Unit

Objective
1
Haloalkanes and

s
After s t u d y i n g t h i s Un it , yo u will b e
able to
 n a m e h a l oa l k an es a n d h a l oa ren e s
according to t h e IUPAC s y s t e m of
n o m e n c l a t u r e from their given
structures;
 describe t h e react ions involved in
t h e pre parati on of ha l o al k a ne s a n d
haloarenes and understand
various reactions that they
u n d e rg o ;
 correlate the s t r u c t u r e s of
h a l o a l k a n e s a n d h a l o a r e n e s wit h
various types of reactions;
 u s e s t e reo c he mi s t ry a s a tool for
understanding the reaction
mechanism;
 a p p r e c i a t e t h e a p p l i c a t i o n s of
organo-metallic c o m p o u n d s ;
 highlight t h e environmental effects
of polyhalogen c o m p o u n d s .
0
Haloarenes
Halogenated co mpo u n ds persist in t he environment d u e to their
resistance to b re a k d o w n b y soil bacteria.
The r e p l a c e m e n t of h y d r o g e n atom(s) in a n a l i p h a ti c
or a r o m a t i c h y d r o c a r b o n by h a l o g e n atom(s) r e s u l t s
in t h e f o r m at i o n of alkyl ha l i d e (haloalkane) a n d aryl
h a l i d e (haloarene), respectively. H a l o a l k a n e s
contain halogen atom(s) a t t a c h e d to t h e s p 3
hybridised c a r b o n a t o m of a n alkyl g r o u p w h e r e a s
h a l o a r e n e s c o n t a i n h a l o g e n atom(s) a t t a c h e d to s p 2
h y b r i d i s e d c a r b o n atom(s) of a n aryl g r o u p . M a n y
halogen containing o rg a n i c c o m p o u n d s o c c u r in
n a t u r e a n d s o m e of t h es e a re clinically useful. These
classes of c o m p o u n d s find wide a p p l i c a t i o n s in
i n d u s t r y a s well a s in d a y - t o-d ay life. They a r e
used as sol vent s for relatively non-polar
c o m p o u n d s a n d a s s t a r t i n g m a t e r i a l s for the
s y n t h e s i s of wide r a n g e of org a ni c c o m p o u n d s .
Chlorine c o n ta in in g an tibio tic, chloramphenicol,
p r o d u c e d by m i c r o o rg a n i s m s is very effective for t h e
t r e a t m e n t of t ypho id fever. O u r body p r o d u c e s iodine
containing h o r mo n e , thyroxine, t h e deficiency of
which c a u s e s a d i s e a s e called goiter. Sy n t h e t i c
h a l o g e n c o m p o u n d s , viz. chloroquine is u s e d for t h e
treatment of m a l a r i a ; h a l o t h a n e is u s e d a s a n
anaesthetic during s u rg e r y. Certain fully
f lu o r i n a te d c o m p o u n d s a r e b eing c o n s i d e r e d a s
p o t e n t i a l blood s u b s t i t u t e s i n s u rg e r y.
In this Unit, you will s t u d y t h e i m p o r ta n t m e t h o d s
of prep ara tio n, physical a n d chemical properties a n d
u s e s of organohalogen c o m p o u n d s .

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 10.1 Haloalkanes a n d ha l o a r e ne s m a y be classified a s follows:
Classification These m a y be classified a s mono, di, or polyhalogen (tri-,tetra-, etc.)
1 0 . 1 . 1 On t h e compounds depending on whether they contain one, two or more halogen
Basis of a t o m s in their s t r u c t u r e s . For example,
Number of
Halogen
Atoms

Monohalocompounds m a y further be classified according to t h e

hybridisation of t h e c a r b o n a t o m to which t h e halogen is bo nded , a s
d i s c us s e d below.
1 0 . 1 . 2 Compounds This class includes
Conta ining (a) A l k y l h a l i d e s o r h a l o a l k a n e s (R—X)
s p 3 C—X
Bond (X= F, In alkyl halides, th e halogen ato m is bonded to a n alkyl group
Cl, Br, I) (R). They form a homologous series represented by C n H 2 n + 1 X. They
are further classified a s primary, secondary or tertiary according to
the na t u r e of carbon to which halogen is attached. If halogen is
attached to a primary carbon a tom in a n alkyl halide, the alkyl
halide is called primary alkyl halide or 1° alkyl halide. Similarly, if
halogen is attached to s ec o n d a r y or tertiary c a r b o n a t o m , t h e
alkyl halide is called secondary alkyl halide (2°) a n d tertiary (3°)
alkyl halide, respectively.

(b) Al l y l i c h a l i d e s
These are t h e c o m p o u n d s in which t h e halogen a t o m is b o nd e d to a n
sp 3 -hybridised ca r b o n a t o m adjacent to car bo n-ca rbon double b o n d
(C=C) i.e. to a n allylic ca rbo n.
Allylic c ar b o n

Allylic c a r bo n
(c) B e nz y l i c h a l i d e s
These ar e t h e c o m p o u n d s in which t h e halogen a t o m is b o n de d to a n
sp 3 -hybridised c ar b o n a t o m a t t ac he d to a n aromatic ring.
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 1 0 . 1 . 3 C o mpo un ds This class includes:
Containing
(a) Vinylic h a l i d e s
s p 2 C—X
B o nd These ar e t h e c o m p o u n d s in which t h e halogen a t o m is bo n d e d to
a sp 2 -hybridised c a r bo n a t o m of a c arbo n-c arb on double b o n d (C
= C).

(b) Ary l h a l i d e s
These a r e t h e c o m p o u n d s in which t h e halogen a t o m is directly
b o nd e d to t h e sp 2 -hybridised c ar b o n a t o m of a n aromatic ring.

10.2 Having learnt the classification of halogenated compounds, let u s now

Nomenclature learn how these are n a me d . The com mon n a m e s of alkyl halides are
derived by naming the alkyl group followed by the n a m e of halide. In the
IUPAC system of nomenclature, alkyl halides are na med a s
halosubstituted hydrocarbons. For mono halogen substituted derivatives
of benzene, common a n d IUPAC n a m e s are t he same . For dihalogen
derivatives, t he prefixes o-, m-, p- are u s e d in comm on system b u t in
IUPAC system, a s you have learnt in Class XI, Unit 12, th e nu m e r al s
1,2; 1,3 a n d 1,4 are us ed .

The dihaloalkanes having the s a m e type of halogen a t om s are n a m e d

a s alkylidene or alkylene dihalides. The dihalo-compounds having
both the halogen atoms are further classified a s geminal halides or gem-
dihalides w h e n both t he halogen a to m s are present o n the s a m e carbon
ato m of the

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 chain a n d vicinal halides or vic-dihalides when halogen atom s are
present on adjacent carbon atoms. In co mmon n a m e system, gem-
dihalides are n a m e d a s alkylidene halides a n d vic-dihalides are
n a m e d a s alkylene dihalides. In IUPAC system, they are n a m e d a s
dihaloalkanes.

Some commo n examples of halocompounds are mentioned in Table 10.1.

Table 1 0 . 1 : C o m m o n and IUPAC Na mes of s o m e Halides

Structure Common name IUPAC n a m e

CH 3 CH 2 CH(Cl)CH 3 sec -B utyl chloride 2-Chlorobutane

(CH 3 )3 CCH 2 Br neo-Pe nty l b ro mi d e 1 - B r o m o -2 , 2 -d i me t h y l p r o p a n e

(CH 3 ) 3 CBr tert -B uty l b romi d e 2-Bromo-2-methylpropane

CH 2 = CHCl Vinyl chloride Chloroethene

CH 2 = Allyl bromi de 3-Bromopropene

CHCH 2 Br

o -C h l or o t o l u e n e 1-Chloro-2-methylbenzene
or
2-Chlorotoluene
Benzyl chloride Chlorophenylm
ethane
CH 2 Cl 2 Me t h yl e n e c hl o ri d e Dichloromethane

CHCl 3 C h l o ro fo rm Tr i c h l o r o m e t h a n e

B ro mofo rm Tr i b r o m o m e t h a n e

C H B r3 C a r b o n t et ra c h l o ri d e Te t r a c h l o r o m e t h a n e

CCl 4 n-Propyl fluoride 1-Fluoropropane

CH 3 C
Example 10.1 Draw
H CHt h e s t r u c t u r e s of all t h e eight s t r u c t u r a l isomers t h a t have t h e
2 2

F
molecular formula C 5 H 1 1 Br. Name each isomer according to IUPAC
system a n d classify t h e m a s primary, secondary or tertiary bromide.
Solution CH CH CH CH CH Br
3 2 2 2 2 1 - B ro m o p en t a n e o

(1 )
CH 3 CH 2 CH 2 CH(Br)CH 3 2-Bromopentane(2o )
CH 3 CH 2 CH(Br)CH 2 CH 3 3 - B ro m o p en t a n e o
(CH
(2 ) ) CHCH CH Br 1-
Bro 3mo
2
-3- methy lbu tan e (1 o
) 2 2

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 (CH 3 )2 CHCHBrCH 3 2-Bromo-3-methylbutane(2 o )
(CH 3 ) 2 CBrCH 2 CH 3 2- Bro mo -2- meth ylb utan e (3o )
CH 3 CH 2 CH(CH 3 )CH 2 Br 1-Bromo-2-methylbutane(1 ) o
o
(CH 3 ) 3 CCH 2 Br 1-Bromo-2, 2-
dimethylpropane (1 )

Write IUPAC n a m e s of t h e following:

Example 10.2

(i) 4-Br omop ent- 2-e ne (ii) 3-B romo- 2-me thy lbut -1-e ne Solution
(iii) 4-Bromo-3-methylpent-2-ene (iv) 1-Bro mo- 2-me thyl but- 2-e ne
(v) 1 - B r o m o b u t - 2 - e n e (vi) 3-Bromo-2-methylpropene

Intext Question
1. Write s t r u c t u r e s of t h e following c o m p o un d s :
(i) 2-Chloro-3-methylpentane
(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1, 4- Dibr omobu t-2 -ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene.

