HALOGEN COMPOUNDS

2) Vicinal dihalides: In these, the halogen atoms

SYNOPSIS
are attached to adjacent carbon atoms. These are
ALKYL HALIDES: Compounds derived called as alkylene halides.
from hydrocarbons by the replacement of one eg: CH2Cl–CH2Cl CH3–CHCl–CH2Cl
or more hydrogen atoms by the corresponding Ethylene chloride Propylene chloride
number of halogen atoms are known as Alkyl 3) Terminal dihalides:In these, both the
Halides. halogen atoms are attached to terminal carbon
HALOGEN DERIVATIVES OF ALKANES atoms. These are also called    halides or
(OR) HALOALKANES:- polymethylene halides.
 These are derived from the alkanes by the eg : CH2BrCH2CH2Br Trimethylene bromide
replacement of one or more hydrogen atoms by ClCH2CH2CH2CH2Cl Tetramethylene chloride
halogen atoms.  Terminal halides are also called as Poly
methylene halides.
H
RH R X  Trihalogen derivatives are also called as
L
K
A
N
E
A

X
L
K
Y
L
H
A
L
I
D
E
A

Haloforms.
Eg:- CHCl3 (Chloroform)
 Depending on number of halogen atoms present
 The general formula of trihalogen derivatives
in the halogen derivative, they are classified as
mono, di, tri and tetra halogen derivatives is Cn H 2 n 1 X 3 .
Eg:- Halogen derivatives of unsaturated
CH H H H H hydrocarbons: Replacement of some
CH 3 X CHX 3 CX
E
T
R
A

CH 2 X 2
T
M
O
N
O

T
R
I

4
D

X X  X  X
4

hydrogen atoms in alkenes or alkynes by some

CLASSIFICATION OF ALKYL HALIDES:- halogen atoms yields these compounds.
Monohalogen derivatives : Monohalogen Vinyl chloride CH2=CH–Cl
derivatives of alkanes are called alkyl halides. Allyl chloride CH2=CH–CH2Cl
 They have the general formula RX, where R is  In vinyl halides halogen atom is bonded to
an alkyl group and X is a halogen atom. vinylic carbon i.e. one of the carbon atoms C=C
eg : CH3Cl, C2H5Br, C3H7I, etc. Eg:- H 2C  CH  Cl
 Alkyl halides are classified as primary,
secondary and tertiary depending on whether Br
the halogen atom is attached to a primary,
secondary and tertiary carbon atom respectively
-
B
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1

Dihalogen derivatives:Dihalogen derivatives

of alkanes are derived by the replacement of two
hydrogen atoms by two halogen atoms.  In vinyl halides halogen atom is bonded to sp2
 The dihalogen derivatives are mainly of three carbon.
types.  In halo alkynes halogen atom is attached to one
1) Geminal dihalides: In these, both the halogen of the carbon atoms of C  C .
atoms are attached to the same carbon atom. Eg;- HC  C  Br Bromo ethyne
These are called alkylidene halides.
Cl H 3C  C  C  Cl 1 - Chloro prop 1 yne
CH3 C CH3
eg : CH3 CH  In Allylic halides halogen atom is bonded to
Cl Br Br allylic carbon i.e. sp3 carbon attached to sp2
Ethylidene chloride Isopropylidene bromide carbon.


)
2
In Allylic halides also halogen atom is bonded
to sp3 carbon. H 2C  CH  CH  CH 3
Eg:-
Br

0
2
H 2C  CH  CH 2  Cl

3
l
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a
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)
a

IUPAC name: 3 chloro prop -1 - ene

Common name: Allyl chloride
 Allylic halides may be 10, 20 or 30.
Eg;-
NOMENCLATURE: In common system
alkyl part is named first followed by the name
of halogen.
Eg:- CH 3  Cl Methyl chloride
CH 3  CH 2  Br Ethyl bromide

COMMON AND IUPAC NAMES OF SOME HALOGEN DERIVATIVES

S.No. Structure Common name IUPAC name

1 C

3CH2CH2CH2Cl
H n-Butyl chloride 1-Chlorobutane
2 (CH3)2CHCH2Cl Iso-butyl chloride 1-Chloro-2-methylpropane
3 CH3CH(Cl) CH2CH3 sec-Butyl chloride 2-Chlorobutane
4 (CH3)3CBr tert-Butyl bromide 2-Bromo-2-methylpropane
5 (CH3)3CCH2Br neo-Pentyl bromide 1-Bromo-2,2-dimethylpropane
6 CH2=CHCH2Cl Allyl chloride 3-Chloropropene
7 CH2Cl–CH2Cl Ethylene di chloride 1,2-Dichloroethane
8 CH3–CHCl2 Ethylidene chloride 1,1–Dichloroethane
9 CHCl3 Chloroform Trichloromethane
10 CCl4 Carbontetrachloride Tetrachloromethane
11 CF3CHClBr Halothane 2-Bromo-2-chloro-1,1,1-trifluoroethane
Cl
12 ortho-Chlorotoluene 1-Chloro-2-methylbenzene
CH3
CH2Cl
13 Benzyl chloride Chlorophenylmethane
CHCl2
14 Benzal chloride Dichlorophenylmethane
Br

15 sym-Tribromobenzene 1,3,5-Trimethylbenzene
Br Br
 Preparation methodS of alkyl halides:  Groove’s reaction is nucleophilic substitution
From alcohols: Alkyl halides are prepared from reaction in which the nucleophile i.e halide ion
alcohols by replacing -OH group of alcohols by attacks the protonated alcohol with the expulsion
halogen atom. of H 2O  a good leaving group by the formation
Cn H 2 n 1OH  HX  Cn H 2 n 1 X  HOH of a protonated alcohol.
Alkylhalide 
R  OH  H   R  OH 2

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Eg : R  OH  HX  R  X  H 2O
 Alkyl halides can be prepared by treating

alcohols either by R  OH 2  X   R  X  H 2O
1) Hydrogen Halides (HX)
2) Phosphorous Halides  PCl3 , PCl5 

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3) Thionyl Chloride  SOCl2 
 The purpose of anhydrous ZnCl2 in Groove’ss
Preparation of alkyl halides by Hydrogen process is to help the cleavage of C-O bond
Halides: (GROOVE’S PROCESS)
because anhydrous ZnCl2 is a Lewis acid
 The order of reactivity of halogen acids is
HI  HBr  HCl (Parallel to their acidity  H
C H 3  C H 2  O H  ZnC
 l2
 CH 3  CH 2  O 
order of nucleophilicity I   Br   Cl  ) ZnCl2

