10.

HALOGEN DERIVATIVES
Can you recall ? CH3 - CH2 - X CH2 = CH - X
Identify the functional group (Haloalkane) (Haloalkene)
in the following compounds.
HC ≡ C - X X
i. ii. CCl2F2
Br (Haloalkyne)
(Haloarene)
(Benzyl bromide) (Freon - 12) b. On the basis of number of halogen atoms,
iii. Cl iv. Cl - CH = CCl2 halogen derivatives are classified as mono,
Cl Cl di, tri or poly halogen compounds.
(Westrosol)
X
Cl Cl CH3 - CH2 - X
Cl
(Hexachlorobenzene) Monohalogen compounds

v. Cl CH3 - CH - X CH2 - CH2 X

Cl Cl
X X X X
Cl Cl
Dihalogen compounds
Cl
(Benzene hexachloride)
(Hexachlorocyclohexane) X
CH2 - CH - CH2 X
The parent family of organic compounds X X X
is hydrocarbon. Replacement of hydrogen X
atom/s in aliphatic or aromatic hydrocarbons Trihalogen compounds
by halogen atom/s results in the formation of
halogen derivatives of hydrocarbons. We will consider classification of mono
halogen derivatives in more detail.
In this chapter we will study halogen
derivatives in a systematic way. 10.1.1 Classification of monohalogen
compounds : Monohalogen compounds are
Internet my friend further classified on the basis of position of
Find out the structures halogen atom and the type of hybridization of
of two thyroid hormones T3 carbon to which halogen is attached.
(triiodothyronine) and T4 (thyroxine). a. Alkyl halides or haloalkanes : In alkyl
How do these help our body ?
halides or haloalkanes the halogen atom is
10.1 Classification of halogen derivatives : bonded to sp3 hybridized carbon which is
a part of saturated carbon skeleton. Alkyl
Halogen derivatives of hydrocarbons are
halides may be primary, secondary or tertiary
classified mainly in two ways.
depending on the substitution state of the
a. On the basis of hydrocarbon skeleton to carbon to which halogen is attached : (Refer
which halogen atom is bonded, the halogen to Std. XI Chemistry Textbook, section 14.3).
derivatives are classified as haloalkanes,
haloalkenes, haloalkynes and haloarenes.
210
 R d. Vinylic halides : In vinylic halides halogen
R - CH2- X R - CH- R R − C − X atom is bonded to a sp2 hybridized carbon
X R atom of aliphatic chain. Vinylic halide is a
haloalkene.
Primary Secondary Tertiary
halide halide halide X
(1 halide)
0
(2 halide)
0
(3 halide)
0 CH2= CH - X

b. Allylic halides : In allylic halides, halogen e. Haloalkyne : When a halogen atom is

atom is bonded to a sp3 hybridized carbon bonded to a sp hybridized carbon atom it is
atom next to a carbon-carbon double bond. a haloalkyne.
X CH ≡ C - X
CH2= CH - CH2 - X
f. Aryl halides or haloarenes : In aryl
halides, halogen atom is directly bonded to
c. Benzylic halide : In benzylic halides the sp2 hybridized carbon atom of aromatic
halogen atom is bonded to a sp3 hybridized ring.
carbon atom which is further bonded to an CH3
aromatic ring. X X
CH3
CH2 - X C X
CH3

Table 10.1 Names of some halogen derivatives

Formula Common name IUPAC name
CH2Cl2 Methylene chloride Dichloromethane
CH3CH2Br Ethyl bromide Bromoethane
CH3CH(Cl)CH3 Isopropyl chloride 2-Chloropropane
(CH3)2 CH - CH2Br Isobutyl bromide 1-Bromo-2-methylpropane
(CH3)3 C Br Tert-butyl bromide 2-Bromo-2-methyl-propane
(CH3)3 C CH2Cl Neopentyl chloride 1-Chloro-2, 2-dimethyl pro-
pane
CH2 = CH - Cl Vinyl chloride 1-Chloroethene
CH2 = CH - CH2Br Allyl bromide 3-Bromopropene
CH ≡ C - Cl Chloro acetylene Chloroethyne
CH2I Benzyl iodide Iodophenylmethane

I p-Iodotoluene 1-Iodo-4-methyl benzene or

4-Iodotoluene
H3C
Cl m-dichlorobenzene 1, 3-dichlorobenzene

Cl

211
10.2 Nomenclature of halogen derivatives a wide variety. The hydroxyl group may be
replaced by halogen atom using (a) halogen
Can you recall ? acid, (b) phosphorous halide or (c) thionyl
• In IUPAC system of chloride.
nomenclature does the a. By using halogen acid or hydrogen
functional group 'halogen' appear halide (HX) : The conditions for reaction
as a suffix or prefix ? of alcohol with halogen acid (HX) depend
• What are the trivial names of laboratory on the structure of the alcohol and particular
solvents CHCl3 and CCl4 ? halogen acid used. The order of reactivity of
alcohols with a given haloacid is 30>20>10.
The common names of alkyl halides are (Refer to section 11.2.1 a)
derived by naming the alkyl group followed R - OH + HX
suitable
R - X + H2O
condition
by the name of halogen as halide. For
example, methyl iodide, tert-butyl chloride. (Alcohol) (Alkyl halide)
According to IUPAC system of nomenclature Hydrogen chloride is used with zinc
(Std. XI Chemistry Textbook Chapter 14, chloride (Grooves' process) for primary and
section 14.4.7) alkyl halides are named as secondary alcohols, but tertiary alcohols
haloalkanes. Aryl halides are named as readily react with concentrated hydrochloric
haloarenes in common as well as IUPAC acid in absence of zinc chloride.
system. For dihalogen derivative of an arene, anhydrous
R - OH + HCl ZnCl2 R - Cl + H2O
prefix o-, m-, p- are used in common name
system but in IUPAC system the numerals
1,2 ; 1,3 and 1,4 respectively are used. Do you know ?
Common and IUPAC names of some halogen Zinc chloride is a Lewis acid
derivatives are given in Table 10.1. and consequently can coordinate
with the alcohol, weakening R - O bond.
Use your brain power Mixture of concentrated HCl and anhydrous
Write IUPAC names of the ZnCl2 is called Lucas reagent.
following.
Constant boiling hydrobromic acid
i. CH3 - CH - CH3 ii. CH3 - CH - CH2I (48%) is used for preparing alkyl bromides.
Br CH3 Primary alkyl bromides can also be prepared
by reaction with NaBr and H2SO4. Here HBr
iii. CH3 - CH = CH - CH2Cl is generated in situ.
NaBr, H2SO4
iv. CH3 - C ≡ C - CH2 - Br R-CH2-OH+HBr heat R-CH2-Br+H2O