10.3 Halogen a t o m s a r e m o r e electronegative t h a n c a r b o n , therefore,

carbon-halogen bo nd of alkyl halide is polarised; the carbon atom bears
Nature of a partial positive charge w here as t h e halogen a t o m b e a r s a partial
C-X Bond negative charge.

As we go down t h e group in t h e periodic table, t h e size of halogen

a t o m increases. Fluorine a t o m is t h e smallest a n d iodine a t o m is t he
largest. Consequently t h e carbon-halogen b o n d length also i ncre ases
from C—F to C—I. Some typical b o n d lengths, b o n d enthalpies a n d
dipole m o m e n t s ar e given in Table 10. 2.
Alkyl halides are best prepared from alcohols, which are easily
accessible.

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 Table 1 0 . 2 : Carbon-Halogen (C—X) Bond Lengths, Bond
Ent halpi es and Dipole M o m e n t s
B o nd B ond l e n g t h / p m C-X B ond e n t h a l p i e s / kJ mol - 1 Dipol e m o m e n t / D e b y e
CH 3 –F 139 452 1.847
CH 3 – Cl 178 351 1.860
CH 3 –Br 193 293 1.830
CH 3 –I 214 234 1.636

4. Methods of The hydroxyl group of a n alcohol is replaced by halogen on reaction with

Preparation concentrated halogen acids, p h o s p h o r u s halides or thionyl chloride.
Thionyl chloride is preferred because in this reaction alkyl halide is formed
of along with gases SO 2 a n d HCl. The two g aseo us products are escapable,
Haloalkanes hence, the reaction gives pu re alkyl halides. The reactions of primary
a n d secondary alcohols with HCl require t he presence of a catalyst,
1. From ZnCl 2 . With tertiary alcohols, t he reaction is conducted by simply
Alcohols shaking the alcohol with concentrated HCl a t room temperature.
C onst ant boiling with HBr (48%) is u s e d for preparing alkyl bromide.
Good yields of R—I may be obtained by heating alcohols with s odi um
or po tass ium iodide in 95% orthophosphoric acid. The order of
reactivity of alcohols with a given haloacid is 3°>2°>1°. Ph osp horu s
tribromide a n d triiodide are usually generated in situ (produced in th e
reaction mixture) by the reaction of red p h o s p h o r u s with bromine a n d
iodine respectively.

The preparation of alkyl chloride is carried o u t either by pa ssi ng

dry hydrogen chloride gas t h r o u g h a solution of alcohol or by heating
a mixtu re of alcohol a n d c onc entr ated a q u e o u s halogen acid.
The above m e t h o d s ar e no t applicable for t h e preparation of aryl
halides because the carbon-oxygen bond in phenols h a s a partial double
b o n d c hara cte r a n d is difficult to b re a k being stronger t h a n a single
b o n d (Unit 11 , Class XI).
1 0 . 4 . 2 From (I) From a l k a n e s b y f r e e r a d i c a l h a l o g e n a t i o n
Hydrocarbons Free radical chlorination or bromination of alka nes gives a
complex mixture of isomeric mono- a n d polyhaloalkanes, which is
difficult to
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 se p a r a t e a s p u r e c o m p o u n d s . Consequently, t h e yield of a n y single
c o m p o u n d is low (Unit 13, Class XI).

(II) From a l k e n e s
(i) Addition of h y d ro g e n h a l i d es : An a l k e n e is c o n v e r t e d t o
corresponding alkyl halide by reaction with hydrogen chloride,
hydrogen bromide or hydrogen iodide.

Propene yields two prod uct s, however only one pre domi nate s a s
per Markovnikov’s rule. (Unit 13, Class XI)

(ii) Addition of halogens: In t h e laboratory, addition of b romi ne in

CCl 4 to a n alkene resulting in discharge of reddish brown colour
of bromine constitutes a n important m e t h od for t h e detection
of double bo nd in a molecule. The addition results in the
synthesis of vic-dibromides, which ar e colourless (Unit 13 ,
Class XI).

Identify all t h e p o s s i b l e m o n o c h l o r o s t r u c t u r a l i s o m e r s e x p e c t e d t o b e Example 10.3

formed o n free radical monochlorination of (CH 3 ) 2 CHCH 2 CH 3 .
I n t h e given m o l e c u l e , t h e r e a r e f o u r differe nt t y p e s of h y d r o g e n a t o m s . Solution
Replacement of t h e se hydrogen a t o m s will give t h e following
(CH 3 )2 CHCH 2 CH 2 Cl (CH 3 )2 CHCH(Cl)CH 3

(CH 3 )2 C(Cl)CH 2 CH 3 CH 3 CH(CH 2 Cl)CH 2 CH 3

1 0 . 4 . 3 Halogen Alkyl iodides a re often prep ared by t h e reaction of alkyl c h l o ri d e s /

Exchange bromides with NaI in dry acetone. This reaction is known a s Finkelstein
reaction.

NaCl or NaBr t h u s formed is precipitated in dry acetone. It facilitates

t h e forward reaction according to Le Chatelier’s Principle.
The s ynth esi s of alkyl fluorides is best accomplished by heating a n
alkyl chloride/bromide in t h e presence of a metallic fluoride s u c h a s

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 AgF, Hg 2 F 2 , CoF 2 or SbF 3 . The reaction is t ermed a s Swarts reaction.

10.5 From h y d r o c a r b o n s b y e l e c t r o p h i l i c s u b s t i t u t i o n
Preparation of (i) Aryl chlorides a n d bromides c a n be easily pr epa red by electrophilic
su bst itut ion of ar e n e s with chlorine a n d bromine respectively in
Haloarenes the presence of Lewis acid catalysts like iron or iron(III) chloride.

The ortho a n d para isomers c a n be easily s e p a r a t e d d u e to large

difference in their melting points. Reactions with iodine are reversible
in n a t u r e a n d require t h e pr esen ce of a n oxidising agen t (HNO 3 ,
HIO 4 ) to oxidise t he HI formed during iodination. Fluoro com pou nds
ar e no t p re p a r e d by thi s m e t h o d d u e to high reactivity of fluorine.
(ii) From a m i n e s b y S a n d m e y e r ’s r e a c t i o n
Wh e n a p r i m a r y a r o m a t i c a m i n e , dissolved or s u s p e n d e d in cold
a q u e o u s mine ral acid, is t re a t e d with s o d i u m nitrite, a diaz oniu m
s a l t is for med (Unit 1 3 , C l a s s XII). Mixing t h e so l u t i o n of freshly
p r e p a r e d d i a z o n i u m s a l t w i t h c u p r o u s ch l o r i d e or c u p r o u s
b r o m i d e r e s u l t s i n t h e r e p l a c e m e n t of t h e d i a z o n i u m g r o u p by
–Cl or –Br.

Replacement of t h e diazonium group by iodine does no t require

t h e presence of cup rou s halide a n d is done simply by shaking the
diazonium salt with p o t a s s i u m iodide.

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 Example 10.4 Write t h e p r o d u c t s of t h e following reactions:

Solution

Intext Questions
2. Why is s ul p h u r i c acid no t u s e d du ring t h e reaction of alcohols with KI?
3. Write s t r u c t u r e s of different dihalogen derivatives of propane.
4. Among t h e isomeric a l k a n es of molecular formula C 5 H 1 2 , identify t h e one t h a t
o n photochemical chlorination yields
(i) A single monochloride.
(ii) Three isomeric monochlorides.
(iii) Fou r isomeric monochlorides.
5. Draw t h e s t r u c t u r e s of major m ono halo p r o d u c t s in e a c h of t h e following
reactions:

10.6 Physical Alkyl halides a r e colourless w h e n p u r e . However, br omide s a n d iodides

develop colour w h e n exposed to light. Many volatile halogen c o m p o u n d s
Properties have sweet smell.

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 Melting and boiling p o i nt s
Methyl c h l or i d e , m e t h y l b r o m i d e , e t h y l c h l o r i d e a n d s o m e
chlorofluoromethanes ar e gases a t room tem pera ture . Higher m e m b e r s
a r e liquids or solids. As we have already learnt, molecules of organic
halogen c o m p o u n d s ar e generally polar. D u e to greater polarity a s well
a s higher molecular m a s s a s comp ared to t h e p a r e n t hydrocarbon, t h e
intermolecular forces of a ttra cti on (dipole-dipole a n d v an d er Waals)
a r e stronger in t h e halogen derivatives. That is why t h e boiling points
of chlorides, bromides a n d iodides ar e considerably higher t h a n t ho s e
of t h e h y d r o c ar b o n s of co mpa rable molecular m a s s .
The attractions get stronger a s t h e molecules get bigger in size a n d
have more electrons. The pattern of variation of boiling points of
different halides is depicted in Fig. 10 . 1. For t h e s a m e alkyl group,
t h e boiling points of alkyl halides decrease in t h e order: RI> RBr>
RCl> RF. This is b e c a u s e with t h e increase in size a n d m a s s of
halogen a t o m, t h e m a g n it u d e of v an der Waal forces increases.

Fig. 1 0 . 1 : Comparison of boiling points of s o me alkyl hal ides

The boiling points of isomeric h a l oa l k a n e s decrease with increase

i n b r a n c h i n g (Unit 1 2 , C l a s s XI). F o r e x a m p l e , 2 - b r o m o - 2 -
m ethy lpr opan e h a s t h e lowest boiling point a m o n g t h e thr ee isomers.

Boiling points of isomeric dihalobenzenes ar e very nearly t h e s a m e .

However, t h e para-isomers are high melting a s compared to their ortho-
a n d meta-isomers. It is d u e to s ymmet ry of para-isomers t h a t fits in
crystal lattice better a s c o mp a r e d to ortho- a n d meta -isomers.

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 Density
Bromo, iodo a n d polychloro derivatives of hydrocarbons are heavier
t h a n water. The density inc reas es with increase in n u m b e r of c a r b o n
a t o m s , halogen a t o m s a n d atomic m a s s of t h e halogen a t o m s (Table
10.3).