 Order of reactivity of alcohols

Cl 
CH 3  CH 2  Cl

 There can be 1,2 hydride or 1,2 methyl shift to

attain a greater stability of carbocation
Eg.
 The reaction of conc. HCl and anhydrous
ZnCl2 is known as Groove’s process.
R  OH  HCl 
anhyd . ZnCl2
R  Cl  H 2O
 Conc. HCl and anhydrous ZnCl2 is known as
Lucas reagent
 The reaction rates with Lucas reagent for
different types of alcohols follows the order
3o  2o  1o
1o alcohol   No turbidity appears
Lucas Re agent

2o alcohol   turbidity appears with

Lucas Re agent

in 5 min
3o alcohol 
Lucas Re agent
 turbidity appears
immediately
 Conc. HCl does not react with 1o alcohols in
presence anhyd. ZnCl2
W.E-1: Find the products in the following  Bromo alkanes are prepared from HBr and
Conc. H 2 SO4
R  OH  HBr  
Conc . H 2 SO4
 R  Br  H 2O
Eg:-
? CH 3  CH  OH  HBr 
H 2 SO4
 CH 3  CH  Br  H 2O

CH 3 CH 3

-
P
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-
b
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2

2
Sol:
 HBr is genarated by the action of conc.
H 2 SO4 on KBr
KBr  H 2 SO4  HBr  KHSO4
CH 3  CH 2  OH  HBr 
Conc . H 2 SO4
CH 3  CH 2  Br  H 2O

Preparation of alkyl halides from

phosphorous halides: Chloro alkanes are
prepared by the action of
either PCl3 or PCl5 on alcohols.
3R  OH  PCl3  3R  Cl  H 3 PO3
[Basicity = 2]
R  OH  PCl5  R  Cl  POCl3  HCl
Eg:-
3 CH 3  CH  CH 3  PCl3  3 CH 3  CH  CH 3  H 3 PO3

OH Cl
 Similary bromo alkanes are prepared by the
action of PBr3 on alcohol
P4  6 Br2  4 PBr3
 Normally free radicals do not undergo 3R  OH  PBr3  3R  Br  H 3 PO3
rearrangement Preparation of alkyl chloride from
 Hence neo pentyl chloride from neo pentane is
alcohols using thioNyl chloride  SOCl2  :
obtained by photo chemical free redical
chlorination R  OH  SOCl2 
Pyridine
R  Cl  SO2   HCl
Cl2 
hr
 2Cl .  This method is known as Darzen’s method.
 This is the best method to get good yield of alkyl
CH 3 CH 3
chlorides because the by products are gases

+

Alkyl bromides and iodides cannot beobtained

+

CH 3  C  CH 3 Cl CH 3  C  CH 2

H  Cl
by this method because SOBr2 is unstable while
CH 3
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CH 3
B

SOI 2 do not exist.

CH 3
Halogen exchange method: Iodo alkanes
CH 3
can easily be obtained from corresponding
+
+


CH 3  C  CH 2 C l2 C H 3  C  C H 2C l Cl  bromoalkanes or chloro alkanes by heating with
CH 3 CH 3
NaI in acetone.
N
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CH 3  CH 2  Br  NaI 
Acetone
CH 3  CH 2  I  NaBr
 This reaction is called Finkelstein reaction.  This reaction is known as Swart’s reaction
 It is based on the fact that NaBr being  Allylic and Benzylic compounds are both more
lesssoluble than NaI in acetone gets deposited reactive than saturated compounds in radical
as a result equilibrium shifts towards the forward catalysed halogenation.
direction.  N-Bromo succinimide (NBS) is used for
Halogenation of alkanes: bromination generally at allylic and Benzylic
position.
Cn H 2 n  2 
X2
 HX
 Cn H 2 n 1 X
Alkane Alkylhalide
R  H 
X2
 R  X  HX

W.E-2: Which one of the following is the best

condition for the better yield of CH 3Cl during
the chlorination of methane in presence of
sunlight
h
CH 4  Cl2  
a) b) CH 4  Cl2 
hv

Excess
Eg:
h
CH 4  Cl2 
c) d) CH 4  Cl2 
dart

Excess
Sol. ' c ' because chlorine free radicals formed will Borodine-Hunsdiecker Reaction:
 This reaction is used to descend series
colloide with excess of CH 4 molecules again
RCOOAg  Br2 
CCl4
 R  Br  CO2  AgBr
and again to give CH 3Cl as a main product.
 The yield of alkyl halides follows the order
Iodination: Iodination of alkanes is a slow 10  20  30
and reversible process because of formation of
 Yield of alkyl chloride is less than alky
strong reducing agent HI, as a by product which
reduces iodo alkane back to alkane. bromide
 It follows free radical mechanism.
CH 4  I 2  CH 3 I  HI
 

 Hence Iodination is carried out in presence of RCOOAg  Br2  RCOOBr  AgBr
strong oxidising agent like HIO3 (Iodic acid) or RCOOBr  Br .  RCOO .
HIO4 (per iodic acid) or HNO3 , or HgO which RCOO.  R.  CO2
converts HI to I 2 or destroy HI. R.  Br2  RBr  Br .
5 HI  HIO3  3I 2  3H 2O  Iodine forms esters instead of alkyl halide
2 HI  2 HNO3  I 2  2 H 2O  2 NO2  This reaction is known as Birnbaumsimmonini
2HI  HgO  HgI 2  H 2O reaction.