Br Good yield of alkyl iodides may be

v. Br vi. obtained by heating alcohols with sodium or
potassium iodide in 95 % phosphoric acid.
Here HI is generated in situ.
Br
NaI/H3PO4
R - OH + HI R - I + H2O
10.3 Methods of preparation of alkyl halides
10.3.1 From alcohol : The most widely used Can you tell ?
method of preparation of alkyl halide is Why phosphoric acid is preferred to
replacement of hydroxyl group of an alcohol H2SO4 to prepare HI in situ ?
by halogen atom. Alcohols are available in
212
b. By using phosphorous halide : An Addition of hydrogen halide to alkene
alkyl halide may be prepared by action of
Alkyl halides are formed on addition
phosphorous halide on alcohol. Phosphorous
of hydrogen halide to alkenes. Refer to Std
tribromide and triiodide are usually generated
XI Chemistry Textbook Chapter 15, section
in situ (produced in the reaction mixture) by
15.2.4 for all the details including order of
the action of red phosphorous on bromine and
reactivity of HX, Markownikov rule and
iodine respectively. Phosphorous pentachloride
peroxide effect.
reacts with alcohol to give alkyl chloride.
3R - OH + PX3 3R - X + H3PO3 Problem 10.1 : How will you obtain
1-bromo-1-methylcyclohexane from alkene?
R - OH + PCl5 R - Cl + HCl + POCl3
Write possible structures of alkene and the
Do you know ? reaction involved.
Some times during replacement Solution :
of -OH by -X, alcohols tend to
undergo rearrangement. This tendency CH3 CH3 Br
can be minimized by use of phosphorous
halides. Straight chain primary alcohols + HBr
react with phosphorous trihalide to give
unrearranged alkyl halides. CH2 CH3 Br
c. By using thionyl chloride : Thionyl + HBr
chloride reacts with straight chain primary
alcohols to give unrearranged alkyl chloride.
The byproducts obtained are gases. There
Use your brain power
is no need to put extra efforts for its
separation. Therefore this method is preferred Rewrite the following reaction
for preparation of alkyl chloride. by filling the blanks :
∆ • CH3 - CH = CH2 + HBr +
R - OH + SOCl2 R - Cl + SO2↑+ HCl↑
(major)(minor)
Can you recall ? • (CH3)2C=CHCH3+HBr
peroxide
+
Identify the products of the (major)(minor)
following reactions. • CH3 - CH = CH2+HBr
peroxide
+
hν
i. CH4 + Cl2 ? (major)(minor)
HCl
ii. CH3 - CH = CH2 ?
Peroxide Do you know ?
iii. CH3 - CH = CH2 + HBr ?
CCl4 Alkenes form additon product,
iv. CH2 = CH - CH3 + Br2 ?
vicinal dihalide, with chlorine or
10.3.2 From hydrocarbon bromine usually in inert solvent like CCl4
at room temperature.
Alkyl halides are formed from saturated
as well as unsaturated hydrocarbons by
various reactions. Halogenation of alkanes is
C =C + X2 C-C
not suitable for preparation of alkyl halides
as a mixture of mono and poly halogen X X
compounds is formed. (X = Cl, Br)

213
 When toluene is brominated in presence
Do you know ? of iron, a mixture of ortho and para bromo
When alkenes are heated toluene is obtained.
with Br2 or Cl2 at high temperature,
hydrogen atom of allylic carbon is CH3 CH3 CH3
substittued with halogen atom giving Fe
Br
+ Br2 dark
+
allyl halide.
CH2 = CH - CH3 + Cl2 Br
(o - Bromotoluene) (p-Bromotoluene)
CH2 = CH - CH2Cl + HCl
+ HBr
10.3.3 Halogen exchange : Alkyl iodides Aromatic electrophilic substitution
are prepared conveniently by treating alkyl with iodine is reversible. In this case use
chlorides or bromides with sodium iodide in of HNO3/HIO4 removes HI by oxidation to
methanol or acetone solution. The sodium I2, equilibrium is shifted to right and iodo
bromide or sodium chloride precipitates from product is formed. F2 being highly reactive,
the solution and can be separated by filtration. fluoro compounds are not prepared by this
acetone method.
R - Cl + NaI R - I + NaCl ↓
10.3.5 Sandmeyer's reaction : Aryl halides
The reaction is known as Finkelstein reaction.
are most commonly prepared by replacement
Alkyl fluorides are prepared by heating of nitrogen of diazonium salt. (For details
alkyl chlorides or bromides with metal refer to Chapter 13 section 13.6).
fluorides such as AgF, Hg2F2, AsF3, SbF3 etc.
10.4 Physical properties : Physical properties
R - Cl + AgF R - F + AgCl ↓ of alkyl halides are considerably different
The reaction is known as Swartz reaction. from those of corresponding alkanes. The
boiling points of alkyl halides are determined
10.3.4 Electrophilic substitution :
by polarity of the C-X bond as well as the
size of halogen atoms.
Can you recall ?
10.4.1 Nature of intermolecular forces:
• Identify the product of the Halogens (X = F, Cl, Br and I) are more
following reaction. electronegative than carbon.

+ Cl2
anhyd. Carbon atom that carries halogen
AlCl3
develops a partial positive charge while the
• Name the type of halide produced in halogen carries a partial negative charge.
the above reaction. Thus carbon-halogen bond in alkyl halide is a
• What type of reactions are shown by polar covalent bond. Therefore alkyl halides
benzene ? are moderately polar compounds.

δ⊕ δ
C X
Aryl chlorides and bromides can be
prepared by direct halogenation of benzene Size of the halogen atom increases from
and its derivatives through electrophilic fluorine to iodine. Hence the C-X bond length
substitution. It may be conveniently carried increases. The C-X bond strength decreases
out in dark at ordinary temperature in presence with an increase in size of halogen. This is
of suitable Lewis acid catalyst like Fe, FeCl3 because as the size of p-orbital of halogen
or anhydrous AlCl3. increases the p-orbital becomes more diffused
214
and the extent of overlap with orbital of Haloalkane Boiling point (K)
carbon decreases. Some typical bond lengths,
CH3CH2CH2CH2Br 375
bond enthalpies and dipole moments of C-X
bond are given in Table 10.2. CH3 - CH - CH2 - CH3
364
Br
Table 10.2 : Bond parameters of C-X bond
CH3
Bond Bond Bond Dipole CH3− C − CH3 346
length enthalpy moment Br
(pm) (kJ mol-1) (debye)
CH3 - F 139 452 1.847 10.4.3 Solubility : Though alkyl halides
are moderately polar, they are insoluble in
CH3 - Cl 178 351 1.860
water. It is due to inability of alkyl halides to
CH3 - Br 193 293 1.830 form hydrogen bonds with water. Attraction
CH3 - I 214 234 1.636 between alkyl halide molecules is stronger
than attraction between alkyl halide and
10.4.2 Boiling point : Boiling points of alkyl
water. Alkyl halides are soluble in non-polar
halides are considerably higher than those of
organic solvents.
corresponding alkanes due to higher polarity
and higher molecular mass. Within alkyl Aryl halides are also insoluble in water
halides, for a given alkyl group, the boiling but soluble in organic solvents. If aryl halides
point increases with increasing atomic mass are not modified by presence of any other
of halogen, because magnitude of van der functional group, they show properties similar
Waals force increases with increase in size to corresponding alkyl halides. The isomeric
and mass of halogen. dihalobenzenes have nearly the same boiling
points, but melting points of these isomers
Thus boiling point of alkyl halide
show variation. Melting point of para isomer
decreases in the order RI > RBr > RCl > RF
is quite high compared to that of ortho or meta
For example, : isomer. This is because of its symmetrical
structure which can easily pack closely in
Haloal- CH3F CH3Cl CH3Br CH3I
kane
the crystal lattice. As a result intermolecular
forces of attraction are stronger and therefore
Boiling
194.6 248.8 276.6 315.4 greater energy is required to overcome its
point (K)
lattice energy.
For the given halogen, boiling point rises
with increasing carbon number. Cl
Cl Cl
For example, Cl
Haloalkane Boiling point (K)
Cl
CH3Cl 248.8 Cl
CH3CH2Cl 285.5 b.p./K 453 446 448
CH3CH2CH2Cl 320.0 m.p./K 256 249 323
CH3CH2CH2CH2Cl 351.5
For isomeric alkyl halides, boiling point
decrease with increased branching as surface
area decreases on branching and van der
Waals forces decrease. For example :
215
 Let us, now, jot down the atoms/groups
Problem 10.2 Arrange the following attached to each carbon in 2 - chlorobutane.
compounds in order of increasing boiling 1 2 3 4
points : bromoform, chloromethane, CH3 - CHCl - CH2 - CH3
dibromomethane, bromomethane. 2 3 4
C-1 : - H, -H, -H, -CHCl-CH2-CH3
Solution : The comparative boiling points
of halogen derivatives are mainly related 1 3 4
C-2 : -H, -Cl, -CH3, -CH2-CH3
with van der Waals forces of attraction
4 2 1
which depend upon the molecular size. In C-3 : -H, -H, -CH3, -CHCl-CH3
the present case all the compounds contain
3 2 1
only one carbon. Thus the molecular size C-4 : -H, -H, -H, -CH2-CHCl-CH3
depends upon the size of halogen and
number of halogen atoms present. It can be seen that the four groups bonded
to C-2 are all different from each other.
Thus increasing order of boiling point is, Carbon atom in a molecule which carries
CH3Cl < CH3Br < CH2Br2 < CHBr3 four different groups/atoms is called chiral
carbon atom. Thus, the C-2 in 2-chlorobutane
10.5 Optical isomerism in halogen is a chiral carbon. Chiral atom in a molecule
derivatives : is marked with asterisk (*). For example,
CH3-*CHCl-CH2-CH3.
Can you recall ? When a molecule contains one chiral
• What is the relationship between atom, it acquires a unique property. Such a
two compounds having the same molecule can not superimpose perfectly on its
molecular formula? mirror image. It is called chiral molecule. A
• What is meant by stereoisomerism ? chiral molecule and its mirror image are not
identical (see Fig. 10.1).
Isomers having the same bond connectivities,
that is, structural formula are called
CH3
stereoisomers. Knowledge of optical CH3
isomerism, which is a kind of stereoisomerism *C
will be useful to understand nucleophilic C* Cl H
H Cl C2H5
substitution reactions of alkyl halides (see
C2H5 mirror plane
10.6.3).
10.5.1 Chiral atom and molecular chirality CH3 CH3