Compound
Table 1 0 . 3 : D e n s i t y of S o mCeo m
D e n s i t y (g/ mL)
Haloalkanes
pound D e n s i t y (g/ mL )

n–C 3 H 7 Cl 0.89 CH 2 Cl 2 1.336

n–C 3 H 7 B r 1.335 CHCl 3 1.489
n-C 3 H 7 I 1.747 CCl 4 1.595

So l ub i l i t y
The haloalkanes are very slightly soluble in water. In order to dissolve
haloalkane in water, energy is required to overcome the attractions
between t h e haloalkane molecules a n d brea k t h e hydrogen b o n d s
between water molecules. Less energy is released when new attractions
are set u p between t he haloalkane a n d t h e water molecules a s thes e a re
no t a s strong a s the original hydrogen bon ds in water. As a result, t he
solubility of haloalkanes in water is low. However, haloalkanes t en d to
dissolve in organic solvents b e ca us e t h e new intermolecular
attractions between haloalkanes a n d solvent molecules have m u c h t he
s a m e strength a s t he ones being broken in th e separate haloalkane a n d
solvent molecules.

Intext Question
1 0 . 6 Arrange e a c h set of c o m p o u n d s in order of
increasing boiling points.
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.
10.7 Chemical The reactions of haloalkanes may be divided into the following categories:
Reactions 1. Nucleophilic subs titu tio n
2. Elimination reactions
1 0 . 7 . 1 R e a c t i o ns of
Haloalkanes 3. Reaction with metals.
(1) N ucl e o p hi l i c s u b s t i t u t i o n r e a c t i o n s
You have learnt in Class XI t hat nucleophiles are electron rich species.
Therefore, they a t t a c k a t t h a t p a r t of t h e s u b s t r a t e molecule which
is electron deficient. The r eac tio n in w hich a nucleophile
repl ace s

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 already existing nucleophile in a molecule is called nucleophilic
s u bs t i t u t i on reaction. Haloalkanes ar e s u b s t r a t e in t h e s e reactions.
In t his type of reaction, a nucleophile r e a ct s with h aloa lka ne (the
substrate) having a partial positive charge on the carbon atom bonded
to halogen. A s u b st i t u t i on reaction t a k e s place a n d halogen at o m ,
called leaving gro up d e p a r t s a s halide ion. Since t h e s u b s t it u t i o n
reaction is initiated by a nucleophile, it is called nucleophilic
s u bs t i t u t i on reaction.

It is one of t h e m o s t useful classes of organic reactions of alkyl

halides in which halogen is bo nd e d to s p 3 hybridised c arb on. The
pr o d u c t s formed by t h e reaction of ha loal kan es with som e c o m mo n
nucleophiles are given in Table 10. 4.

Table 1 0 . 4 : Nucleophilic Sub s ti t ut io n of Alkyl Halides (R–X)

Reagent Nucleophile Substitution Class of m a i n

(Nu – ) p ro d uct R– p ro d u c t
Nu
NaOH (KOH) HO – ROH Alcohol
H2 O H2 O

NaOR R O – ROH Alcohol

NaI ROR R Ether

I–
NH 3 —I Alkyl iodide
NH 3
RNH 2 P ri m ary a m i n e
RNH2
RNH 2 Sec. a m i n e
RNHR
RRNH
RRN Tert. a m i n e
KCN H 
RNRR
RC N Nitrile
AgCN Ag-CN: RNC (cyanide)
(isocyanide)
Isonitrile
KNO2 O=N—O Ag R—O—N=O Alkyl nitrite

AgNO2 —Ö—N=O R—NO 2 Nitroalkane

RCOOAg RCOO– RCOOR RH Ester

H RR Hydrocarbon
LiAlH4
R– Alkane
R– M+

G r o u ps like cyanides a n d nitrites po s s e s s two nucleophilic centres

a n d ar e called a m b i d e n t nu c l e o p h i l e s . Actually cyanide group is a
hybrid of two contributing s t r u c t u r e s a n d therefore c a n ac t a s a
nucleophile in two different ways [VCN  :C=NV], i.e., linking t h r o u g h

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 Haloalkanes react with KCN to form alkyl cyanides a s m a i n p r od u c t Example 10.5
while AgCN forms isocyanides a s t h e chief pro duc t. Explain.
KCN is predominantly ionic a n d provides cyanide ions in solution. Solution
Although b o t h c a r b o n a n d nitrogen a t o m s ar e in a position to d o n at e
electron pairs, t h e at t a c k t a k e s place mainly t h r o u g h c a r b o n a t o m
a n d no t t h r o u g h nitrogen a t o m since C—C b o n d is more stable t h a n
C—N bo nd. However, AgCN is mainly covalent in n a t u r e a n d nitrogen
is free to d o n at e electron pair forming isocyanide a s t h e m a i n product.

c a r b o n a t o m resulting in alkyl cyanides a n d t h r o u g h nitrogen a t o m

leading to isocyanides. Similarly nitrite ion also repres i ei n t s a n ambident
n u c l e o p h i l e w i t h t w o d i ff e r e n t p o i n t s of l i n k a g e [–O— N =O]. T h e l i n k a g e
t h r o u gh oxygen results in alkyl nitrites while t h r o u gh nitrogen atom, it
leads to nitr oal kan es.
Mechanism: This reaction h a s b ee n fo und to proceed by two different
m e c h a n i m s which a r e described below:
(a) S u b s t i t u t i o n nu c l e o p h i l i c b i m o l e c u l a r (S 2)
N
The reaction between CH 3 Cl a n d hydroxide ion to yield me tha nol a n d
chloride ion follows a se con d order kinetics, i.e., t h e r a t e d e p e n d s
u p o n t h e concentration of b o th t h e r e a c t an t s .

You have already l ea rnt in Section 1 2 .3 .2 of Cl ass XI, t h e solid wedge re p re s e n t s t h e b o n d

coming o u t of t h e paper, d a s h e d line going down t h e p a p e r a n d a st ra i g ht line rep resent ing
b o n d in t h e pl a n e of t h e paper.

The above reaction c a n be rep res ente d diagrammatically a s s h o w n in

Fig. 10.2.

Fig. 1 0 . 2 : R ed ball represents the incoming hydroxide ion a n d green ball represents the
outgoing halide ion

In t h e y e a r 1 9 3 7 , It d e p i c t s a b i m o l ec u l a r nu cleo phi lic s u b s t i t u t i o n (S N 2) r e ac t i o n ;

E d w a rd Davies Hugh es
a n d Sir C h r i s t o p h e r
I n g o l d p ro p o s e d a
mech a ni sm for a n S N 2
reaction.
t h e in comi ng nu cl e o p hi l e i n t e r a c t s with alkyl h a l i de c a u s i n g t h e
c a r b o n - h a l i d e b o n d to b r e a k a n d a n e w b o n d is f orme d b e t w e e n
c a r b o n a n d attacking nucleophile. Here it is C-O b o n d formed between
C a n d -OH. Th e s e two p r o c e s s e s t a k e pla ce s i m u l t a n e o u s l y in a

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 single s t e p a n d n o int erme diat e is formed. As t h e reaction pro gres ses
a n d t h e b o n d be t w e e n t h e inc omin g n u cl e o p h i le a n d t h e c a r b o n
a t o m s t a r t s forming, t h e b o n d b e t w e e n c a r b o n a t o m a n d leaving
g r o u p w e a k e n s . As t h i s h a p p e n s , t h e t h r e e c a r b o n - h y d r o g e n b o n d s
of t h e s u b s t r a t e s t a r t moving away from t h e atta cki ng nucleophile.
In transition s tate all t h e three C-H b o n d s a r e in t h e s a m e p l a n e a n d
t h e a t t a c k i n g a n d leaving n u c l e o p h i l e s a r e partially a t t a c h e d to t h e
ca rbo n. As t h e attacking nucleophile a p p r o a c h e s closer to t h e
car bon , C-H b o n d s still keep o n moving in t h e s a m e direction till t h e
attacking n ucl eop hile a t t a c h e s to c a r b o n a n d leaving g r o u p leaves
t h e c a r b o n . As a r e s u l t con figu rati on is i nver ted , t h e con fig urat ion
(See box) of c a r b o n a t o m u n d e r a t t a c k i nver ts in m u c h t h e s a m e
way a s a n u m b r e l l a is t u r n e d in sid e o u t w h e n c a u g h t i n a s t r o n g
wind . This p r o c e s s is called a s i n v e r s i o n of c o n f i g u r a t i o n . In t h e
t r a n s i t i o n s t a t e , t h e c a r b o n a t o m is s i m u l t a n e o u s l y b o n d e d to
incoming n u c l eo p h i l e a n d t h e outgoing leaving g r o u p . S u c h
structures are u n s t a b l e a n d c a n n o t be isolated. Th u s , in t h e
tran sit ion st ate, c a r b o n is s i m u l t a n e o u s l y b o n d e d to five a t o m s .

Configuration
Spacial a r r a n g e m e n t of functional gr o u p s a r o u n d c a r b o n is called its configuration.
See t h e s t r u c t u r e s (A) a n d (B) given below carefully.

These are the two st ruct ures of the s a m e compound. They differ in spacial arrangement
of functional groups a t ta c h e d to carbon. St r u c t u r e (A) is mirror image of St r uc t u r e
(B). We s ay configuration of c a r b o n in s t r u c t u r e (A) is mirror image of t h e
configuration of c a r bo n in s t r u c t u r e (B).

Hug hes w o rk ed under Since thi s reaction requires t h e a p p r o a c h of t h e nucleophile to t h e

Ingold a n d e a r n e d a c a r b o n bearing t h e leaving group, t h e presence of bulky s u b s t i t u e n t s
D.Sc. degree from the o n or n e a r t h e c ar b o n a t o m have a dr amat ic inhibiting effect. Of t h e
University of London.
simple alkyl halides, methyl halides react m os t rapidly in S N2 reactions
b e c a u s e t h e r e a r e only t h r e e sma ll hy drog en a t o m s .
Tertiary h a l i de s
a r e t h e lea st reactive b e c a u s e bul ky g r o u p s h i n d e r t h e
approaching

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 nucleophiles. T h u s t h e o rder of reactivity followed is:
Primary halide > Secondary halide > Tertiary halide.