Fluorination: Fluoro alkanes can be obtained 2 RCOOAg  I 2  RCOOR  CO2  2 AgI

either by carrying out the reaction by dilluting
fluorine with an inert gas like nitrogen or
argon or more conveniently by halogen 1.
exchange method using inorganic fluorides
such as
SbF3 , AgF , Hg 2 F2 , CoF2 etc.
2C2 H 5 Br  Hg 2 F2  2C2 H 5 F  HgBr2
Physical properties of alkyl halides:
For the same alkyl group the order of B.P
is R  I  R  Br  R  Cl  R  F
2. For the same halogens B.P decrease as the size
of the alkyl part decreases
CH 3  CH 2  CH 2  X  CH 3  CH 2  X  CH 3  X
3. The decreasing order of B.P among the isomeric
Chemical properties: Alkyl halides
alkyl halides is 1o  2o  3o generally gives two types of reactions. They are
* Nucleophilic substitution reactions
* Elimination reactions
Eg. S N2 mechanism: The type of concerted
substitution reaction in which bond breaking and
bond making occur at same time is known as
4. Decreasing order of density among the alkyl
halides will be SN 2 reaction.
RI  RBr  RCl  RF  The reaction of CH 3 Br with CH 3COO  is an
5. For alkyl iodides decreasing order of density
example of SN 2 reaction.
is CH 3  I  CH 3  CH 2  I  CH 3  CH 2  CH 2  I
6. Bond strength of C-X bond follows the order
CH 3  F  CH 3  Cl  CH 3  Br  CH 3  I
7. Order of dipole moment is
CH 3  Cl  CH 3  F  CH 3  Br  CH 3  I
Substrate Nucleophile product leaving
8. Stability of C-X bond decreases as the strength group Kinetics:
of the C-X bond decreases. Thus stability order
of R-X is R  F  R  Cl  R  Br  R  I Rate  K [CH 3 Br ][CH 3COO  ]
9. It is alkyl iodide only decomposes in the
 An SN2 reaction exhibits second order kinetics.
presence of sunlight. Which iodide on standing
That the reaction is bimolecular and both alkyl
becomes violet or brown. 2 RI 
hv
 R  R  I2 halide and nucleophile appear in the rate
Aliphatic nucleophilic substitution equation.
reactions: Replacement of an atom or group Mechansim: The C-Br bond breaks as the C-
by another atom or group is known as O bond forms
substitution reaction
 If the reaction is carried out by a nucleophilie,
then it is known as nucleophilic substitution
reaction.
 Generally a nucleophilic substituion reaction
is represented as R  L  Nu   R  Nu  L Stereo chemistry of SN2 reaction:
Where L is a leaving group Nu  is a incoming
nucleophilie
 Nucleophiles may be neutral or negatively
charged, where as substrate undergoing
nucleophilic substitution may be neutral or
positively charged
Eg: Nu  replaces Br  from the opposite side
CH 3  Cl  CN   CH 3  CN  Cl 
  All SN2reactions proceed with back side attack
CH 3  O H 2  I   CH 3  I  H 2O of nucleophilie, resulting in inversion of
CH 3  OTS  NH 3  CH 3  NH 2  TsOH configuration at a stereogenic centre.
OTS = Tosylate  Inversion of configuration in an SN2 reaction is
It is the best leaving group. called as Walden inversion
W.E-3:Write the product in the following S N2 4. Polar aprotic solvents are especially good for
reaction SN2 reactions.
5. Presence of hetero atom on   carbon in
halides also increases reactivity of substrate for
SN2 reaction, lone pair of electrons present on
hetero atom stabilize the stability of transition
state by resonance.
Eg:

Sol: Br  is the leaving group and CN  is the nu

cleophile 6. Presence of carbonyl group at   carbon is
one of the most suitable substrate for SN 2
reaction. Electron with drawing groups always
increases the rate of SN2 reaction.
Eg:

7. Vinyl and aryl halides do not undergo SN2

reaction.
W.E-4:Which SN2 reaction is faster in each pair.

 Back side attack converts the starting material

which has two group, cis to each other, to a
poduct with two groups trans to each other
because the nucleophile CN  attacks from
below the plane of the ring.
Factors affecting rate of SN2 reactions:
1. As the no. of ‘R’ groups on carbon with leaving
group increases, the rate of SN2 decreases Sol. (i) A  B (ii) A  B (iii) B  A (iv) A  B

Characteristics of SN2 mechanism:

2. A better leaving group increases the rate of SN2

reactions.
Eg: CH 3  F  CH 3  Cl  CH 3  Br  CH 3  I
3. Since S N 2 involves the substrate and the
nucleophile the rate of reaction depends largely
on the concentration of nucleophile so strong
nucleophiles present in high concentration
favour SN2 reaction.
 SN1 reaction: The reaction of  CH 3 3 CBr  Because there is no preference for nucleophilic

with CH 3COO is an example of S N 1
mechansim.
 SN1 reactions proceed with racemization at a
W.E-5: Find the major product in the following.
Kinetics: The SN1 reaction exhibits first order
kinetics. Rate  k  CH 3 3 CBr 
Sol.
Mechanism: SN1 mechanism invloves two
steps.
 In this mechanism bond breaking occurs before
bond making.
Step-1 :
1.
Step-2:
2.
Stereo chemistry of SN1 reaction :
3.
4.
 Loss of the leaving group in Step-1 generates a
planar carbocation that is now achiral.
 Attack of the nucleophile in Step-2 can ocur
from either side to afford two products B and
C. These two products are different compounds 5.
containing one stereogenic centre.
 B and C are stereo isomers i.e. enantiomers.
attack from either direction, an equal amount
of two enantiomers are formed i.e. a Racemic
Mixture is formed.
single stereogenic center.
Factors affecting rate of SN1 reactions :
As the number of R groups on the carbon with
the leaving group increaes, the rate of SN1
reaction increases.
Ex:
A better leaving group increases rate of SN1
reactions.
Ex:-
Since, SN1 reaction is unimolecular, involving
only alkyl halide, so the identity and
concentration of the nucleophile have no effect
on the reaction rate.
Polar protic sovents like H 2O , R  OH ,
HCOOH , CH 3COOH are especially good for
S N1 reaction, because polar protic solvent
solvate carbocation by ion dipole interaction
and leaving group is solvated by hydrogen
bonding.
SN1 reactions are highly favoured if there is a
hetero atom at the   carbon, because it highly
stabilise the carbocation.
Ex:
 W.E-6:Determine the mechanism of nucleophilic
substitution for each reaction and draw the
products.
(a) CH 3  CH 2  CH 2  Br  : C  CH 

6. Vinyl and aryl halides do not undego S N 1 Sol. (a) The alkyl halide is 10 so it must react by an
reactions beause they form highly destabilised SN2 mechanism
carbocation.
Ex:

Elimination Reactions: Reactions in which

7. Because of its rigid structure, bridge head C-
atoms cannot assume planarity, hence
heterolysis leading to formation of carbocation 
is also prevented. The bridge head C-atoms are
resistant towards SN1 and SN2
Ex:
two atoms or groups are removed from a
compound are known as elimination reactions.
There are two mechanisms for elimination. They
are (i) E2 mechanism (ii) E1 mechanism.
 The E2 and E1 mechanisms differ in the timing
of bond cleavage and bond formation.
E2 Mechanism: The type of elimination
reaction which proceed through strong bae

8. Substrate containing carbonyl group on (alc.KOH, C2 H 5O  , NaNH 2 ,  CH 3 3 C  O 

  carbon does not give SN1 reaction because
carbonyl has strong-I power which destabilise 
the carbocation intermediate.
Ex :
.
CHARACTERISTICS OF SN1 MECHANISM:
etc is known as elimination reaction.
Such reactions occur in one step.
 In E2 reaction as the stability of transition state
increases, rate of reaction increases.
 The most common mechanism for dehydro
halogenation is the E2 mechanism.
Ex:

Kinetics: An E2 reaction exahibits second

order kinetics. Hence the reaction is bimolecular
and both the alkyl halide and the base appear in
the rate equation.
Rate  K[(CH3 )3 C  Br] OH  
 Mechanism:In E2 mechanism all bonds are  E2 reaction is regeoselective which means that
broken and formed in single step. more of one constitutional isomer is formed
than the other.
Ex:

 E2 reaction is also stereo selective which means

Characteristics of E2 Mechanism:
that More of one stereo isomer is formed than
Characteristic Result the other.
1. Kinetics Second Order Ex:
2. Mechanism One step
3. Identity of R (i) More substituted
halides react fastest
(ii) Rate :
R3CX  R2CHX  RCH 2 X The E1 mechanism: Type of elimination
4. Base Favoured by strong bases reaction,which proceed in two steps,in which
5. Leaving group Better leaving group  faster first step is slow ionisation to form carbocation,
reaction while the second step is fast attack of base to
produce more substi tuted alkene (Saytzeef
6. Solvent Favoured by polar aprotic alkene).
solvents
 The dehydrohalogenation of  CH 3 3 CI with
W.E-7: Predict the major products in the following H 2O to form  CH 3 2 C  CH 2 can be used to
explain E1 Mechanism.
E2 reaction

Kinetics: An E1 reaction exhibits first order

Sol. kinetics. Rate  k  CH 3 3 CI 
Mechanism: E1 mechanism is a two step
mechanism.
Step-1 :
Step-2 : Determining whethera Alkyl Halide
reacts by an S N 1 , S N 2 E1 or E2
Mechanisms:
 30 Alkyl halide + Strong Base  E2 Product
Ex:
 The E1 and E2 both mechanisms involve the
same number of bonds broken and formed. The Br
CH 3

+
only difference is the timing.
CH3  C  CH3 OH  CH 3  C  CH 2

E
2
 In an E1 reaction the leaving group comes offf
CH3
before the   proton is removed and the

t
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b
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P
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S

E
2
reaction occurs in two steps.
 In an E2 reaction, the leaving group comes offf  30Alkyl halide + weak nucleophiles or bases
as the   proton is removed and the reaction  SN1 product + E1 product
occurs in one step.
Characterisitics of E1 Mechanism :
Characteristic Result

1. Kinetics First Order

2. Mechanism Two step
3. Identity of R (i) More substituted
halides react fastest
(ii) Rate :
 10Alkyl halide + Strong nucleophiles or bases
R3CX  R2CHX  RCH 2 X
 SN2 product
4. Base Favoured by weaker bases
like H 2O and ROH CH 3  CH 2  Br  OH  
SN 2
 CH 3  CH 2  OH
5. Leaving group Better leaving group Strong nucleophile
makes the reaction faster.
 10Alkyl halide + Strong Sterically hindered
6. Solvent Favoured by polar aprotic
bases  E2 product
solvents
CH 3  CH 2  Br  K  O  (CH 3 )3 C 
E2
 CH 2  CH 2
W.E-8:Which elimination reaction in each pair is
faster.  20Alkyl halide + Strong bases & nucleophiles
 E2 product + SN2 product

Sol. (i) P (ii) Q (iii) P

 20Alkyl halide + Strong sterically hindered
bases  E2 product

For SN1:

 20Alkyl halide + Weak nucleophiles or bases

For E1
 SN1 product + E1 Product

W.E-9:Write the products of the following reaction.

Sol. In this case alkyl halide is 20 and  CH 3O   is  In this reaction, these products are formed:
a strong base and nucleophile, so products of one from an S N 1 reaction and two from E1
both S N 2 and E2 mechanisms are formed. reactions.
W.E-10: Write the products formed in the
following reaction and include the
mechanism showing how each product is
formed.

Sol. In this case alkyl halide is 30 and the reagent

 CH 3OH  is a weak base and nucleophile, so
Chemical properties: The reactions of
products of both S N 1 and E1 mechanisms are haloalkanes may be divided into the
formed. following categories
 Both mechanisms begin with the same first step a) Nucleophilic substitution
i.e. loss of the leaving group to form a b) Elimination reactions
carbocation. c) Reaction with metals
 Action of aqueous KOH:Haloalkanes on C2H5NH2 + ClC2H5 
HCl
 (C2H5)2NH
treating with boiling aqueous alkali solution give (Secondary amine)
alcohols. (C2H5)2NH + ClC2H5   (C2H5)3N
HCl