Try this... C * *C
H Cl Cl H
• Make a three - dimensional C2H5 C2H5
model of 2 - chlorobutane.
• Make another model which is a mirror Fig. 10.1 : Nonsuperimposable mirror images
image of the first model. A chiral molecule and its mirror image
• Try to superimpose the two models on both have the same structural formula and,
each other. of course, the same molecular formula. The
• Do they superimpose on each other spatial arrangement of the four different
exactly ? groups around the chiral atom, however, is
• Comment on whether the two models different. In other words, a chiral molecule
are identical or not. and its mirror image are stereoisomers of each

216
other. (Refer to Std. XI Chemistry Textbook,
Chapter 14). Do you know ?
Nicol prism is a special type of
The relationship between a chiral prism made from pieces of calcite,
molecule and its mirror image is similar to a crystalline form of CaCO3, arranged
the relationship between left and right hands. in a specific manner. Nicol prism is also
Therefore it is called handedness or chirality. called polarizer.
(Origin : Greek word : Cheir means hand)
10.5.3 Optical activity : When an aqueous
The stereoisomerism in which the isomers
solution of certain organic compounds like
have different spatial arrangements of groups/
sugar, lactic acid is placed in the path of
atoms around a chiral atom is called optical
plane polarized light, the transmitted light
isomerism. The optical isomers differ from
has oscillations in a different plane than
each other in terms of a measurable property
the original. In other words, the incident
called optical activity.
light undergoes rotation of its plane of
To understand optical activity, we must polarization. The plane of polarization rotates
know what is plane polarized light. either to the right (clockwise) or to the left
(anticlockwise). This property of a substance
Remember... by which it rotates plane of polarization
of incident plane polarized light is known
The phenomenon of optical as optical activity. The compounds which
isomerism in organic compounds rotate the plane of plane polarized light are
was observed first and its origin in called optically active compounds and those
molecular chirality was recognized later. which do not rotate it are optically inactive
compounds. Optical activity of a substance
10.5.2 Plane polarized light : An ordinary is expressed numerically in terms of optical
light consists of electromagnetic waves having rotation. The angle through which a substance
oscillations of electric and magnetic field in rotates the plane of plane polarized light on
all possible planes perpendicular to direction passing through it is called optical rotation.
of propagation of light. In accordance with the direction of optical
When ordinary light is passed through rotation an optically active substance is either
Nicol's prism, oscillations only in one plane dextrorotatory or laevorotatory. A compound
emerge out. Such a light having oscillations which rotates the plane of plane polarized
only in one plane perpendicular to direction light towards right is called dextrorotatory
of propagation of light is known as plane and designated by symbol d- or by (+)
polarized light. sign. A compound which rotates plane of
plane polarized light towards left is called
laevorotatory and designated by symbol l-
or by (-) sign.
Isomerism in which isomeric compounds
have different optical activity is known as
optical isomerism. French scientist Louis
Pasteur first recognized that optical activity is
associated with certain type of 3-dimensional
structure of molecules. Pasteur introduced
the term enantiomers for the optical isomers
having equal and opposite optical rotation.
217
 Figure 10.2 indicates a few objects in our Enantiomers have identical physical
day to day life which exhibit superimposable properties (Such as melting point, boiling
and non-superimposable mirror image points, densities, refractive index) except the
relationship. sign of optical rotation. The magnitude of
their optical rotation is equal but the sign
of optical rotation is opposite. They have
identical chemical properties except towards
optically active reagent.
An equimolar mixture of enantiomers
(dextrorotatory and laevorotatory) is called
racemic modification or racemic mixture.
A racemic modification is optically inactive
because optical rotation due to molecules
of one enatiomer is cancelled by equal and
Non superimposable Superimposable opposite optical rotation due to molecules of
the other enantiomer. A racemic modification
Fig. 10.2 : Superimposable and is designated as (dl) or by (±) sign.
nonsuperimposable mirror image 10.5.5 Representation of configuration of
molecules :

Remember... Can you recall ?