F i g . 1 0 . 3 : Steric effects in S N 2 reaction. The relative rate of S N 2 reaction is given in parenthes is

(b) S u b s t i t u t i o n n u c l e o p hi l i c u n i m o l e c u l a r (SN 1)
S N 1 r e a ct i o n s a r e generally car rie d o u t in polar protic solvents
(like water, alcohol, acetic acid, etc.). The r eact ion bet ween tert-
bu tyl br omid e a n d hydroxide ion yields tert-butyl alcohol a n d
follows t h e first or der kinetics, i.e., t h e r a t e of r eact ion d e p e n d s
u p o n t h e c o n c e n t r a t i o n of only o n e r e a c t a n t , w h i c h is tert- b u t y l
bromide.

It occurs in two steps. In step I, t he polarised C—Br bo nd undergoes

slow cleavage to pr o d u c e a carbocation a n d a bromide ion. The
carbocation t h u s formed is t h e n a t t a c ke d by nucleophile in s t e p II
to complete t h e s ub s t i t ut i o n reaction.

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 St e p I is t h e s lowe st a n d reversible. It involves t h e C–Br b o n d b r e a k i n g for w h i c h t h e
energ y is o b t a i n e d t h r o u g h so lva tio n of ha l i d e ion wit h t h e p r o t o n of p rot ic sol vent . S i n c e
t h e r a t e of r e a ct i o n d e p e n d s u p o n t h e slowest s t e p , t h e r a t e of r e a ct i o n d e p e n d s only o n
t h e c o n c e n t ra t i o n of alkyl halide a n d n o t o n t h e c o n c e n tr a t i o n of hydroxide ion. F u r t h e r,
grea ter t h e stability of c a r bo c a t i o n, gr eat er will b e its e a s e of for mati on from alkyl ha lid e
a n d bfas
will e tter
h e r a t e of r ea c t i o n . In c a s e of alkyl h al i d e s , 3 0 alkyl h a l i d e s u n d e rg o S 1N r e a c t i o n
very fast b e c a u s e of t h e high stability of 3 0 carbocations. We c a n s u m u p t h e order of reactivity
of alkyl h a l i d e s t o w a r d s S N 1 a n d S N 2 r e a c t i o n s a s follows:

For t h e s a m e r e a s o ns , allylic a n d benzylic halides sho w high reactivity tow ards t h e S N 1

reaction. The carbocation t h u s formed gets stabilised t h r o u g h r e so n a n c e (Unit 12 , Class XI) a s
s h o w n below:
+ +
H2C C CH2
H H2C HC CH2

For a given alkyl group, t h e reactivity of t h e halide, R-X, follows t h e s a m e order in b o t h t h e

m e c h a n i s m s R–I> R–Br>R–Cl>>R–F.

In t h e following pa irs of halogen c o m p o u n d s , which would Example 10.6

u n d e rg o S N 2 reaction faster?

It is primary halide a n d therefore un dergo es S N 2 Solution

reaction faster.

As iodine is a better leaving group b e c a u s e of its

large size, it will be released a t a faster rate in
t h e presence of incoming nucleophile.

Predict t h e order of reactivity of t h e following c o m p o u n d s in S N 1 a n d Example 10.7

S N 2 reactions:
(i) The four isomeric b r o m o b u t a n e s
(ii) C 6 H 5 CH 2 Br, C 6 H 5 CH(C 6 H 5 )Br, C 6 H 5 CH(CH 3 )Br, C6 H 5 C(CH 3 )
(C 6 H 5 )Br
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 Solution (i) CH 3 CH 2 CH 2 CH 2 Br < (CH 3 ) 2 CHCH 2 Br < CH 3 CH 2 CH(Br)CH 3 < (CH 3 ) 3 CBr (SN1)
CH 3 CH 2 CH 2 CH 2 Br > (CH 3 ) 2 CHCH 2 Br > CH 3 CH 2 CH(Br)CH 3 > (CH 3 ) 3 CBr (SN 2)

Of t h e two primary bromides, t h e carbocation intermediate derived from

(CH 3 ) 2 CHCH 2 Br is more stable t h a n derived from CH 3 CH 2 CH 2 CH 2 Br because
of greater electron donating inductive effect of (CH 3 ) 2 CH- group. Therefore,
(CH 3 ) 2 CHCH 2 Br is more reactive t h a n CH 3 CH 2 CH 2 CH 2 Br in S N 1 reactions.
CH 3 CH 2 CH(Br)CH 3 is a sec ond ary bromide a n d (CH 3 ) 3 CBr is a tertiary
bromide. Hence t h e above order is followed in S N 1. The reactivity in S N 2
reactions follows t h e reverse order a s t h e steric h i nd e r a n c e a r o u n d t h e
electrophilic c a r b o n incr eas es in t h a t order.
(ii) C6 H 5 C(CH 3 )(C 6 H5 )Br > C 6 H 5 CH(C 6 H 5 )Br > C 6 H 5 CH(CH 3 )Br > C 6 H 5 CH 2 Br (SN1)
C 6 H5 C(CH 3 )(C 6 H 5 )Br < C 6 H 5 CH(C 6 H 5 )Br < C 6 H 5 CH(CH 3 )Br < C 6 H 5 CH 2 Br (SN2)
Of t h e two secondary bromides, t h e carbocation intermediate obtained from
C 6 H 5 CH(C 6 H 5 )Br is more stable t h a n obtained from C 6 H 5 CH(CH 3 )Br
b e ca us e it is stabilised by two phenyl groups d u e to resonance. Therefore,
t h e former bromide is more reactive t h a n t h e latter in S N 1 reactions. A
phenyl group is bulkier t h a n a methyl group. Therefore, C 6 H 5 CH(C 6 H 5 )Br
is less reactive t h a n C 6 H 5 CH(CH 3 )Br in S N 2 reactions.
(c) S t e r e o c h e m i c a l aspects of n u c l e o p hi l i c substitution
r e a c t i o n s In order to u n d e r s t a n d t h e stereochemical a s p e c t s of
su b s t i t ut i o n reactions, we ne ed to learn some basic
stereochemical principles a n d n otat ion s (optical ac t i v i ty,
chirality, re t e nt i o n , i nver sion , r acemi sat ion, etc.).
(i) Optical activity: Plane of plane polarised light prod uce d by
pa ssi ng ordinary light t h r o u g h Nicol p ris m is rotated w h e n it
is p a s s e d t h r o u g h t h e solutions of certain c o mp o u n d s . S u c h
c o m p o u n d s a re called optically ac t i v e c o m p o u n d s . The angle
Wi l l i a m Nicol ( 1 7 6 8 - by which t h e plane polarised light is rotated is m e a s u r e d by
1851) developed the first a n instrument called polarimeter. If the compound rotates the
p r i s m t h a t p ro d u c e d plane of plane polarised light to t h e right, i.e., clockwise
plane polarised light.
direction, it is called dextrorotatory (Greek for right rotating)
or t h e d-form a n d is indicated by placing a positive (+) sign
before t h e degree of rotation. If t h e light is rotated towards left
(anticlockwise direction), t h e c o m p o u n d is said to be laevo-
rotatory or t he l-form a n d a negative (–) sign is placed before
t h e degree of rotation. S u c h (+) a n d (–) isomers of a
c o m p o u n d are called optical i s o me r s a n d t h e p h e n o m e n o n
is t ermed a s optical isomerism.
(ii) Mole cula r a s y m m e t r y , c h i r al i t y a n d e n a n t i o m e r s : T h e
observation of Louis Pa s t e u r (1848) t h a t crystals of certain
c o m p o u n d s exist i n t h e form of m i r r o r i m a g e s laid t h e
foundation of m o d e r n stereochemistry. He d e mo n s t r at e d t h a t
a q u e o u s solutions of b o t h types of crystals sh owed optical
rotation, equal in magnitude (for solution of equal concentration)
b u t opposite in direction. He believed t h a t this difference in
optical activity w a s associated with t h e t hre e dimensional
a r r a n g e m e n t s of a t o m s in t h e molecules (configurations ) of

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 two types of crystals. D u t c h scientist, J. Van’t Hoff a n d F r e n ch
scientist, C. Le Bel in t h e s a m e year (1874), independently
a rg u e d t h a t t h e spatial a r r a n g e m e n t of four gr oup s (valencies)
Jacobus Hendricus
Van’t Hoff (1852-1911)
a r o un d a central carbon is tetrahedral a n d if all the
received the first Nobel substituents a t t a c h e d to t h a t c a r b o n ar e different, t h e mirror
Prize in C h e mi st r y in image of t h e molecule is no t sup erimp ose d (overlapped) o n
1 9 0 1 for h is w o r k on t h e molecule; s u c h a c a r bo n is called a s y m me t r i c carbon or
solutions. s t e re o c en t re . The resulting molecule would lack symmetry
a n d is referred to a s asymmetric molecule. The asymmetry of
t h e molecule along with n o n superimposability of mirror
images is responsible for t h e optical activity in s u c h organic
c o mp o u n d s .
The symmetry a n d asymmetry are also observed in m a n y day to day
objects: a sphere, a cube, a cone, are all identical
to their mirror images a n d c an be
superimposed. However, many objects are non
superimposable on their mirror images. For
example, your left and right h a n d look similar
b u t if you p u t your left h a n d on your right ha n d
by moving them in the same plane, they do not
coincide. The objects which are non-
superimposable on their mirror image (like a pair
of hands) are said to be chiral a n d this property
is known a s chirality. Chiral molecules are
optically active, while the objects, which are,
superimposable on their mirror images are
called achiral. These molecules are optically
inactive.
The above test of molecular chirality c an be
applied to organic molecules by constructing
models a n d its mirror images or by drawing
three
chiral molecules. d i m e nOne
s i o ns ua cl h aid
s t risu the
c t u rpresence
es and
Fig 1 0 . 4 : S o m e co mmon e x a m p l e s of chiral a n d aof
t t eamsingle
p t i n gasymmetric
to superimpose
achiral objects carbon atom. Let u s our
t h e m in
minds. There are other aids, however, t h a t c a n
two simple molecules consider propan-2-ol (Fig.10.5) a n d bu t a n - 2 -o l
assist u s in recognising
(Fig.10.6) a n d their mirror images.