C2 H 5Cl  CH Ethyl 3  CH 2OH

aq . KOH / NaOH
(Tertiary amine)
alcohol
–
 Action of moist silver oxide: Haloalkanes (C2H5)3N + ClC2H5 
 [(C2H5)4N]+ Cl
are hydrolysed to corresponding alcohols by
 Action of NaBr or KI: Alkyl chlorides react
moist silver oxide.
Ag2O + H2O   2AgOH
with sodium or potassium bromide or iodide to
form alkyl bromide or alkyl iodide. The reaction
C2H5Cl + AgOH   C2H5OH + AgCl is conducted with acetone as solvent.
 Action of alcoholic KCN: Haloalkanes on
C2 H 5Cl  Na Br 
 C2 H 5 Br  NaCl
treatment with alcoholic potassium cyanide
solution give alkane nitriles as the major product C2 H 5Cl  KI 
 C2 H 5 I  KCl
with a small amount of isocyanide. KCN is  Action of Sodium ethoxide ( Williamson’s
predominantly ionic
synthesis): Ethers are formed when
 alcoholic   CH 3  CH 2CN  ethyl cyanide 
C2 H 5Cl  KCN
haloalkanes are treated with alcoholic sodium
 Action of AgCN: Alkyl halides react with or potassium alkoxide. This reaction is known
aqueous ethanolic silver cyanide to form alkyl as “Williamson’s synthesis”.
isocyanide as major product with a small amount CH 3  CH 2  ONa
C2 H 5Cl  C2 H 5  O  C 2 H 5
of alkyl cyanide. Silver cyanide is mainly
covalent.  This reaction can also be carried with dry silver
oxide.
C2 H 5Cl  CHethyl
3  CH 2 NC
AgCN

iso cyanide
R–X + Ag–O–Ag + X–R 
 R–O–R + 2AgX
 Action of KNO2: Alkyl halides react with
potassium or sodium nitrite to give nitro ethane C2H5Cl+AgOAg+ClC2H5 

as the major product. Dimethyl formamide C2H5–O–C2H5+2AgCl
(DMF) is used as solvent. About 30%  Action of Benzene:[Friedel-Craft’s
ethylnitrite is formed. alkylation]: Alkyl halides react with benzene
C2 H 5Cl   
potassium Nitrite / DMF
KNO2  aqueous ethanolic 
in the presence of anhydrous aluminium halides
(Lewis acids) to form alkyl benzene.
CH 3  CH 2  O  N  O  CH 3  CH 2  NO2
6 6   3
C H  anhy AlCl
Ethyl nitrite(30%) Nitro ethane (70%) C2 H 5Cl   C6 H 5CH 2  CH 3
ethyl benzene
 Action of AgNO 2: On treating ethanolic
solution of halo alkanes with silver nitrite, the  Action of CH3COOAg:Alkyl halides react
major product formed is alkyl nitrite and the with silver acetate in alcoholic solution to form
minor product is nitroalkane. esters.
C2 H 5Cl 
AgNO2
 CH 3  CH 2  NO2  CH 3  CH 2  O  N  O C2 H 5Cl 
CH3COOAg
 CH3  COOC2 H5
(Minor) (Major) ethyl acetate
Reaction with ammonia: On heating with Reaction with Metals:
aqueous or alcoholic solution of ammonia in a Action of magnesium: Alkyl halides form
sealed tube at 100°C, alkyl halides yield a Grignard reagents when treated with magnesium
mixture of amines and quaternary ammonium
powder in dry ether.
salt.
dry
R–X + NH3   R–NH2 + HX R–X + Mg 
ether
 R–Mg–X
C2H5Cl + NH3   C2H5NH2 dry
HCl C2H5Cl + Mg 
ether
 C2H5MgCl
(Primary amine)
 Action of Sodium (Wurtz reaction ): Alkyl CH3  C  CH 2  H 2  CH3  CH – CH3
halides react with sodium in dry ether to give | |
CH3 CH3
hydrocarbons containing double the number of
(56) (58)
carbon atoms present in the alkyl halide. This Now 56 g of isobutene gives 58 g of isobutane.
reaction is known as Wurtz reaction. 58  7
 7 g of isobutene gives = 7.25 g of
2C2 H5Cl 
CH3CH2CH2CH3  2NaCl
Wurtzreaction
Sodium/ Dryether
56
isobutane
 Reduction:Alkanes are formed when alkyl
halides are reduced with nascent hydrogen W.E-12:Predict the product(s) of the reaction.
obtained by Zn and HCl or sodium and alcohol
- +
or lithium aluminium hydride or hydrogen in Br  S Na  
H3C
the presence of Nickel or Palladium.
(a) To what functional group classes do the
C2 H 5Cl   CH 3CH 3
Re duction

Ethane
Elimination reaction;
 Dehydrohalogenation: Ethyl chloride
undergoes dehydrohalogenation with alcoholic
KOH and forms alkenes. Alc.KOH acts as
dehydrohalogenating agent.
C2 H 5Cl  alc . KOH
 CH 2  CH 2
MISCELLANEOUS SOLVED EXAMPLES
W.E-11: A 10 gm mixture of isobutane and
isobutene requires 20 gm of Br2 (in CCl4) for Sol. (a) One reactant is an alkyl halide, the other is a
complete addition. If 10 gm of the mixture is
catalytically hydrogenated and the entire
alkane is monobrominated in the presence of
light at 127ºC, which exclusive product and
how much of its would be formed? (At. Wt. of
bromine = 80).
Sol. isobutane + isobutene
ag bg
 a + b = 10 g
Br
|
CH3  C  CH 2  Br2  CH 3 – C – CH 2 Br ;
| |
CH3 CH3
CH3  CH – CH 3  Br2  No addition
reactants belong?
(b) Does either reactant have a leaving group?
(c) Are any of the reactants acids, bases, nucleo
philes, or electrophiles?
(d)What is the most likely first step for the
reaction? Most common reactions classified
as either protonation – deprotonation reactions
or reactions of a nucleophile with an
electrophile.
(e)What are the properties of the species
present in the reaction mixture after this first
step? Is any further reaction likely to occur?
sulfur anion (remember that sodium ions are
usually spectator ions, they are to balance charge
but not to participate in the reaction).
(b) Yes, the bromine atom in 1-brompropane is
a leaving group.
(c)The sulfur anion is a nucleophile. The alkyl
halide contains an electrophilic carbon atom.
(d) No strong acids (pKa < 1) or bases (pKa of
conjugate acid > ~13) are present this reaction
mixture so a protonation-deprotonation reaction
is not probable. Reaction of the nucleophilic
sulfur atom with the electrophilic carbon atoms
is most likely.
 S
 Br H3C
H3C


|
CH3 
Br
(56) (80 × 2) S

160 g of Br2 reacts with 56 g of isobutene

(e) All species formed are stable. No further
56  20
 20 g of Br2 reacts with = 7 g of reaction will occur. The complete equation is:
160
S
isobutene (b) Br  -
S Na
+