• Optical activity is an • Identify the type of following
experimentally observable 3-D representation (I) and
property of compounds. Chirality is (II) of a molecule and state
a description of molecular structure. significance of the lines drawn.
Optical activity is the consequence of W W
chirality.
X C X Y
• Molecules which contain one chiral
Z
atom are chiral, that is, they are Y Z
nonsuperimposable on their mirror
(I) (II)
image.
a. Fischer projection formula (cross
• The two non-superimposable mirror formula) : Two representations are used to
image structures are called pair of represent configuration of chiral carbon and
enantiomers. the 3-dimensional structure of optical isomers
• Enantiomers have equal and opposite on plane paper. These are (a) wedge formula
optical rotation. Thus, enantiomers are and (b) Fischer projection formula (also called
a kind of optical isomers. cross formula) (Std. XI Chemistry Textbook
Chapter 14 section 14.2.3).
10.5.4 Enantiomers : The optical isomers Cl Chiral carbon Cl Bonds below
the plane
which are non-superimposable mirror image
I Br I C Br
of each other are called enantiomers or
enantiomorphs or optical antipodes. For Bonds above
H the plane H
example, 2 - chlorobutane exists as a pair of Fischer projection Convention of vertical
enantiomers (Fig. 10.1). and horizontal lines
Fig. 10.3 Fischer projection formula
218
b. Wedge formula : When a tetrahedral Can you recall ?
carbon is imagined to be present in the plane
• What is meant by substitution
of paper all the four bonds at this carbon
reaction ?
cannot lie in the same plane. The bonds in
the plane of paper are represented by normal • Can you identify substitution reaction
lines, the bonds projecting above the plane from the following ?
of paper are represented by solid wedges (i) CH3 - CH2 - OH + HCl
ZnCl2

(or simply by bold lines) while bonds going

CH3 - CH2 - Cl + H2O
below the plane of paper are represented by
broken wedges (or simply by broken lines). (ii) CH2 = CH2 + HI
CH3 - CH2 - I
Br
• Is the carbon carrying halogen in alkyl
below the plane In the plane
C halide, an electrophilic or a nucleophilic
I Cl centre ?
H
Above the plane
hybridization of that carbon the reaction is
Try this... called substitution reaction. The C-X bond
in alkyl halides is a polar covalent bond
1. Draw structures of enantiomers
and the carbon in C-X bond is positively
of lactic acid (CH3-CH-COOH)
polarized. In other words, the C-X carbon is
OH an electrophilic centre. It has, therefore, a
using Fischer projection formulae.
tendency to react with a nucleophile. (Refer to
2. Draw structures of enantiomers of Std. XI Chemistry Textbook Chapter 14.) Alkyl
2-bromobutane using wedge formula. halides react with a variety of nucleophiles
10.6 Chemical properties : to give nucleophilic substitution reactions
(SN). The reaction is represented in general
10.6.1 Laboratory test of haloalkanes : form as shown below.
Haloalkanes are of neutral type in aqueous
δ⊕ δ
medium. On warming with aqueous sodium Nu + − C − X − C − Nu + X
or potassium hydroxide the covalently bonded
halogen in haloalkane is converted to halide When a substrate reacts fast it is said to
ion. be reactive. The reactivity of alkyl halides
∆
in SN reaction depends upon two factors,
R - X + OH R - OH + X
namely, the substitution state (10, 20 or 30)
When this reaction mixture is acidified of the carbon and the nature of the halogen.
by adding dilute nitric acid and silver nitrate The order of reactivity influenced by these
solution is added a precipitate of silver halide two factors is as shown below.
is formed which confirms presence of halogen tertiary alkyl halide (30) > secondary alkyl
in the original organic compound. halide (20) >primary alkyl halide (10) and
Ag⊕ (aq) + X (aq) AgX↓ (s) R - I > R - Br > R - Cl
Examples of some important nucleophilic
10.6.2 Nucleophilic substitution reactions of substitution reactions of alkyl halides are
haloalkanes : shown in Table 10.3.
When a group bonded to a carbon in
a substrate is replaced by another group to
get a product with no change in state of

219
 10.3 Nucleophilic substitution reactions of alkyl halides

Sr. No. Alkyl halide Reagent Substitution product

1. R-X + NaOH(aq) ∆ R - OH + NaX
(or KOH) (alcohol) (or KX)
⊕
NaOR' ∆ R - O - R' + NaX
2. R-X +
(sodium alkoxide) (ether)
O ⊕
O
3. R-X + R' - C - OAg ∆
R' - C - OR + AgX ↓
(silver carboxylate) (ester)
∆
NH3(alc.) R - NH2 + HX
4. R-X + pressure
(excess) (primary amine)
KCN (alc.) ∆ R - CN + RX
5. R-X + (nitrile)(alkyl cyanide)
AgCN (alc.) ∆ R-N C + AgX ↓
6. R-X + (isocyanide)
⊕
KO - N = O R-O-N=O + KX
7. R-X +
(potassium nitrite) (alkyl nitrite)

Ag - O - N = O ⊕ O
8. R-X + R N + AgX ↓
(silver nitrite) O
(nitroalkane)

Can you tell ?