Fig 1 0 . 5 : B is mirror image of A; B is rotated b y 180 o a n d C is

obtained; C is superimposable on A.

As you can see very clearly, propan-2-ol (A) does not contain a n
asymmetric carbon, a s all the four groups attached to the tetrahedral
carbon are not different. We rotate the mirror image (B) of the molecule by
180° (structure
C) a n d try to overlap the structure (C) with the structure (A), these
structures completely overlap. Thus propan-2-ol is a n achiral molecule.
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 Fig 10.6: E is mirror image of D; E is rotated b y 180 o to get F a n d F is
non superimposable on its mirror image D.

B u t a n - 2 - o l h a s four d iffer ent g r o u p s a t t a c h e d t o t h e

tetr ahe dra l c a r b o n a n d a s expected is chiral. So me c o m m o n
examples of chiral molecules such as 2-
chlorobutane, 2, 3-dihyroxypropanal, (OHC–CHOH–CH 2 OH),
br omoc hlo ro-i odo meth ane (BrClCHI), 2 - br o m o p r op a n o i c acid
(H 3 C–CHBr–COOH), etc.
Fig. 10.7: A c h i r a l m o l e c u l e The s t e r e o i s o m e r s r e l a te d to e a c h o t h e r a s n o n -
a n d its mirror image s u p e r i m p o s a b l e mirror im age s are called e n a n t i o m e r s
(Fig. 10.7). A a n d B in Fig. 10 .5 a n d D a n d E in Fig. 10 .6 ar e
enantiomers.
E n a nt i o me r s p o s s e ss identical physical properties namely,
melting point, boiling point, refractive index, etc. They only differ
with respect to t h e rotation of plane polarised light. If one of t he
e n a n ti o m e r is dextro rotatory, t h e other will be laevo
rotatory.
However, t h e sign of optical rotat ion is n o t necessarily related to t h e
ab s o l ut e (actual) configuration of t h e molecule.

A mixt ure containing two e n a n t i om e r s in equal proportions

will have zero optical rotation, a s t h e rotation d u e to one
isomer will be cancelled by t h e rotation d u e to t h e oth er
isomer. S u c h a m i x t u r e is k n o w n a s r a c e m i c m i x t u r e or
r a c e m i c modif ica tion . A racemic mixture is re pres ent ed by
prefixing dl or () before t h e n a m e , for example () butan-2-ol.
The process of conversion of enantiomer into a racemic
mixture is kn own a s race misa tion .

Example 10.8 Identify chiral a n d achiral molecules in e a c h of t h e following pair of

c o m p o u n d s . (Wedge a n d D a s h re pres ent atio ns according to Class
XI, Fig. 12.1).

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 Solution

(iii) Retention: Retention of configuration is the preservation of the spatial

a r r a n g e m e n t of b o n d s to a n asymmetric centre duri ng a chemical
reaction or transformation.
In general, if during a reaction, n o bo nd to the stereocentre is broken,
t h e p r o d u c t will h ave t h e s a m e general configuration of g r o u p s
a r o u n d t h e stereocentre a s t h a t of r e a ct a n t . S u c h a reaction is s aid
to proceed with r ete ntio n of t h e configuration. Cons ide r a s a n
example, t h e reaction t h a t t ak e s place w h e n (–)-2-methylbutan-1-ol
is h e a t e d with c onc ent rate d hydrochloric acid.

It is i mp o r ta n t to note t h a t configuration a t a symmetric centre in

t h e r e a c t a n t a n d pr o d u c t is s a m e b u t t h e sign of optical rotation
h a s c h a n g e d in t h e prod uct . This is so b e c a u s e two different
c omp ound s with s a m e configuration a t asymmetric centre may have
different optical rotation. O ne m a y be dextrorotatory (plus sign of
optical rotation) while ot her m a y be laevorotatory (negative sign of
optical rotation).
(iv) Inversion, retention a n d racemisation: There a r e th ree o u t c o me s
for a reaction a t a n asymmetric ca rbo n atom, w h e n a b o nd directly
linked to a n asym metr ic c a r b o n a t o m is br oke n. Consider t h e
r epl acem ent of a gr oup X by Y in t h e following reaction;

If (A) is t h e only c o m p o un d obtained, t he process is called retention

of configuration. Note t h a t configuration h a s b e e n r ota ted in A.
If (B) is th e only c o mp ou n d obtained, the process is called inversion
of configuration. Configuration h a s b e e n inverted in B.

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 If a 50:50 mixture of A a n d B is obtained t h e n t he process is called
racemisation a n d the product is optically inactive, a s one isomer will
rotate th e plane polarised light in th e direction opposite to another.
Now l e t us h a v e a fresh lo ok a t S N 1 and S N 2 m e c h a n i s m s by
taking e x a mpl e s of optically a c t i v e alkyl halides.
In ca s e of optically active alkyl halides, t h e pr o d u c t formed a s a
re sul t of S N 2 m e c h a n i s m h a s t h e inverted configuration a s c om p a r ed
to t h e r e ac t a n t . This is b e c a u s e t h e nucleophile a t t a c h e s itself o n t h e
side opposite to t h e one where t h e halogen a t o m is p r e se n t . Wh en
(– )-2 -br omooc tane is allowed to r e a c t w it h s o d i u m h y d r o x i d e , (+)-
octan-2-ol is formed with t h e –OH grou p occupying t h e position
opposite to w h a t bromide h a d occupied.

T h us , S N 2 reactions of optically active halides ar e accompanied by

inversion of configuration.
In c a s e of optically active alkyl h a l i d e s , S N 1 r e a c t i o n s a r e
ac comp ani ed by racemisation. C a n you t h i n k of t h e r e a s o n why it
h a p p e n s ? Actually t h e carbocation formed in t h e slow s t e p being sp2
hybridised is p l a n a r (achiral). The a t t a c k of t h e nucleophile m a y be
accomplished from either side of t h e pl ane of carbocation resulting in
a mixt ure of p ro d u c t s, one having t h e s a m e configuration (the –OH

at tach ing o n t h e s a m e position a s halide ion) a n d t h e oth er having

Location of  and opposite configuration (the –OH attaching on the side opposite to halide
 carbon in a ion). T h is m a y b e i l l u s t r a t e d by h y d r o l y s i s of optically a c t i v e 2 -
mo l e c u l e b r o m o b u t a n e , which r e s u l ts in t h e formation of ()-butan-2-ol.
Carbon on which 2 . Elimination reactions
halogen atom is Wh en a ha loa lkan e with -hydrogen a t o m is h e a t e d with alcoholic
directly a t ta c h e d is solution of p o t a s s i u m hydroxide, t her e is elimination of hydrogen
called  -carbon a n d a t o m from -carbon a n d a halogen a t o m from t h e -carbon a t o m .
the carbon atom
adjacent to
this
c a r b o n is c a l le d
-carbon.

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 As a result, a n alkene is formed a s a p rod uct . Since -hydrogen
a t o m is involved in elimination, it is often called -elimination .

If th ere is possibility of formation of mo re t h a n one alkene d u e to

t he availability of more t h a n one -hydrogen a toms , usually one alkene
is formed a s t h e major pr odu ct. These form p a r t of a p a t t e r n first
observed by R u s s i a n chem ist, Alexander Zaitsev (also p r o n o u n c e d a s
Saytzeff) who in 1 8 7 5 formulated a rule which c a n be s u m m a r i s e d a s
“in d e h y dro ha l o g e n at i o n reactions, t h e preferred product is t h a t
alkene which h a s the greater numb er of alkyl groups attached to the
d o u b l y b o n d e d carbon a t o ms . ” T h u s , 2 - b r o m o p e n t a n e gives pe nt-
2-en e a s t h e major pr od uct.

Elimination

versus

substitution

A chemical reaction is t h e re su l t of competition; it is a race t h a t is won by t h e fast est r u n n e r.

A collection of molecules t e n d to do, by a n d large, w h a t is easi est for t h e m . An alkyl halide
with -hydrogen a t o m s w h e n react ed with a b a s e or a nucleophile h a s two competing routes:
su b s t i t ut i o n (S N 1 a n d S N 2) a n d elimination. Which ro u t e will be t a k e n u p d e p e n d s u p o n t h e
n a t u r e of alkyl halide, s t re n g t h a n d size of b a s e / n u c l e o p h i l e a n d reaction conditions. T h u s , a
bulkier nucleophile will prefer to ac t a s a b a s e a n d a b s t r a c t s a pro ton ra t h er t h a n a p p roa c h a
tetravalent c a rb o n a t o m (steric reasons) a n d vice versa. Similarly, a pri mary alkyl halide will
prefer a S N 2 reaction, a s ec o nd a ry halide- S N 2 or elimination depend ing u p o n t h e s t re n g t h of
b a s e / n u c l e o p h i l e a n d a tertiary halide- S N 1 or elimination de pending u p o n t h e stability of
carbocat ion or t h e mo re s u b s t i t u t e d alkene.

3 . Reaction wi th m e t a ls
Most organic chlorides, bromides a n d iodides react with certain
m e t a ls to give c o m p o u n d s containing car bon- meta l b o n d s . S u c h
c o m p o u n d s a r e k n o w n a s o r g a n o - m e t a l l i c c o m p o u n d s . An
i m p o rt a n t class of organo-metallic c o m p o u n d s discovered by Victor
Grignard in 1 9 0 0 is alkyl m a g n e s i u m halide, RMgX, referred a s
Grignard Rea gent s . These r eage nts a r e obtained by t h e reaction of
ha l o a l k an es with m a g n e s i u m metal in dry ether.