 H3C  Na+Br
 amount of isobutane is = a = 10 – 7 = 3 g H3C
W.E-13:Treatment of 2-bromobutane with hot W.E-15:A hydrocarbon (A) of molecular weight
alcoholic KOH gives a mixture of three 54 reacts with excess of Br2 in CCl4 to give a
isomeric butenes (A), (B) and (C). Ozonolysis compound (B) whose molecular weight is
of the minor product (A), gives formaldehyde 593% more than that of (A). However on
and another aldehyde in equimolar amounts. catalytic hydrogenation with excess of
Both (B) and (C) gave the same single product hydrogen (A) forms (C) whose molecular
(D) on ozonolysis. What are the structural weight is only 7.4% more than that of (A). (A)
formula of (A), (B), (C) and (D) ? reacts with CH 3CH2Br in the presence of
NaNH2 to give another hydrocarbon (D) which
Sol. CH 3 – CH – CH 2 – CH 3  on ozonolysis yields diketone (E). (E) on
|
Br oxidation gives propanoic acid. Give structures
of (A) to (E) with reasons.
Alc. KOH
CH3 —CH2 —CH = CH2 (A)
Compound (A) 
Br2 / CCl4
 Compound (B)
(20%) Molecular weight 54 excess
Molecular weight
CH3CH2Br
(593% more than A)
in NaNH2

Catalytic
Hydrogenation
(C)
(D) Molecular weight 7.4% of (A)
O3
Alc. KOH Sol.
CH3—CH=CH—CH3 (Cis & Trans) Diketone (E)
(B and C) (80%) (Major product) (O)

Diketone (E)
O3

CH3 – CH2 – CH = CH2 Zn / H 2 O CH3CH2CHO
100gm of (A) add Br2 and the new weight is 593gm
O3
  54 gm of (A) add Br2 and the new weight is
+ HCHO (B,C) CH3 – CH = CH – CH3 Zn/H2O
593  54
2CH3CHO = 320.2 gm  No. of moles of
100
Weight 360.2
Br2=  = 2 mole
W.E-14:Alkyl halide are most often prepared from Molecular weight 160
alcohols, rarely by direct halogenation, supply (i) As two moles of Br2 adds hence compound
structure formulas for the alkyl halides has two p bonds hence general formula should
synthesized in the reactions. (CnH2n–2) CnH2n-2 = 54 ; 12n + 2n – 2 = 54;
NaBr, H 2SO4
n = 4  molecular formula = C4H6
(a) CH3CH2CH2CH2CH2OH  
 (ii) (A) reacts with CH3CH2Br in presence of
NaNH2Compound (A) should be terminal
Conc. HCl
(b) (CH3)3COH   alkyne i.e. 1-butyne
room temp.
Br

(c) CH3CH(OH)CH2CH2CH3 PBr3 CH 

Br2
 H3C
  CCl 4
Br
H3C (A) Br
PI3 (form P  I2 )
(d) CH3CH2CH2OH   CH3CH2Br Br
in NaNH2 CH3
SOCl2
(e) Me2CHCH2OH  
C 2H5

Catalytic
Hydrogenation
 H3C
(C)
Sol. (a) CH3CH2CH2CHBrCH3 H3C (D)
O3
(b) (CH3)3 CCl O

(c) CH3 – CH – CH2CH2CH3

| H3C C 2H5
Br
O
(d) CH3CH2CH2I (O)

(e) Me2CHCH2Cl 2CH3CH 2 COOH

W.E-16:How will you bring about the following (g) 1-Chlorobutane to n-octane
conversions in not more than two steps ? CH 3  CH 2  CH 2  CH 2  CH 2  CH 2  CH 2  CH 3  2NaCl
n  oc tan e
(a) Ethene to bromoethene
(b) Propene to 1-nitropropane (h) Bromoethane to cis-hex-3-ene
(c) Propene to propyne 2C 2 H 5 Br + NaC  CNa   CH3 –
bromoethane 2NaBr
disodium
(d) Ethanol to ethyl fluoride ethylide
(e) Bromomethane to propanone
 H 2 , Pd
(f) But-1-ene to but-2-ene CH2 – C  C – CH2 – CH3 
heat

(g) 1-chlorobutane to n-octane H H
(h) Bromoethane to cis-hex-3-ene C=C
(i) Benzyl alcohol to phenylethanenitrile CH3CH2 CH2CH3
(j) Benzene to biphenyl
(k) Cyclopentene to cyclopenta-1, 3-diene (i) Benzyl alcohol to phenylethanenitrile
(l) Aniline to phenyl isocyanide CH2OH CH2Cl
Sol. (a) Ethene to bromoethene KCN (alc.)
+ SOCl2 
 

CH2= CH2+Br2(g)  500ºC BrCH = CH2 + HBr heat
ethene bromoethene Benzyl alcohol
(b) Propene to 1-nitropropane
CH2CN
CH3 – CH = CH2 + HBr  peroxide
 CH3 – CH2
AgNO 2 (ethanol) + KCl
– CH2Br 
 AgBr
 CH – CH CH NO
3 2 2 2
Phenyl ethanenitrile
propene
(c) Propene to propyne (j) Benzene to biphenyl
CH3  CH  CH 2  Br2 

2 2 Cl , FeCl

3
2
Na (dry ether)
Cl 

propene  HCl heat

KOH (alc.)
CH3  CH  CH 2 
2HBr
 CH 3  C  CH
propyne
| |
Br Br biphenyl

(d) Ethanol to ethylfluoride (k) Cyclopentene to cyclopenta-1, 3-diene

Br
C 2 H 5 OH  SOCl 2 
 C 2 H5 Cl
ethanol chloroethane Br
CCl4
+ Br2   KOH (alc.)