Do you know ?
Alkyl halides when treated with
Cyanide ion is capable of alcoholic solution of silver nitrite give
attacking through more than one nitroalkanes whereas with sodium nitrite
site (atom). they give alkyl nitrites Explain.
C≡N C=N 10.6.3 Mechanism of SN reaction :
Such nucleophiles are called ambident Can you recall ?
nucleophiles. KCN is predominantly ionic • What is meant by order and
(K⊕C ≡ N) and provides cyanide ions. Both molecularity of a reaction ?
carbon and nitrogen are capable of donating
electron pair. C-C Bond being stronger than • What is meant by mechanism of
C-N bond, attack occurs through carbon atom chemical reaction ?
of cyanide group forming alkyl cyanides as It can be seen from the Table 10.3 that in
major product. However AgCN (Ag-C ≡ N) a nucleophilic substitution reactions of alkyl
is mainly covalent compound and nitrogen halides the halogen atom gets detached from
is free to donate pair of electron. Hence the carbon and a new bond is formed between
attack occurs through nitrogen resulting in that electrophilic carbon and nucleophile.
formation of isocyanide. The covalently bonded halogen is converted
Another ambident nucleophile is nitrite into halide ion (X ). It means that the two
ion, which can attack through ‘O’ or ‘N’. electrons constituting the original covalent
bond are carried away by the halogen along
O-N=O with it. The halogen atom of alkyl halide
is, therefore, called ‘leaving group’ in the
220
 [ [
context of this reaction. Leaving group is
the group which leaves the carbon by taking H 1 H 1
2 2
away the bond pair of electrons. The substrate HO C Br HO C Br
undergoes two changes during a SN reaction. H H H
The original C-X bond undergoes heterolysis H
Transition state
and a new bond is formed between the carbon (T.S.)
and the nucleophile using two electrons of the
H
nucleophile. These changes may occur in one
or more steps. The description regarding the HO C + Br
sequence and the way in which these two H
changes take place in SN reaction is called H
mechanism of SN reaction. The mechanism is Fig. 10.4 : SN2 mechanism
deduced from the results of study of kinetics Salient features of SN2 mechanism :
of SN reactions. Two mechanisms are observed i. Single step mechanism with simultaneous
in various SN reactions. These are denoted as bond breaking and bond forming.
SN1 and SN2 mechanisms.
ii. Backside attack of nucleophile : The
a. SN2 Mechanism : The reaction between nucleophile attacks the carbon undergoing
methyl bromide and hydroxide ion to give substitution from the side opposite to that
methanol follows a second order kinetics, of the leaving group. This is to avoid steric
that is, the rate of this reaction depends on repulsion (repulsion due to bulkyness of
concentration of two reacting species, namely, the groups) and electrostatic repulsion
methyl bromide and hydroxide. Hence it is between the incoming nucleophile and
called subtitution nucleophilic bimolecular, the leaving group.
SN2.
iii. In the transition state (T.S.) the nucleophile
CH3Br + OH CH3OH + Br and leaving groups are bonded to the
rate = k [CH3Br] [OH ] carbon with partial bonds and carry
partial negative charge. (Thus, the total
Rate of a chemical reaction is influenced by negative charge is diffused.)
the chemical species taking part in the slowest
step of its mechanism. In the above reaction iv. The T.S. contains pentacoordinate
only two reactants are present and both are carbon having three σ (sigma) bonds in
found to influence the rate of the reaction. one plane making bond angles of 1200
This means that the reaction is a single step with each other and two partial covalent
reaction which can also be called the slow bonds along a line perpendicular to this
step. This further implies that the two changes, plane.
namely, bond breaking and bond forming at v. When SN2 reaction is brought about at
the carbon take place simultaneously. This chiral carbon (in an optically active
SN2 mechanism is represented as shown in substrate), the product is found to have
Fig. 10.4. opposite configuration compared to
that of the substrate. In other words,
SN2 reaction is found to proceed with
inversion of configuration. This is like
flipping of an umbrella (See Fig. 10.4).
It is known as Walden inversion. The
inversion in configuration is the result of
backside attack of the nucleophile.
221
b. SN1 Mechanism : The reaction between iv. When SN1 reaction is carried out at chiral
tert-butyl bromide and hydroxide ion to give carbon in an optically active substrate,
tert-butyl alcohol follows a first-order kinetics, the product formed is nearly racemic.
that is the rate of this reaction depends on This indicates that SN1 reaction proceeds
concentration of only one species, which is mainly with racemization. This means
the substrate molecule, tert-butyl bromide. both the enantiomers of product are formed
Hence it is called substitution nucelophilic in almost equal amount. Racemization in
unimolecular, SN1. SN1 reaction is the result of formation
of planar carbocation intermediate (Fig.
CH3 CH3
10.5). Nucleophile can attack planar
CH3− C − Br + OH CH3− C − OH + Br carbocation from either side which results
CH3 CH3 in formation of both the enantiomers of
rate = k [(CH3)3CBr] the product.
It can be seen in this reaction that
Use your brain power
concentration of only substrate appears
in the rate equation; concentration of the • Draw the Fischer projection
nucleophile does not influence the reaction formulae of two products
rate. In other words, tert-butyl bromide reacts obtained when compound (A) reacts
with hydroxide by a two step mechanism. with OH by SN1 mechanism.
In the slow step C-X bond in the substrate C2H5
undergoes heterolysis and in the subsequent
H3C− C − Br (A)
fast step the nucleophile uses its electron
pair to form a new bond with the carbon n-C3H7
undergoing change. This SN1 mechanism is • Draw the Fischer projection formula of
represented as shown in Fig. 10.5. the product formed when compound (B)
Step I reacts with OH by SN2 mechanism.
CH3
(CH3)3C - Br
slow ⊕ CH3
C + Br
H− C − Cl (B)
H 3C CH3
C2H5
(carbocation intermediate)
10.6.4 Factors influencing SN1 and SN2
Step II
mechanism :
CH3
a. Nature of substrate : SN2 : The T.S. of
C⊕ + OH (CH3)3C - OH SN2 mechanism is pentacoordinate and thus
H3C CH3 crowded (See Fig. 10.4). As a result SN2
mechanism is favoured in primary halides
Fig. 10.5 : SN1 mechanism
and least favoured in tertiary halides.
Salient features of SN1 mechanism :
SN1 : A planar carbocation intermediate
i. Two step mechanism.
is formed in SN1 reaction. It has no steric
ii. Heterolyis of C-X bond in the slow crowding. Bulky alkyl groups can be easily
and reversible first step to form planar accommodated in planar carbocation See
carbocation intermediate. (Fig. 10.5). As a result SN1 mechanism is
iii. Attack of the nucleophile on the most favoured in tertiary halides and least
carbocation intermediate in the fast favoured in primary halides. (Formation of
second step to form the product. planar carbocation intermediate results in a
222
 H H H
H H H H H H
1
H 1 1
C 1 1
C 1 1
C 1
2 2 2 2 2 2 2 2
(a) Nu C X Nu C X Nu C X Nu C X
H H H H H C H H C C H
H H H H H H

crowding and destabilization increases

H
H H αH
H αH H
H H H C
(b) C C
C⊕ C⊕
C⊕ C⊕
H H α
H Cα C H
H H H Cα H
H H H H
H H

steric relief, stabilization by +I and hyperconjugation of

α - hydrogens increases
Fig. 10.6 : Influence of substrate in SN1 and SN2 (a) Transition states (T.S.) in SN2
(b) Carbocation intermediates in SN1

relief from steric crowding present in the

Problem 10.4 : Primary allylic and
tertiary halide substrate).
primary benzylic halides show higher
Secondly the carbocation intermediate is reactivity by SN1 mechanism than
stabilized by +I effect of alkyl substituents other primary alkyl halides. Explain.
and also by hyperconjugation effect of alkyl Solution : SN1 reaction involves
substituents containing α-hydrogens. As a formation of carbocation
result, SN1 mechanism is most favoured intermediate. The allylic and benzylic
in tertiary halides and least favoured in carbocation intermediate formed are
primary halides. This can be represented
resonance stabilized, and hence SN1
diagramatically as shown below.
mechanism is favoured.
SN1 rate increases
⊕ ⊕
CH2 = CH - CH2 CH2 - CH = CH2
CH3 - X 10 20 30
Resonance stabilization of allylic carbocation
SN2 rate increases

⊕
Tertiary halides undergo nucleophilic CH2 CH2 CH2
substitution by SN1 mechanism while primary ⊕
⊕
halides follow SN2 mechanism. Secondary
⊕
halides react by either of the mechanism or ⊕
CH2 CH2
by mixed mechanism depending upon the
exact conditions.
Resonance stabilization of benzylic carbocation

223
b. Nucleophilicity of the reagent : carbocation is relatively poor and solvation
of anion is particularly important. Anions are
Can you recall ? solvated by hydrogen bonding solvents, that
• Give some examples of is, protic solvents. Thus SN1 reaction proceeds
nucleophiles that are electrically more rapidly in polar protic solvents than in
neutral. aprotic solvents.

• Give some examples of anionic Polar protic solvents usually decrease the
nucleophiles. rate of SN2 reaction. In the rate determining
step of SN2 mechanism substrate as well
• What is the difference between a base as nucleophile is involved. A polar solvent
and a nucleophile ? stabilizes nucleophile (one of the reactant)
by solvation. Thus solvent deactivates the
A nucleophile is a species that uses its nucleophile by stabilizing it. Hence aprotic
electron pair to form a bond with carbon. solvents or solvents of low polarity will
Nucleophilic character of any species is favour SN2 mechanism.
expressed in its electron releasing tendency,
which can be corelated to its strength as
Problem 10.5 : Which of the following
Lewis base.
two compounds would react faster by SN2
A more powerful nucleophile attacks the mechanism and Why ?
substrate faster and favours SN2 mechanism.
CH3-CH2-CH2-CH2Cl CH3-CH-CH2-CH3
The rate of SN1 mechanism is independent of
the nature of nucleophile. Nucleophile does Cl
1-Chlorobutane 2-Chlorobutane
not react in slow step of SN1. It waits till
the carbocation intermediate is formed, and Solution : In SN2 mechanism, a
reacts fast with it. pentacoordinate T.S. is involved. The order
of reactivity of alkyl halides towards SN2
Do you know ? mechanism is,
1. A negatively charged Primary > Secondary > Tertiary, (due to
nucleophile is more powerful increasing crowding in T.S. from primary
than its conjugate acid. For example to tertiary halides. 1-Chlorobutane being
R-O is better nucleophile than R-OH. primary halide will react faster by SN2
mechanism, than the secondary halide
2. When donor atoms are from same 2-chlorobutane.
period of periodic table, nucleophilicity
decreases from left to right in a period. Can you recall ?
For example H2O is less powerful
nucleophile than NH3. • How are alkenes prepared
3. When donor atoms are from same group from alkyl halides ?
of the periodic table, nucleophilicity • Which is stronger base from the
increases down the group. For example, following ?
I is better nucleophile than Cl . i. aq. KOH ii. alc. KOH
c. Solvent polarity : SN1 mechanism proceeds
via formation of carbocation intermediate.
A good ionizing solvent, polar solvent,
stabilizes the ions by solvation. Solvation of