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 Victor Grignard h a d a strange start in academic life for a chemist - h e
took a m a t h s degree. W h e n h e eventually s w i t c he d to chemistry, it w a s
not to the mathematical province of physical chemistry but to organic
chemistry. While attempting to find a n efficient catalyst for t he process
of methylation, h e not ed that Zn in diethyl ether h a d b e e n u s e d for this
purpose a n d w o n d e re d w h et he r t he M g / e t he r combination might b e
successful. Grignard reagents w e re first reported in 1 9 0 0 a n d Grignard
u s e d this w o rk for his doctoral t hesi s in 1 9 0 1 . In 1 9 1 0 , Grignard obtained
a professorship at t he University of N a n cy a n d in 19 1 2 , h e w a s
a w a rd e d t he Nobel prize for Chemistry w h i ch h e s h a re d w i t h Paul
Sabatier w h o h a d m a d e a d v a n c e s in nickel c a t al y s e d hydrogenation.

In t h e Grignard reagent, t h e c a r b o n - m a g n e s i u m b o n d is covalent

b u t highly polar, with c a r b o n pulling electrons from electropositive
m a g n e s i u m ; t h e m a g n e s i u m halogen b o n d is essentially ionic.

Grignard r eage nts a r e highly reactive a n d react with a n y s o u r c e of

proton to give hydrocarbons. Even water, alcohols, amines are sufficiently
acidic to convert t h e m to corresponding hy droc arbo ns.

It is therefore necessary to avoid even traces of moisture from a Grignard

reagent. Th at is why reaction is carried o u t in dry ether. O n t h e o the r
h a n d , this could be considered a s one of t h e m e t h o d s for converting
halides to hydr oca rbon s.
Wu r t z r e a c t i o n
Alkyl halides react with s o d i u m in dry eth er to give hy d r o c a rb o n s
containing double t h e n u m b e r of c a r b o n a t o m s p r e s e n t in t h e halide.
This reaction is k n o w n a s Wurtz reaction (Unit 1 3, Class XI).

1 0 . 7 . 2 R e a c t i o ns of
1. N uc l e o phi l i c s u b s t i t u t i o n
Haloarenes
Aryl h a l i d e s a r e extremely les s reactive t o w a r d s nuc leop hili c
s ub s t i t ut i o n reactions d u e to t h e following r e a so n s :
(i) Resonance effect : In haloarenes, t h e electron pairs o n halogen
a t o m a r e in conjugation with -electrons of t h e ring a n d t he
following resonating s t r u c t u r e s ar e possible.

C—Cl b o n d acquires a partial double b o n d c har act er d u e to

resonance. As a result, the bond cleavage in haloarene is difficult
t h a n haloalkane a n d therefore, they ar e less reactive towards
nucleophilic s u bs t i t u t i on reaction.

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 (ii) Difference in hybridisation of carbon atom in C—X bond: In
h a l oa l k a n e , t h e c a r b o n a t o m a t t a c h e d to ha log en is s p 3
hybridised while in case of haloarene, the carbon at om attached
to halogen is sp 2 -hybridised.

The sp 2 hybridised c ar b o n with a greater s- char act er is more

electronegative a n d c a n hold t h e electron pair of C—X b o n d
more tightly t h a n sp 3 -hybridised c a r b o n in ha loal kan e with
less s-chararcter. Th u s , C—Cl b o n d length in halo alk ane is
1 7 7 p m while in haloarene is 1 6 9 p m . Since it is difficult to
b reak a shorter bo nd t h a n a longer bond, therefore, haloarenes
a r e le ss reactive t h a n h a l o a l k a n e s t o w a r d s n ucl eoph ili c
s u b s t i tu t i o n reaction.
(iii) Instability of phenyl cation: In case of haloarenes, t h e phenyl
cation formed a s a result of self-ionisation will not be stabilised
by r e s on a n c e a n d therefore, S N 1 m e c h a n i s m is ruled out.
(iv) Because of the possible repulsion, it is less likely for the electron
rich nucleophile to a p p r o a c h electron rich a r en e s .
Replacement by hydroxyl group
Chlorobenzene c a n be converted into phenol by heating in a q u e o u s
s o d i um hydroxide solution a t a t e m p er a t u re of 623K a n d a p r e s s u r e
of 3 0 0 a t mo s p he r e s .

The presence of a n electron withdrawing group (-NO 2 ) a t ortho- a n d

para-positions i ncr ease s t h e reactivity of ha loa rene s.

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 The effect is p ro n o u n ce d w h e n (-NO2 ) group is introduced a t ortho-
a n d para- positions. However, n o effect on reactivity of h a l oa r e n e s is
observed by the presence of electron withdrawing group at meta-position.
Mec han ism of t h e reaction is a s depicted:

C a n you t h i n k why do es NO 2 g rou p s h ow its effect only a t ortho- a n d para- positions a n d

no t a t meta - position?
As s h o wn , t h e p re s e n ce of nitro gro up a t ortho- a n d para-positions wi t hd raws t h e
electron density from t h e be n ze n e ring a n d t h u s facilitates t h e a t t a c k of t h e nucleophile o n
ha l o are n e. The ca rb an i o n t h u s formed is stabilised t h r o u g h re s o n a n c e . The negative ch arge
a p p e a r e d a t ortho- a n d para- positions with respect to t he halogen s u b s t i t u e n t is s t a b i l i s e d
by –NO 2 g r o u p while i n c a s e of m e t a - n i t r o b e n z e n e , n o n e of t h e r e s o n a t i n g s t r u c t u r e s b e a r
t h e negative ch arge o n c a rb on a t o m bearing t h e –NO2 group. Therefore, t h e p re se n ce of nit ro
gro up a t met a - position does n o t stabilise t h e negative charge a n d n o effect o n reactivity is
observed by t h e p re s e nc e of –NO 2 g ro up a t meta-position.

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 2 . Electrophilic substitution reactions
Haloarenes un d e rg o t h e u s u a l electrophilic reactions of t h e be nze ne
ring s u c h a s halogenation, nitration, s u l p ho na t i o n a n d Friedel-Crafts
reactions. Halogen a t o m besides being slightly deactivating is o, p-
directing; therefore, further s ub s t i t u ti o n oc cur s a t ortho- a n d para-
positions with respect to t h e halogen atom. The o, p-directing influence
of halogen a t o m c a n be easily un ders too d if we consider t h e
resonating s t r u c t u r e s of halobenzene a s s hown :

D u e to resonance, t h e electron density increases more a t ortho- a n d

para-positions t h a n a t meta -positions. F u rt h e r, t h e halogen a t o m
b e c a u s e of its –I effect h a s som e tendency to withdraw electrons from
t h e benzene ring. As a result, t h e ring gets s o me w h at deactivated a s
compared to benzene a n d hence th e electrophilic substitution reactions
in ha loa rene s occur slowly a n d require more drastic conditions a s
c o m p a re d to t h o s e in benzene.
(i) Halogenation

(ii) Nitration

(iii) Sul phon atio n

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 (iv) Friedel-Crafts reaction

Example 10.9 Although chlorine is a n electron withdrawing group, yet it is ortho-,

para- directing in electrophilic aromatic s u b s t i tu t i o n reactions. Why?
Solution Chlorine withdraws electrons t h r o u g h inductive effect a n d releases
electrons t h r o u g h r e s o n a n c e . T h r o u g h inductive effect, chlorine
destabilises the intermediate carbocation formed during the electrophilic
substitution.

Thr ough r e s o n an ce , halogen t e n d s to stabilise t h e carbocation a n d

t h e effect is more p r on o u n c e d a t ortho- a n d para- positions. The
inductive effect is stronger t h a n r e s o n an ce a n d c a u s e s n e t electron
withdrawal a n d t h u s c a u s e s n e t deactivation. The re s o n a n ce effect
t e n d s to oppose t h e inductive effect for t h e a t t a c k a t ortho- a n d para-
positions a n d h e n c e m a k e s t h e deactivation less for ortho- a n d
para- at tac k. Reactivity is t h u s controlled by t h e stronger inductive
effect a n d orientation is controlled by r e s on a n c e effect.

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 3. Reaction w ith m e t a ls
Wur tz-F itt ig r e a c t i o n
A mixt ure of a n alkyl halide a n d aryl halide gives a n alkylarene w h e n
t reat ed with s o d i u m in dry eth er a n d is called Wurtz-Fittig reaction.

Fi ttig r e a c t i o n
Aryl halides also give analogous c o m p o u n d s w he n treated with sodi um
in dry ether, in which two aryl gr o u p s a r e joined together. It is called
Fittig reaction.

Intext Questions
1 0 . 7 Which alkyl halide from t h e following pairs would you expect to react more
rapidly by a n S N 2 m e c h a n i s m ? Explain your answer.

1 0 . 8 In the following pairs of halogen co mpo unds , which co m p o u nd undergoes faster

S N 1 reaction?

1 0 . 9 Identify A, B, C, D, E, R a n d R 1 in t h e following:

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10.8 Polyhalogen Carbon comp oun ds containing more t h a n one halogen atom are usually
referred to a s polyhalogen c o m p o u n d s . Many of t he s e c o m p o u n d s are
Compounds useful in i n du s t r y a n d agriculture. Some polyhalogen c o m p o u n d s a r e
described in this section.
1 0 . 8 . 1 Dichloro- Dichloromethane is widely u s e d a s a solvent a s a paint remover, a s a
methane propellant in aerosols, a n d a s a process solvent in the ma nufa ctu re of
(Methylene drugs. It is also u s ed a s a metal cleaning a n d finishing solvent. Methylene
chloride) chloride h a r m s the h u m a n central nervous system. Exposure to lower
levels of methylene chloride in air c a n lead to slightly impaired hearing
a n d vision. Higher levels of methylene chloride in air cau se dizziness,
n aus ea, tingling a n d n u m b n e s s in the fingers a n d toes. In h u m a n s , direct
skin contact with methylene chloride c a us e s intense burning a n d mild
redness of t he skin. Direct contact with t he eyes c a n b u r n the cornea.
1 0 . 8 . 2 Trichloro- Chemically, chloroform is employed a s a solvent for fats, alkaloids,
methane iodine a n d othe r s u b s t a n c e s . The major u s e of chloroform today is in
(Chloroform) t h e pr odu ctio n of t h e freon refrigerant R-22. It wa s once u s e d a s a
general a n a e s th e t i c in surgery b u t h a s b e e n replaced by less toxic,
safer anaesthetics, s u c h a s ether. As might be expected from its u s e a s
a n a nae sthe tic , inhaling chloroform v a p ou r s d e p r e ss e s t h e central
n e r v o u s sys tem. Breathing a b o u t 9 0 0 p a r t s of chloroform pe r million
p a r t s of air (900 p a r t s per million) for a sho rt time c a n c a u s e dizziness,
fatigue, a n d headache. Chronic chloroform exposure ma y caus e damage
to t h e liver (where chloroform is metabolised to phosgene) a n d to t h e
kidneys, a n d s o me people develop so res w h e n t h e s k i n is i mm e r se d in
chloroform. Chloroform is slowly oxidised by air in t h e pre senc e of
light to a n extremely pois ono us gas, carbonyl chloride, also k n o w n a s
p h o s g e n e . It is therefore s t o r e d in closed d a r k c olo ured bot tles
completely filled so t h a t air is k ept o ut.