AgF, heat
 C2 H5 F  AgCl room temp. 2HBr
fluoroethane cyclopentene
(ethyl fluoride)
3
(e) Bromomethane to propanone 2
KCN (ethanolic)
CH3 Br  CH3CN 1
bromomethane  KBr Cyclopenta-1, 3-diene

CH MgI/H O
(l) Aniline to phenyl isocyanide

3 2  CH  C  O  NH  Mg(OH)I
3 3
| NH2
CH3
propanone
+ CHCl3 + 3KOH (alc.) 
heat

(f) But-1-ene to but-2-ene chloroform

CH3  CH 2  CH  CH 2  HBr 
 Aniline
but 1 ene
N=C
CH3  CH 2  CH  CH3 
KOH (alc.)

| + 3KCl + 3H2O
Br
Phenyl isocyanide
CH 3  CH  CH  CH 3 (phenyl carbylamine)
but  2  ene
W.E-17:Which compound in each of the following 
pairs will react faster in SN2 reaction with HO–?
(a) CH3Br or CH3I
(b) (CH3)3CCl or CH3Cl
(c) CH2 = CHBr or CH2 = CH – CH2Br
Sol. (a) CH3I will react faster than CH3Br in SN2
reaction with OH– because the leaving group I
is bigger than Br.
(b) CH3Cl will react faster than (CH3)3CCl in
SN2 reaction with OH–, because the CH3– group
is smaller than the (CH3)3C - group. The smaller
group offers less steric hindrance.
(c) CH2 = CH – CH2Br will react faster than
CH2 = CHBr in SN2 reaction with OH–, because
The C - X bond in aryl halides is shorter and
stronger than the C - X bond of alkyl halides.
 The strength of the C - X bond causes arylhalides
to react very slowly in reactions in which
cleavage of C - X bond is rate determining i.e.
nucleophilic substitution.
Preparation Methods of Halo Benzene:
1) Direct Halogenation of Benzene: This reaction
is carried out in absence of sunlight but in
presence of halogen carrier.
 This reaction is an electrophilic substitution
reaction.
a) Chlorination:

+
in vinylic halides (CH2 = CHBr), C – Br bond Cl
develops a partial double bond character due to Cl2  A
lC l
3

 HCl
resonance. This makes C – Br bond stronger and
less polar, and hence breaking of C – Br bond  In this reaction AlCl3 is halogen carrier which
becomes more difficult.
is an electron deficient species, and hence acts
.. – + as Lewis acid.
.. :
CH2 = CH – Br .. :
CH2 – CH = Br
 It is the tendency of halogen carrier that it will
Primary allylic halides may react by both SN1 polarise chlorine molecule to produce
and S N 2 depending upon the nature of electrophile chloronium ion.
nucleophile and the solvent.
Cl  Cl  AlCl3  Cl   AlCl 4 
ARYL HALIDES
 Aryl halides are the compounds having halogen
L
E
C
T
R
O
P
H
I
L
E
E

atom directly attached to the sp 2 carbon of

aromatic ring
 They are represented by the general formula  This electrophile attacks the benzene ring giving
Ar-X, where Ar may be phenyl, substituted an arenium ion which is stabilised by resonance.
phenyl or other aromatic system.
H
+

L
O
W
S

H
+

+
Cl Cl  Cl Cl

Eg:-
H
L
O
R
O+
B
E
N
ZS
EL
NO
EW

+
C

H
+

H H
+

H
+


 Cl
Cl Cl Cl
 In Benzyl halides, the halogen atom is attached Cl

to sp3 carbon which is attached to aromatic ring

 This step is slow step and hence rate determining
CH 2  Cl step.
 In the second step the carbocation looses a
Eg:- proton to the base AlCl4  to give chlorobenzene.
B
E
N
Z
Y
L
C
H
L
O
R
I
D
E

Cl
+

A
S
T
F

Cl
+

H
 In aryl halides, halogen atom is bonded to sp2 AlCl4 
HCl
carbon while in benzyl halides, halogen atom is
bonded to sp3 carbon.
 On using excess of chlorine then the products  This benzene diazonium chloride when heated
are ortho, para disubstituted benzene. with CuCl / HCl or CuBr / HBr produces
corresponding aryl halide.
Cl Cl Cl
+

+
Cl
Cl2   3 
A lC l Cl2 , AlCl3
Cl CuCl
Cl

A
R
AB
D
I
C
H
L
O
R
O
P
R
T
OE
H
D
I
C
H
L
O
R
O
O

N 2 Cl  HCl

E
N
Z
E
N
E
B
N
Z
E
N
b) Bromination: E
Br
+

Br

+
CuBr
Br2  AlC l 3 HBr
HBr

 This reaction is known as Sandmeyer’s

c) Iodination: Iodination of benzene is not reaction.
possible because of formation HI. This being
strong reducing agent reduces alkyl iodide back Gattermann Reaction:
to alkane. 
N 2 Cl  Cl
+

I
I2 HI

+

Cu / HCl
N2
T
R
O
N
G
R
E
D
U
C
I
N
G
A
G
E
N
T
S

 To get iodo benzene strong oxidising agents like Preparation of Chlorobenzene from
HNO3 , HIO3 , HgO etc are used which destroy Phenol:Chlorobenzene can be prepared by the
HI. action of PCl5 on phenol.
d) Fluorination: Direct fluorination of  The yield in this method is very poor because
benzene is not done as this reaction is highly
of side product POCl3 which readily reacts with
explosive and cannot be easily controlled and
hence it is prepared from benzene diazonium phenol to give triphenyl phosphate.
chloride. Raschig Process (Exclusive for Advance):
2) Decarboxylation of Sodium Salt of
Cl
+

+
2
2

Chloro Benzoic Acid:

O2 
CuCl2
2HCl  2H 2 O
+

Cl
+

Cl
NaOH  C
aO
 Na2CO3 Hunsdiecker Method:
COONa
C6 H 5COOAg  Cl2  C6 H 5Cl  CO2  AgCl
 The acid salt may be ortho, meta or para
derivative. Physical properties: On going down the
group M.P. and B.P. increases because of
3) From Benzene Diazonium Chloride: increase in size of atoms. Hence, decrease in
 Benzene diazonium chloride is obtained on B.P. follows the order
diazotisation of aniline.
IODO ARENES > BROMO ARENES >
NH 2 N 2  Cl  CHLORO ARENES > FLUORO ARENES
 With the same halogen atom these properties
NaNO2  HCl , 0  50 C
     increase as size of the aryl group increases.
 B.P. of isomeric dihalo benzenes are nearly the
E
N
Z
E
N
E
D
I
A
Z
O
N
I
U
M
C
H
L
O
R
I
D
E
B

same. But their M.P’s are quite different.