224
10.6.5 Elimination reaction : The different products of elimination do
Dehydrohalogenation not form in equal proportion. After studying
When alkyl halide having at least one a number of elimination reactions, Russian
β-hydrogen is boiled with alcoholic solution of chemist Saytzeff formulated an empirical rule
potassium hydroxide, it undergoes elimination given below.
of hydrogen atom from β-carbon and halogen In dehydrohalogenation reaction, the
atom from α - carbon resulting in the formation preferred product is that alkene which has
of an alkene. greater number of alkyl groups attached to
doubly bonded carbon atoms.
Remember...
Therefore, in the above reaction but-2-ene
The carbon bearing halogen is
is the preferred product, and is formed as the
commonly called α-carbon (alpha
major product. It turned out that more highly
carbon) and any carbon attached to α-carbon
substituted alkenes are also more stable alkenes.
is β-carbon (beta carbon). Hydrogens
Hence Saytzeff elimination is preferred
attached to β-carbon are β-hydrogens.
formation of more highly stabilized alkene
during an elimination reaction. The stability
This reaction is called β-elimination order of alkyl substituted alkenes is :
(or 1,2 - elimination) reaction as it involves
elimination of halogen and a β - hydrogen R2C = CR2 > R2C = CHR > R2C = CH2,
atom. RCH = CHR > RCH = CH2
H
β α alc. KOH
B+ C C ∆ C = C + B⊕H +X Do you know ?
X Elimination versus substitution:
(base) (alkyl halide) (alkene)
Alkyl halides undergo sunstitution as
As hydrogen and halogen is removed well as elimination reaction. Both reactions
in this reaction it is also known as are brought about by basic reagent, hence
dehydrohalogenation reaction. there is always a competition between these
two reactions. The reaction which actually
If there are two or more non-equivalent
predominates depends upon following
β-hydrogen atoms in a halide, then this
factors.
reaction gives a mixture of products. Thus,
2-bromobutane on heating with alcoholic a. Nature of alkyl halides : Tertiary alkyl
KOH gives mixture of but-1-ene and but-2- halides prefer to undergo elimination
ene. reaction where as primary alkyl halides
prefer to undergo substitution reaction.
β1 α β2
CH3 − CH2 − CH − CH3 b. Strength and size of nucleophile :
Br Bulkier electron rich species prefers to act
(2-bromobutane) as base by abstracting proton, thus favours
alc. KOH ∆
elimination. Substitution is favoured in the
case of comparatively weaker bases, which
loss of β - hydrogen loss of β1 -hydrogen
2
prefer to act as nucleophile
c. Reaction conditions : Less polar solvent,
HC3 − CH2 − CH = CH2 high temperature fovours elimination where
(But-1-ene) as low tempertaure, polar solvent favours
CH3− CH = CH - CH3 substitution reaction.
(But-2-ene)
225
10.6 Reaction with active metals b. Wurtz reaction : Alkyl halides react with
Active metals like sodium, magnesium metallic sodium in dry ether as solvent, and
cadmium readily combine with alkyl chlorides, form higher alkanes containing double the
bromides and iodides to form compounds number of carbon atoms present in alkyl halide.
containing carbon-metal bonds. These are This reaction is called Wurtz reaction. (Refer
known as organometallic compounds. to Std. XI Chemistry Textbook sec. 1.5.3)
dry
a. Reaction with magnesium : When alkyl 2 R-X + 2 Na ether R - R + 2 NaX
halide is treated with magnesium in dry ether 2C2H5 Br + 2Na
dry
CH3-CH2-CH2-CH3
ether
as solvent, it gives alkyl magnesium halide. It
(Ethyl bromide) (Butane)
is known as Grignard reagent.
+ 2 NaBr
dry ether When a mixture of two different alkyl halides is
R-X + Mg R - Mg - X
alkyl magnesium halide used, all the three possible alkanes are formed.
(Grignard reagent)
For example : CH3-CH3
Grignard reagents are very reactive compounds. (ethane)
They react with water or compounds containing Na
CH3Br + C2H5Br CH3-CH2-CH3
hydrogen attached to electronegative element. dryether
(Methyl (Ethyl (propane)
X bromide) bromide)
CH3-CH2-CH3-CH3
R - Mg -X + CH3OH R - H + Mg
(butane)
(Hydrocarbon)
OCH3 10.6.1 Reaction of haloarenes :
X
R - Mg -X + NH3 R - H + Mg a. Reactions of haloarene with metals
(Hydrocarbon) NH2 The reaction of aryl halide with alkyl
halide and sodium metal in dry ether to give
substituted aromatic compounds is known as
Do you know ? Wurtz- Fittig reaction. This reaction is an
extension of Wurtz reaction and was carried
Carbon-magnesium bond in out by Fittig. This reaction allows alkylation
Grignard reagent is a polar covalant of aryl halides.
bond. The carbon pulls electrons from the CH3
Br
electropositive magnesium. Hence carbon dry
in Grignard reagent has negative polarity + CH3-Br + 2Na ether + 2NaBr
and acts as a nucleophite (Bromobenzene) (Toluene)
δ δ⊕
R- Mg X
In case only aryl halide takes part in the
Victor Grignard received Nobel Prize reaction, the product is biphenyl and the
in 1912 for synthesis and study of organo- reaction is known as Fittig reaction.
magnesium compounds. Grignard reagent
Cl
is a very versatile reagent used by organic
chemist. Vinyl and aryl halides also form dry
+ 2Na ether + 2NaCl
Grignard reagent.
(Chlorobenzene) (Biphenyl)

226
b. Nucleophilic substitution SN of haloarenes: Thus nuclophilic substitution reaction
involving cleavage of C-X bond in haloarene
Can you recall ? proceeds with difficulty. However, the presence
• What is resonance? of certain groups at certain positions of the
• Draw resonance structures of ring, markedly activate the halogen of aryl
bromobenzene. halides towards substitutuion. For example,
presence of electron withdrawing group at
• Identify the type of hybridization of
ortho and/or para postion greatly increases the
carbon to which halogen is attached in
reactivity of haloarenes towards subsitution of
haloarene.
halogen atom. Greater the number of electron
Aryl halides show low reactivity withdrawing groups at o/p position, greater
towards nucleophilic substitution reactions. is the reactivity. Electron withdrawing group
The low reactivity of aryl halides is due to : at meta position has practically no effect on
i. Resonance effect and reactivity.
ii. sp2 hybrid state of C . i. Cl OH
i. One of the lone pairs of electrons (i)NaOH 433 K
on halogen atom is in conjugation with (ii)H3O⊕

π -electrons of the ring. For example the NO2 NO2

following different resonance structures can (p-nitrochlorobenzene) (p-nitrophenol)
be written for chlorobenzene.
+ Cl : +Cl : ii. Cl OH
:
:
:

: Cl :
NO2 NO2
(i)aq.Na2CO3 403 K
(ii)H3O⊕

NO2 NO2
I II III
(2,4-dinitrochlorobenzene) (2,4 - dinitrophenol)
+ Cl :
:
:

: Cl :
iii. Cl OH
NO2 NO2 NO2 NO2
warm
H2O
IV V NO2 NO2
Resonance structures II, III and IV show (2,4,6-trinitrochlorobenzene) (2,4,6 - trinitrophenol)
double bond character to carbon-chlorine bond.
Thus carbon-chlorine bond in chlorobenzene
is stronger and shorter than chloroalkane Can you tell ?
molecule, C-Cl bond length in chlorobenzene Conversion of chlorobenzene
is 169 pm as compared to C-Cl bond length to phenol by aqueous sodium
in alkyl chloride 178 pm. Hence it is difficult hydroxide requires high temperture of
to break. Phenyl cation produced due to self- about 623K and high pressure. Explain.
ionization of haloarene will not be stabilised OH
Cl
by resonance, which rules out possibility of SN1
(i) 623K, OH 300 atm
mechanism. Back side attack of nucleophile is
(ii) H3O⊕
blocked by the aromatic ring, which rules out
SN2 mechanism. Chlorobenzene Phenol

227
 Do you know ? • Identify the product A of following
reaction.
Occurrence of nucleophilic
substitution in p-nitrochlorobenzene + HNO3 conc. H2SO4
A
can be explained on the basis of resonance
stabilization of the intermediate.
Aryl halides undergo electrophilic
Cl Cl OH substitution reaction slowly as compared to
benzene.
+ OH slow
step In resonance structures of chlorobenzene
N N (see section 10.6.5) elelctron density is
O ⊕ O O ⊕ O relatively more at ortho and para position.
(I) Therefore incoming electrophilic group is
more likely to attack at these positions. But
Cl OH Cl OH
due to steric hinderance at ortho position, para
product usually predominates. In haloarenes,
halogen atom has strong electron withdrawing
N N inductive effect (-I). This deactivates the ring
O ⊕ O O ⊕ O and electrophilic substitution reaction occurs
(II) (III) slowly.
Cl OH OH
Remember...
fast
step + Cl The -I effect of Cl is more
powerful than its +R effect.
N N Therefore Cl is o-/p- directing but ring
O ⊕ O O ⊕ O deactivating group.
(IV)
i. Halogenation : It is carried out by reacting
The resonance structure (III) shows haloarene with halogen in presence of ferric
that the electron withdrawing nitro group salt as Lewis acid catalyst.
(-NO2) in the p-position extends the
conjugation. As a result, the intermediate Cl
carbanion is better stabilized which favours
nucleophilic substitution reaction. + Cl2
c. Electrophilic substitution (SE) in (Chlorobenzene)
arylhalides
anhydrous Cl
Can you recall ? FeCl3
2

• What is an electrophile?
Cl Cl
• Give some examples of Cl
electrophiles + + HCl
• What type of reactions are observed in
benzene? Cl
(1,4 - Dichlorobenzene) (1,2 - Dichlorobenzene)
(major) (minor)
228
ii. Nitration : It is carried out by heating Cl
haloarene with conc. HNO3 in presence of O
conc. H2SO4. + CH3-C -Cl
Cl (Chlorobenzene)

+ HNO3 anhyd. AlCl3 Cl

conc. Cl O
(Chlorobenzene) C CH
3
+
conc. H2SO4 ∆
O C CH3
(2-Chloroacetophenone) (4 -Chloroacetophenone)

Cl Cl 10.7 Uses and Environmental effects of some

NO2
polyhalogen compounds
+
10.7.1 Dichloromethane/ methylene chloride
NO2 (CH2Cl2) : It is a colourless volatile liquid
(1-Chloro-4-nitrobenzene) (1-Chloro-2-nitrobenzene) with moderately sweet aroma. It is used as a
solvent, and used as a propellant in aerosols.
iii. Sulfonation : It is carried out by heating
Over exposure to dichloromethane causes
haloarene with fuming H2SO4.
dizziness, fatigue, nausea, headaches,
Cl numbness, weakness. It is highly dangerous
if it comes in direct contact with eyes as it
+ H2SO4 damages cornea.
(chlorobenzene) (fuming) 10.7.2 Chloroform / trichloromethane
∆
(CHCl3) : It is a colourless liquid with
peculiar sweet smell. It is used to prepare
Cl Cl chlorofluromethane, a refrigerant R-22. It
SO3H is used as a solvent for extraction of natural
+ products like gums, fats, resins. It is used as a
source of dichlorocarbene. Chloroform causes
SO3H depression of central nervous system. Inhaling
(1 - Chlorobenzene (4 - Chlorobenzene sulfonic chloroform for a short time causes fatigue,
sulfonic acid) acid) dizziness and headache. Long exposure to
chloroform may affect liver. Chloroform when
iv. Friedel Craft’s reaction : It is carried out
exposed to air and light forms a poisonous
by treating haloarene with alkyl chloride or
compound phosgene so it is stored in dark
acyl chloride in presence of anhydrous AlCl3
as a catalyst. coloured air tight bottles.
10.7.3 Carbon tetrachloride /
Cl
Cl Cl tetrachloromethane (CCl4) :
CH3
anhyd. + It is a colourless liquid with sweet smell. It is
+ CH3-Cl AlCl3 very useful solvent for oils, fats, resins. It serves
CH3 as a source of chlorine. It is used as a cleaning
(Chlorobenzene) (2-Chlorotoluene) (4-Chloro- agent. It is highly toxic to liver. Exposure to
toluene)
high concentration of CCl4 can affect central

229
nervous system and it is suspected to be 10.7.6 Dichlorodiphenyltrichloroethane
carcinogenic. Prolonged exposure may cause (DDT) : It is colourless, tasteless and odorless
death. It is a green house gas. crystalline compound having insecticidal
10.7.4 Idoform or triiodomethane (CHI3): property.

It is a yellow crystalline substance with It kills insects such as houseflies,

disagreeable smell. It is used in medicine as mosquitoes and body lice. It was used for
a healing agent and antiseptic in dressing of controlling maleria and typhus.
wounds, however its use is limited. Exposure to high doses of DDT may cause
It causes irritation to skin and eyes. It may vomiting, tremors or shakiness. Laboratory
cause respiratory irritation or breathing animal studies showed adverse effect of DDT
difficulty, dizziness, nausea, depression of on liver and reproduction. DDT is a pressistent
organic pollutant, readily absorbed in soils
central nervous system, visual disturbance.
and tends to accumulate in the ecosystem.
10.7.5 Freons : These are organic compounds When dissolved in oil or other liquid, it is
of chlorine and fluorine, chlorofluorocarbons, readily absorbed by the skin. It is resistant to
CFC's are commonly used as refrigerants. metabolism. It accumulates in fatty tissues.
The most common representative is There is a ban on use of DDT due to all these
dichlorodifluromethane (Freon-12) others adverse effects .
include chlorodifluromethane (R-22), Cl
Cl
Cl
trichlorofluromethane (R-11) and so on.
They are used as refrigerants in fridge and
airconditioning, propellants in aerosol and
solvents. They are used as blowing agents in Cl Cl
making foams and packing materials.
Do you know ?
Chloroflurocarbons are responsible for
ozone depletion in stratosphere. Regular DDT, the first chlorinated
organic insecticides, was originally
large inhalation of freons results in breathing
prepared in 1873, but it was not until 1939
problems, organ damage, loss of consciousness.
that Paul Muller of Geigy Pharmaceuticals
in Switzerland discovered the effectiveness
Do you know ?
of DDT as an insecticide. Paul Muller
How do CFC is destroy the ozone was awarded the Nobel Prize in Medicine
layer in the atmosphere ? and Physiology in 1948 for this discovery.
When ultraviolet radiation (UV) The use of DDT increased enormously
strikes CFC (CFCl3) molecules in the on a worldwide basis after World War
upper atmosphere, the carbon-chlorine II, primarily because of its effectiveness
bond breaks and produces highly reactive against the mosquito that spreads malaria
chlorine atom (Cl). and lice that carry typhus. Many species
CFCl3 CFCl2 + Cl of insects developed resistance to DDT,
This reactive chlorine atom and it was also discovered to have a
decomposes ozone (O3) molecule into high toxicity towards fish. DDT is not
oxygen molecule (O2). metabolised very rapidly by animals;
O3 + Cl O2 + ClO instead, it is deposited and stored in the
ClO + O O2 + Cl fatty tissues. The use of DDT was banned
One atom of chlorine can destroy upto in the United States in 1973, although it is
100,000 ozone molecules. still in use in some other parts of the world.