1 0 . 8 . 3 Triiodo- It w a s u s e d earlier a s a n antiseptic b u t t h e antiseptic properties a r e

methane d u e to t h e liberation of free iodine a n d n o t d u e to iodoform itself. D u e
(Iodoform) to its objectionable smell, it h a s b e e n replaced by oth er formulations
containing iodine.

1 0 . 8 . 4 Tetrachlo- It is p r o d u ce d in large qua ntit ies for u s e in t h e m a n u f a c t u r e of

ro m e t ha n e refrigerants a n d pr opel lant s for aerosol c a n s . It is also u s e d a s
(Carbon feedstock in t h e synt hes is of chlorofluorocarbons a n d other chemicals,
tetrachloride) ph armac eut ical man ufa ctur ing , a n d general solvent u s e . Until t h e
mid 1 9 6 0 s , it w a s also widely u s e d a s a cleaning fluid, b o t h in
i ndus try, a s a degreasing agent, a n d in t h e h o m e , a s a spot remover
a n d a s fire e x t i n g u i s h e r. T h e re is s o m e e vide nce t h a t e x p o s u r e to
carbon tetrachloride c a u s e s liver ca nce r in h u m a n s . The m o s t
c o mm o n effects are dizziness, light h e a d e dn e s s , n a u s e a a n d vomiting,
which c a n c a u s e p e r m a n e n t damage to nerve cells. In severe cases,
these effects c a n lead rapidly to s t u p o r, coma , u n c o n s c i o u s n e s s or
d e a t h . Ex p o s u r e to CCl 4 c a n m a k e t h e h e a r t b e a t irregularly or stop.
The chemical m a y irritate t h e eyes o n contact. When car bon
tetrachloride is released into t h e air, it rises to the atm osphe re a n d
depletes the ozone layer. Depletion of the

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 ozone layer is believed to increase h u m a n exposure to ultraviolet rays,
leading to i ncr ease d s k i n c anc er, eye di sea ses a n d disorders, a n d
possible di sru ptio n of t h e i m m u n e sys tem .
1 0 . 8 . 5 Freons The chlorofluorocarbon compounds of methane a n d ethane are collectively
kn own a s freons. They are extremely stable, unreactive, non-toxic, non-
corrosive a n d easily liquefiable gases. Freon 1 2 (CCl 2 F2 ) is one of t he
m o s t c o m m o n freons in i ndus tria l u s e . It is m a n u f a c t u r e d from
tetrachloromethane by Swarts reaction. These a re usually produced
for aerosol propellants, refrigeration a n d air conditioning purp ose s. By
19 74, total freon production in t h e world wa s a b o u t 2 billion p o u n d s
annually. Most freon, even t h a t u s e d in refrigeration, eventually m a k e s
its way into t he a tmos pher e where it diffuses u n c h a n g e d into t he
stratosphere. In stratosphere, freon is able to initiate radical cha in
reactions t h a t c a n u p s e t t h e n a t u r a l ozone balance (Unit 14, Class XI).
1 0 . 8 . 6 p,p’-Dichlo- DDT, t h e first chlorinated organic insecticides, w a s originally pr epa red
rodiphe nyl- i n 1 8 7 3 , b u t it w a s n o t u n t i l 1 9 3 9 t h a t P a u l Muller of Geigy
trichloro- Pha rmace uti cal s in Switzerland discovered t h e effectiveness of DDT a s
ethane(DDT) a n insecticide. Pau l Muller w a s a w a r de d t h e Nobel Prize in Medicine
a n d Physiology in 1 9 4 8 for this discovery. The u s e of DDT in cre ased
enormously on a worldwide bas is after World War II, primarily b eca use
of its effectiveness a gai nst t h e mosquito t h a t s p r e a d s mal ari a a n d
lice t h a t carry t y p h u s . However, problems related to extensive u s e of
DDT b eg an to a p p e a r in t h e late 1 9 4 0 s . Many species of insects
developed r esis tan ce to DDT, a n d it w as also discovered to have a
high toxicity t oward s fish. The chemical stability of DDT a n d its fat
solubility c o m p o u n d e d t h e problem. DDT is n o t metabolised very
rapidly by anim als; i nst ead, it is deposited a n d stored in t h e fatty
t i ss u e s . If ingestion c on ti n u e s a t a st ead y rate, DDT builds u p within
t h e a ni m a l over time. The u s e of DDT w as b a n n e d in t h e United
Sta t e s in 1 9 7 3 , a l th o u g h it is still in u s e in s o m e oth er p a r t s of t h e
world.

Summary
A l k y l / Aryl ha li des ma y be classified a s mo no , di, or polyhalogen (tri-, tetra-, etc.)
c o m p o u n d s dependi ng o n wh e t h e r they c o nt a i n one, two or mo re halogen a t o m s in thei r
s t ru c t u r e s . Since halogen a t o m s ar e mo re electronegative t h a n c arb on , t h e c a rb o n-
ha logen b o n d of alkyl halide is polarised; t h e c a r b o n a t o m b e a r s a part ial positive charge,
a n d t h e halogen a t o m b e a rs a partial negative ch arge.
Alkyl ha li des a re p re p a re d by t h e free radical ha l og e na ti o n of a l k an es , addition of
halogen acids to al kenes, re p l ac e me n t of –OH gro up of alcohols with ha logens u s i n g

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p h o s p h o r u s halides, thionyl chloride or halogen acids. Aryl hal ides a re p re p a re d by
el ectrophi lic s u bs ti tuti o n to a re n e s . Fluorides a n d iodides a re b e s t pr ep ar ed by halogen
exchange method.
The boiling point s of organohalogen c o m p o u n d s a re comparatively higher t h a n t he
corresponding h y d ro c a rb o n s b e c a u s e of s t ro ng dipole-dipole a n d v a n d e r Waals forces of
a t t ra c t i o n . These a r e slightly sol ubl e i n wa t er b u t completely so lubl e in o rganic s o l v e n t s .
Th e p ol a ri t y of c a r b o n - h a l o g e n b o n d of alkyl h a l i d e s is r e s p o n s i b l e for t h e i r
nucl eophili c su bs ti tuti o n, e l i m i na ti o n a n d their reaction with met al a t o m s to form
o r ga no m eta l l i c c o m p o u n d s . Nucleophilic s u b s t i t u t i o n re ac t i o ns a re categorised into

S N1 a n d S 2N o n t h e b a s i s of their kinetic properties. Chirality h a s a profoun d role in

u n d e r s t a n d i n g t h e reacti on m e c h a n i s m s of S N 1 a n d S N 2 reacti ons. S N 2 rea c t i on s of chiral
alkyl ha li des a re ch a rac t eri s e d by t h e inversion of configuration while S N 1 reac tion s a re
c h a ra c t e r i s e d by ra c e mi s a t i o n .
A n u m b e r of polyhalogen c o m p o u n d s e.g., d i c hl oro me tha ne , chloroform , iodoform,
carbon te tra c hl o ri d e , freon a n d DDT h a v e m a n y i n d u s t ri a l ap p l i ca t i o ns . However, s o me
of t h e s e c o m p o u n d s c a n n o t be easily d e co mpo s ed a n d even c a u s e depletion of ozone layer
a n d a re proving en v i ro n m e n ta l hazards .

Exercises
10.1 N a me t h e following h a l i de s acc ordin g to IUPAC s y s t e m a n d classify t h e m a s alkyl,
allyl, benzyl (primary, se c on d ary, tertiary), vinyl or aryl halides:
(i) (CH 3 ) 2 CHCH(Cl)CH 3 (ii) CH 3 CH 2 CH(CH 3 )CH(C 2 H 5 )Cl
(iii) CH 3 CH 2 C(CH 3 ) 2 CH 2 I (iv) (CH 3 ) 3 CCH 2 CH(Br)C 6 H 5
(v) CH 3 CH(CH 3 )CH(Br)CH 3 (vi) CH 3 C(C 2 H 5 ) 2 CH 2 Br
(vii) CH 3 C(Cl)(C 2 H 5 )CH 2 CH 3 (viii) CH 3 CH=C(Cl)CH 2 CH(CH 3 ) 2
(ix) CH 3 CH=CHC(Br)(CH 3 ) 2 (x) p-ClC 6 H 4 CH 2 CH(CH 3 ) 2
(xi) m-ClCH 2 C 6 H 4 CH 2 C(CH 3 ) 3 (xii) o-Br-C 6 H 4 CH(CH 3 )CH 2 CH 3
2. Give t h e IUPAC n a m e s of t h e following c o mp o u n d s :
(i) CH 3 CH(Cl)CH(Br)CH 3 (ii) CHF 2 CBrClF (iii) ClCH 2 C CCH 2 B r
(iv) (CCl 3 ) 3 CCl (v) CH 3 C(p-ClC 6 H 4 ) 2 CH(Br)CH 3 (vi) (CH 3 ) 3 CCH=CClC 6 H 4 I-p
10.3 Write t h e s t r u c t u r e s of t h e following organic halogen c o mp o u n ds .
(i) 2 - C h l o r o - 3 - m e t h y l p e n t a n e (ii) p -B r o mo c h l o r o b e n z e n e
(iii) 1-C hl o ro-4 -et h yl cy cl o h ex a ne (iv) 2-(2-C hlorophenyl )-1-iodooct ane
(v) 2 - B r o m o b u t a n e (vi) 4 -t e rt -B u t y l -3 -i od oh e p t a n e
(vii) 1 -B ro mo -4 -s e c -b u t y l -2 -me t h y l b e n z e ne (viii) 1 , 4 -D i b ro mo b u t -2 -e n e
1 0 . 4 W h i ch o n e of t h e following h a s t h e h i g h e s t dipole m o m e n t ?
(i) CH 2 Cl 2 (ii) CHCl 3 (iii) CCl 4
5. A hy d ro c a rb o n C 5 H 1 0 d oe s n o t rea c t with chlorine in d a r k b u t gives a single
monochloro c o mp o u n d C 5 H 9 Cl in bright sunl ight . Identify t h e hy d ro c arb on .
6. Write t h e iso mers of t h e c o m p o u n d having formul a C 4 H 9 Br.
7. Write t he e q ua t i o ns for t he p re pa rat i o n of 1-i odobutane from
(i) 1 - b u t a n o l (ii) 1 -c h l o ro b u t a n e (iii) b u t -1 -e n e .
8. W h at a re a m b i d e n t nucleophiles? Explain with a n example.

