloride?
nucleophilic substitution by OH- ion? a) Zn / methanol
CH3 - CH - CH2Br b) KOH / ethanol
i)
C2H 5 c) aqueous KOH
d) ZnCl2 / Con HCl
CH3
13. Match the compounds given in
ii) H3C C C 2H 5
Column I with suitable items given in
Br Column II
H
Column
iii) CH3 - C - C2H5 I (Com- Column II (Uses)
pound)
Cl
A Iodoform 1 Fire extinguisher
a) (i) b) (ii) and (iii)
c) (iii) d) (i) and (ii) B Carbon 2 Insecticide
tetra
9. The treatment of ethyl formate with chloride
excess of RMgX gives
C CFC 3 Antiseptic
R- CH - R
a) R- C - R b)
O OH D DDT 4 Refrigerants

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 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

(iii) If assertion is true but reason is false. d) 1-chloro-1-nitrobenzene

(iv) If both assertion and reason are false. 20. Which one of the following is
most reactive towards nucleophilic
15. Consider the reaction, substitution reaction ?
CH3CH2CH2Br + NaCN → a) O Cl
CH3CH2CH2CN + NaBr
This reaction will be the fastest in b) Cl
a) ethanol b) methanol
c) Cl
c) DMF (N, N' – dimethyl formamide)
d) water
d) Cl
16.
Freon-12 is manufactured from
21. Ethylidene chloride on treatment with
tetrachloro methane by
aqueous KOH gives
a) Wurtz reaction
a) acetaldehyde
b) Swarts reaction
b) ehtyleneglycol
c) Haloform reaction
c) formaldehyde
d) Gattermann reaction
d) glycoxal
17. The most easily hydrolysed molecule
22. The raw material for Rasching process
under SN1 condition is
a) chloro benzene b) phenol

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 c) benzene d) anisole from n-propyl bromide?
23. Chloroform reacts with nitric acid to 29. Which alkyl halide from the following
produce pair is i) chiral ii) undergoes faster
a) nitro toluene SN2 reaction?

b) nitro glycerine
Br Cl
c) chloropicrin
d) chloropicric acid 30. How does chlorobenzene react with
i) CH3MgI sodium in the presence of ether?
24. acetone X, X is What is the name of the reaction?
ii) H2O / H–1
31. Give reasons for polarity of C-X bond
a) 2-propanol in halo alkane.
b) 2-methyl-2-propanol 32. Why is it necessary to avoid even
traces of moisture during the use of
c) 1-propanol
Grignard reagent?
d) acetonol
33. What happens when acetyl chloride is
25. Silverpropionate when refluxed with treated with excess of CH3MgI?
Bromine in carbontetrachloride gives
34. Arrange the following alkyl halide in
a) propionic acid increasing order of bond enthalpy of
b) chloro ethane RX
c) bromo ethane CH3Br, CH3F, CH3Cl, CH3I
d) chloro propane 35. What happens when chloroform
reacts with oxygen in the presence of
26. Classify the following compounds
sunlight?
in the form of alkyl, allylic, vinyl,
benzylic halides 36. Write down the possible isomers of
C5H11Br and give their IUPAC and
a) CH3 – CH = CH – Cl
common names.
(ii) C6H5CH2I
37. Mention any three methods of
(iii) CH3 - CH - CH3 preparation of haloalkanes from
Br alcohols.
(iv) CH2 = CH – Cl 38. Compare SN1 and SN 2 reaction
mechanisms.
II. Write brief answer to the following 39. Reagents and the conditions used
questions. in the reactions are given below.
27. Why chlorination of methane is not Complete the table by writing down
possible in dark? the product and the name of the
reaction.
28. How will you prepare n propyl iodide

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 Name of and environmental effects
Reaction Product the reac- 45.
Predict the products when
tion bromoethane is treated with the
CH3CH2OH + -------- -------- following
pyridine i) KNO2
SOCl2 ?
ii) AgNO2
CH3CH2Br + -------- --------
AgF ? 46. Explain the mechanism of SN1 reaction
C6H5Cl + Na -------- -------- by highlighting the stereochemistry
ether behind it
?
47. Write short notes on the the following
40. Discuss the aromatic nucleophilic
substitutions reaction of i) Raschig process
chlorobenzene. ii) Dows Process
41. Account for the following iii) Darzens process
(i) t-butyl chloride reacts with 48. Starting from CH3MgI, How will you
aqueous KOH by SN1 mechanism prepare the following?
while n-butyl chloride reacts with SN2 i) Acetic acid
mechanism.
ii) Acetone
(ii) p-dichloro benzene has higher
melting point than those of o-and iii) Ethyl acetate
m-dichloro benzene. iv) Iso propyl alcohol
42. In an experiment ethyliodide in ether v) Methyl cyanide
is allowed to stand over magnesium 49. Complete the following reactions
pieces. Magnesium dissolves and
product is formed Peroxide
i) CH 3 - CH = CH2 + HBr
a) Name the product and write the
equation for the reaction. alcohol
ii) CH3 - CH2 - Br + NaSH
H 2O
b) Why all the reagents used in the
reaction should be dry? Explain
THF
c) How is acetone prepared from the iii) C6H5Cl + Mg
product obtained in the experiment.
43. Write a chemical reaction useful to iv) CHCl 3 + HNO3
prepare the following:
i) Freon-12 from Carbon tetrachloride v) CCl 4 + H2O

ii) Carbon tetrachloride from carbon

50.
Explain the preparation of the
disulphide
following compounds
44. What are Freons? Discuss their uses
i) DDT ii) Chloroform
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 iii) Biphenyl 53. A hydrocarbon C3H6 (A) reacts
iv) Chloropicrin with HBr to form compound (B).
Compound (B) reacts with aqueous
v) Freon-12 potassium hydroxide to give (C) of
51. An organic compound (A) with molecular formula C3H8O. What are
molecular formula C2H5Cl reacts with (A) (B) and (C). Explain the reactions.
KOH gives compounds (B) and with 54. Two isomers (A) and (B) have the
alcoholic KOH gives compound (C). same molecular formula C2H4Cl2.
Identify (A),(B), and (C) Compound (A) reacts with aqueous
52. Simplest alkene (A) reacts with HCl KOH gives compound (C) of molecular
to form compound (B).Compound formula C2H4O. Compound (B) reacts
(B) reacts with ammonia to form with aqueous KOH gives compound
compound (C) of molecular formula (D) of molecular formula C2H6O2.
C2H7N.Compound (C) undergoes Identify (A),(B),(C) and (D).
carbylamine test. Identify (A), (B),
and (C).

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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 hυ 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
R C OR
2o - 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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