230
 Exercises

1. Choose the most correct option.

i. The correct order of increasing iv. The best method for preparation of
reactivity of C-X bond towards alkyl fluorides is
nucleophile in the following a. Finkelstein reaction
compounds is
b. Swartz reaction
X X
c. Free radical fluorination
(CH3)3C-X (CH3)2CH-X d. Sandmeyer's reaction
v. Identify the chiral molecule from the
NO2 following.
(I) (II) (III) (IV)
a. 1-Bromobutane

a. I < II < III < IV b. 1,1- Dibromobutane

b. II < I < III < IV c. 2,3- Dibromobutane

c. III < IV < II < I d. 2-Bromobutane

d. IV < III < I < II vi. An alkyl chloride on Wurtz reaction

gives 2,2,5,5-tetramethylhexane.
HI
ii. CH3-CH=CH2 peroxide
The same alkyl chloride on reduction
with zinc-copper couple in alchol
The major product of the above give hydrocarbon with molecular
reaction is, formula C5H12. What is the structure
a. I-CH2-CH=CH2 b. CH3-CH2-CH2I of alkyl chloride
d. CH3-CH-CH2 CH3 CH3
c. CH3-CH-CH3
I I OH a. CH3-C-CH2Cl b. CH3-C-CH2CH3

iii. Which of the following is likely to CH3 Cl

undergo racemization during alkaline c. CH3-CH2-CH-Cl d. CH3-CH-CH-CHCl
hydrolysis ?
CH3 CH3 CH3
CH2Cl
CH3-CH-C2H5 vii. Butanenitrile may be prepared by
Cl heating
(I) (II) a. propanol with KCN
Cl b. butanol with KCN
CH3
CH3-CH c. n-butyl chloride with KCN
(III) CH2Cl d. n-propyl chloride with KCN
(IV)
a. Only I b. Only II
c. II and IV d. Only IV

231
 viii. Choose the compound from the c. CH3-CH-CH=CH2 + HBr peroxide

following that will react fastest by SN1 CH3

mechanism.
OH
a. 1-iodobutane d. + SOCl2
b. 1-iodopropane
CH3
c. 2-iodo-2 methylbutane
dark
d. 2-iodo-3-methylbutane e. + Cl2 Fe

ix. dry H2O

Cl + Mg ether A B iii. Identify chiral molecule/s from the
The product 'B' in the above reaction following.
sequence is, a. CH3-CH-CH2-CH3
a. OH
Mg b. Mg-Cl
b. CH3-CH2-CH-CH2-CH3
c. Cl Mg d. Br
x. Which of the following is used as c. CH3-CH2-CH2-CH2Br
source of dichlorocarbene
d. CH3-CH-CH3-CH3
a. tetrachloromethane
CH3
b. chloroform
iv. Which one compound from the
c. iodoform following pairs would undergo SN2
d. DDT faster from the?
2. Do as directed. a. CH2Cl and Cl
i. Write IUPAC name of the following
compounds b. CH3CH2 CH2I and CH3CH2CH2Cl

a. CH3-CH=C-CH-Br v. Complete the following reactions

H3C CH3 giving major product.
a. CH3-CH=CH2 HBr
A alc. KOH B
b. CH3-CH-CH-CH2-CH3 peroxide

Cl CH3
b. CH3-CH=CH2 Red P/Br2
A Ag2O/H2O
B
Cl Cl OH
c. d.
CH3
CH3 c. CH3-C-CH2-Cl Na/dry ether
A
C2H5 Cl
CH3
ii. Write structure and IUPAC name
of the major product in each of the Cl
following reaction. d. Mg
dry ether A
a. CH3-CH-CH2Cl + NaI Acetone

CH3
b. CH3-CH2Br + SbF3

232
 vi. Name the reagent used to bring about iv. But-1-ene to n-butyl iodide
the following conversions. v. 2-Chloropropane to propan-1-ol
a. Bromoethane to ethoxyethane vi. tert-Butyl bromide to isobutyl bromide
b.1-Chloropropane to 1 nitropropane vii. Aniline to chlorobenzene
c. Ethyl bromide to ethyl viii. Propene to 1-nitropropane
isocyanide 7. Answer the following
d. Chlorobenzene to biphenyl i. HCl is added to a hydrocarbon 'A'
vii. Arrange the following in the increase (C4H8) to give a compound 'B' which
order of boiling points on hydrolysis with aqueous alkali
forms tertiary alcohol 'C' (C4H10O).
a. 1-Bromopropane Identify 'A' , 'B' and 'C'.
b. 2- Bromopropane ii. Complete the following reaction
c. 1- Bromobutane sequences by writing the structural
formulae of the organic compounds
d. 1-Bromo-2-methylpropane
'A', 'B' and 'C' .
viii. Match the pairs. alc.KOH
a. 2-Bromobutane A Br2 B NaNH C2

Column I Column II ∆
b. Isopropyl alcohol PBr3 A NH excess B
a. CH3CH-CH3 i. vinyl halide 3

X iii. Observe the following and answer the

b. CH2=CH-CH2X ii. alkyl halide questions given below.
⊕
c. CH2=CH-X iii. allyl halide CH2=CH-X CH2-CH=X
iv. benzyl halide
a. Name the type of halogen
v. aryl halide derivative
3. Give reasons b. Comment on the bond length of
i. Haloarenes are less reactive than halo C-X bond in it
alkanes. c. Can react by SN1 mechanism?
ii. Alkyl halides though polar are Justify your answer.
immiscible with water.
iii. Reactions involving Grignard reagent Activity :
must be carried out under anhydrous
condition. 1. Collect detailed information
about Freons and their uses.
iv. Alkyl halides are generally not
prepared by free radical halogenation 2. Collect information about DDT as a
of alkanes. persistent pesticide.
4. Distinguish between - SN1 and SN2 Reference books
mechanism of substitution reaction ?
i. Organic chemistry by Morrison, Boyd,
5. Explain - Optical isomerism in Bhattacharjee, 7th edition, Pearson
2-chlorobutane.
ii. Organic chemistry by Finar, Vol 1, 6th
6. Convert the following.
edition, Pearson
i. Propene to propan-1-ol
ii. Benzyl alcohol to benzyl cyanide
iii. Ethanol to propane nitrile
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