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 1 0 . 9 Which c o m p o u n d in e a c h of t h e following pa i rs will react faster in S N 2 reaction
with – OH?
(i) CH 3 Br or CH 3 I (ii) (CH 3 ) 3 CCl or CH 3 Cl
1 0 . 1 0 Predict all t h e a l k e n e s t h a t would b e formed by d e hy dro ha l o ge n at i o n of t h e
following halides with s o d i u m ethoxide in et hanol a n d identify t h e major alkene:
(i) 1-B ro mo-1 -me t h yl cy cl o h ex a ne (ii) 2 - C h l o ro -2 - me t h y l b u t a n e
(iii) 2 , 2 , 3 -Tri me t hy l -3 -b ro mo p e n t a n e .
1 0 . 1 1 How will you bring a b o u t t h e following conversions?
(i) E t h a n o l t o b u t - 1 - y n e (ii) E t h a n e t o b r o m o e t h e n e (iii) P r o p e n e
t o 1 - n i t r o p r o p a n e (iv) To l u e n e t o b e n z y l a l c o h o l (v) P r o p e n e t o p r o p y n e
(vi) Eth anol to ethyl fluoride (vii) B ro mom et h an e to p ro p an o ne (viii) But-1-ene to
b u t - 2-e n e (ix) 1 -C hl o ro bu t a ne to n-o c t an e (x) Benzene to biphenyl.
1 0 . 1 2 Explain why
(i) t h e dipole m o m e n t of chlorobenzene is lower t h a n t h a t of cyclohexyl chloride?
(ii) alkyl halides, t h o u g h polar, a re immiscible with wat er?
(iii) Gri g na rd re a g e n t s s h o u l d b e p r e p a r e d u n d e r a n h y d r o u s condi ti ons?
13. Give t h e u s e s of freon 1 2 , DDT, c a rb o n tetrachloride a n d iodoform.
14. Write t h e s t r u c t u r e of t h e maj or organic p ro d u c t in e a c h of t h e following reactions:

(i) CH 3 CH 2 CH 2 Cl + NaI

(ii) (CH 3 ) 3 CBr + KOH

(iii) CH 3 CH(Br)CH 2 CH 3 + NaOH

(iv) CH 3 CH 2 Br + KCN
(v) C 6 H 5 ONa + C 2 H 5 Cl
(vi) CH 3 CH 2 CH 2 OH + SOCl 2

(vii) CH 3 CH 2 CH = CH 2 + HBr
(viii) CH 3 CH = C(CH 3 ) 2 + HBr
15. Write t h e m e c h a n i s m of t h e following reaction:
nBuBr + KCN nB uCN
16. A r ra n g e t h e c o m p o u n d s of e a c h s e t i n o r d e r of re a ct i v i t y t o w a r d s S N 2
displacement:
(i) 2 -B ro mo - 2 - me t h y l b u t a n e , 1 -B r o mo p e n t a n e , 2 - B r o m o p e n t a n e
(ii) 1 -B romo -3-me t hy l b ut a n e, 2 -B ro mo-2 -me t h yl b u t an e , 2 -B romo -3-me t hy l b ut a n e
(iii) 1 - B r o m o b u t a n e , 1 - B r o m o -2 , 2 -d i m e t h y l p r o p a n e , 1 - B r o m o - 2 - m e t h y l b u t a n e ,
1-Bromo-3-methylbutane.
17. O u t of C 6 H 5 CH 2 Cl a n d C 6 H 5 CHClC 6 H 5 , which is mo re easily hydrolysed by a q u e o u s
KOH.
18. p-Dichlorobenzene h a s higher m.p . t h a n t ho s e of o- a n d m-iso mers.
Di s c u ss .
19. How t h e following convers ions c a n b e carri ed o u t ?
(i) P ro p en e to propan-1-ol
(ii) E t h a n o l to b u t -1 -y n e
(iii) 1 -B ro mo p r o p a n e to 2 - b r o m o p r o p a n e

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 (iv) Toluene to benzyl alcohol
(v) B e n ze n e to 4 -b ro mo n i t ro b e n z en e
(vi) Benzyl alcohol to 2 -p h e n y l e t h a n o i c acid
(vii) E t h a n o l to pro p an e ni t ri l e
(viii) Aniline to c h l oro b en ze n e
(ix) 2 -C h l o ro b u t a n e to 3, 4 -d i me t h y l h e x a n e
(x) 2 -Met h yl -1 -pro pe n e to 2 -c h l o ro -2 -me t hy l p ro p an e
(xi) Ethyl chloride to pro pa n oi c acid
(xii) B u t -1 -e n e to n-butyliodide
(xiii) 2 -C h l o ro p ro p a n e to 1 -p ro p a n o l
(xiv) Isopropyl alcohol to iodoform
(xv) C h l o ro b e n z e n e to p -n i t ro ph en o l
(xvi) 2 -B ro mo p r o p a n e to 1 - b r o m o p r o p a n e
(xvii) C h l o r o e t h a n e to b u t a n e
(xviii) B e n ze n e to di p h en y l
(xix) tert-Butyl bromide to isobutyl b romi d e
(xx) Aniline to ph e ny l i s oc y an i d e
20. The t r e a t m e n t of alkyl chlorides with a q u e o u s KOH l ea d s to t h e formation of
alcohols b u t in t h e p re s e n c e of alcoholic KOH, a l k e ne s a re ma j or p r o d u c t s . Explain.
21. P r i m a r y alkyl h a l i d e C 4 H 9 Br (a) r e a c t e d wi t h alcoholic KOH to give c o m p o u n d (b).
C o m p o u n d (b) is r e a c t e d wi t h HB r to give (c) w h i c h is a n i s o me r of (a). W h e n
(a) is r e a c t e d wi t h s o d i u m m e t a l it gives c o m p o u n d (d), C 8 H 1 8 w h i c h is different
from t h e c o m p o u n d fo r me d w h e n n - b u t y l b r o m i d e is r e a c t e d w i t h s o d i u m . Give
t h e s t r u c t u r a l f o r m u l a of (a) a n d write t h e e q u a t i o n s for all t h e r e a c t i o n s .
22. What h ap pen s when
(xxi)n - b u t y l chl orid e is t r e a t e d wi t h alcoholic KOH,
(xxii)b r o m o b e n z e n e is t r e a t e d wi t h Mg i n t h e p r e s e n c e of d ry e t h e r,
(xxiii)chlorobenzene is s u bj e c t ed to hydrolysis,
(xxiv)eth yl chl ori de is t r e a t e d wi t h a q u e o u s KOH,
(xxv)me t h y l b r o m i d e is t r e a t e d wi t h s o d i u m i n t h e p r e s e n c e of d ry e t h e r,
(xxvi)me t h y l ch lori de is t r e a t e d wi t h KCN?

Answers t o S o m e Intext Que s ti on s

10.1

2. (i) H 2 SO 4 c a n n o t be u s e d along with KI in t h e conversion of a n alcohol to a n

alkyl iodide a s it converts KI to co rrespo nding acid, HI wh ich is t h e n oxidised
by it to I 2 .
3. (i) ClCH 2 CH 2 CH 2 Cl (ii) ClCH 2 CHClCH 3 (iii) Cl 2 CHCH 2 CH 3 (iv) CH 3 CCl 2 CH 3

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 10.4 All t h e hydrogen a t o m s a re equivalent a n d re p l ac eme n t
of a n y hydrogen will give t h e s a m e p rod uc t .

The equivalent hydrog ens a re g ro u pe d a s a , b a n d

c. The r e p l a c e m e n t of e q ui v al en t h y d r o g e n s will
give t h e s a m e pro du c t .

Similarly t h e equivalent hy drogens a re g ro up ed a s

a, b, c a n d d. T h u s , four isomeric p r o d u c t s a re
possi ble.

10.5

1 0 . 6 (i) C h l oro met h a ne , B ro mo m et h an e, Di b ro mome t h an e, Bromoform.

Boiling point i n c rea s es with increase in molecular m a s s .
(ii) I s o p r o p y l c h l o r i d e , 1 - C h l o r o p r o p a n e , 1 - C h l o r o b u t a n e .
I s o p r o p y l c h l o r i d e b e i n g b r a n c h e d h a s lower b . p . t h a n 1 -
Chloropropane.
10.7 (i) CH 3 CH 2 CH 2 CH 2 Br Being pri mary halide, t he re won’t be a n y
st eri c h i n d r a n c e .
(ii) Secondary halide re ac t s fast er t h a n tertiary

halide.
(iii) The p re se n ce of methyl gro up closer to t h e
h a l i d e g r o u p will i n c r e a s e t h e s t e r i c
h i n d r a n c e a n d de c re a se t h e ra t e.

10.8 (i) Te r t i a r y h a l i d e r e a c t s f a s t e r t h a n s e c o n d a r y h a l i d e
b e c a u s e of t h e greater stability of tert -carbocation.

B e c a u s e of greater stability of s ec o nd a ry carbocat i on t h a n

(ii)
p r i m a r y.

10.9

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