 Generally the M.P. of para isomer is always  Low reactivity of C - Cl bond in chlorobenzene
higher than that of ortho or meta isomer because as compared to alkyl halide can also be
para isomers are more symmetrical and hence explained on the basis of polarity of C - Cl bond.
its molecules are packed closely in the crystal  It is observed that C - Cl bond in chlorobenzene
lattice. This results an increase in intermolecular is less polar than C - Cl bond in alkyl halide.
attractions and finally increase in melting points  This is because in chlorobenzene carbon atom
than the corresponding isomers. is in sp 2 hybridised which is more
 M.P. for isomeric dichloro benzene is in the electronegative than the sp3 hybridised carbon
order of
atom in case of alkyl chloride.
Cl Cl  Therefore, the sp2 hybrid carbon of C - Cl bond
Cl
in aryl halides is less willing to release electrons
Cl to the halogen than a sp3 hybrid carbon in alkyl
chloride.
Cl Nucleophilic substitution reactions of
Cl chloro benzene: It has been observed that
5
6
K
2
.
P
.
M

4
9
K
2

2
5
K
3

electron withdrawing groups such as

Chemical properties: Chlorine of
chlorobenzene is inert nucleophile i.e., far less
reactive than halo alkanes towards nucleophilic
substitution reactions.
 This is because of lone pair of electrons present
at chlorine atom will conjugate with  electrons
of benzene ring, as a result some double bond 
character is developed between the C - Cl bond
and hence this bond becomes shorter and
stronger.
 This can be explained on the basis of following
resonance structures.
 NO2 groups present at ortho and para positions
(not at meta position) with respect to halogen
greatly activates the halogen towards nucleo
philic displacement i.e., these groups withdraw
electrons from benzene ring as well as carbon
atom of the C - Cl bond.
Also greater the number of such groups at ortho
and para positions, more reactive is the halo
arene.
Examples:
Cl OH

Cl Cl Cl Cl Cl
)
1


NaOH
3600 C


 Stronger C - Cl bond in chlorobenzene as Cl OH

compared to alkyl chloride can also be explained
on the basis of hybridisation.
)
2

 In chlorobenzene carbon atom bearing chlorine 

NaOH
1600 C

is sp2 hybridised whereas in alkyl chloride it is x
in sp3 hybridised state.
 Since sp2 hybrid orbital is smaller in size as NO2 NO2
compared to sp3 hybrid orbital, therefore, C-Cl
bond in chlorobenzene should be shorter and
hence stronger than alkyl halide. Cl OH

NO2 NO2
)
3

 NaOH
 
96 0 C

NO2 NO2
,
4
d
i
n
i
t
r
o
2
,
4
d
i
n
i
t
re
on
ce
h
l
o
r
o
2

p
h
e
n
o
l
b
e
n
z
 Cl OH
Other reactions of Chloro Benzene:
1. Halogenation
)
4

O2 N NO2 O2 N NO2
Cl Cl Cl

H2O

Cl
FeCl3 dark
NO2 NO2 +Cl2    +

y
m p
.
t
r
i
n l
i
t
r
o
s
y
m
.
t
r
i
n
i
t
r
o
s

hi
ec
na
oc
h
l
o
r
o
b
e
n
z
e
n
e
c

P
i
c
r

i
d
)
(
Cl

W.E-18:Which of the following does not give white 2. Nitration

precipitate with acidified AgNO3 solution. Cl Cl Cl
NO2
H 2SO 4
Cl +HNO3 60

C
+
)
a

3. Sulphonation NO2
b) CH 2  CH  Cl
Cl Cl Cl
SO3H
c) CH 2  CH  CH 2  Cl d) both a and b. Δ
+H2SO4  +
Sol. ‘d’. In ‘c’ chlorine containing carbon atom is in
3
hybridised state and it is more polar and also
s p

SO3H
it easily gives AgCl precipitate. In case of ‘a’ 4. Friedel Crafts Reactions
and ‘b’ there is double bond character between (a) Alkylation
C - Cl bond and carbon bearing chlorine atom
is in sp2 hybridised state i.e., C-Cl bond is Cl Cl Cl
stronger bond and hence chlorine cannot be anhyd. R
easily replaced. +R – X AlCl
3 +
Δ

W.E-19:Arrange the following in decreasing order (b) Acylation R

of their reactivity towards nucleophilic Cl
substitution.
Cl Cl +CH3COCl or CH 3 C  O  C CH 3 anhyd. AlCl
  3 
Cl Δ
Cl Cl || ||
NO2 NO2 NO2 O O

Cl O Cl
NO2
NO2 NO2 NO2 C – CH3
(I ) ( II ) ( III ) +
( IV ) (V )
Sol. V > IV > III > II > I. More electron withdrawing C=O
groups at ortho and para positions, chlorine can CH3
easily be replaced by nucleophile.Resonance
effect is not observed at meta position. (c) Benzoylation
Cl
Reaction with NaOH (Dow’s process):
AlCl3
Cl OH + C6H5COCl or C6H5 – C – O – C – C6H5 
Δ
ONa
O O
+

2 NaOH  360
   dil
. HCl

0
C
Cl O Cl
h
e
n
o
l
P

C – C6H5
o
d
i
u
m
p
h
e
n
o
x
i
d
e
S

 This reaction proceeds by the formation of

C=O
benzyne intermediate. C6H5
 III. Miscellaneous Reactions  Through inductive effect, chlorine destabilises
the intermediate carbocation formed during the
(a) Fittig Reaction electrophilic substitution.
 Through resonance, halogen tends to stabilise
Cl + 2Na 
dry ether
2 + 2NaCl
the carbocation.
(b) Wurtz-Fittig Reaction Cl Cl
H
Cl + R–Cl + 2Na 
dry ether
R +2NaCl
+E E

Here side products like R – R and

W.E-21: How will you prepare m-bromo iodo
are also formed. benzene from benzene.
W.E-20:Which one of the following structure of NO 2 NO2
HNO
C7 H 7 Cl has weakest C - Cl bond. Sol. 
3

2 Br
H 2SO4 Fe
Cl Br
CH 2  Cl Cl Cl

)
d
NH2 N2Cl
)
c
)

)
a

NaNO /HCl
Sn /HCl

 
2 
0ºC
CH 3 Br Br
CH 3
Cl I
Cl Cl
)
d

KI

)
c
)

Br
CH 3
CH 3 W.E-21:Identify the compounds A to D
(A)   p-nitroToluene
Nitric Acid
Sol. ‘a’ Sulphuric Acid
 Just as in chlorobenzene C - Cl bond in ortho, (D)
meta and para chloro toulene has double bond 
Sn / HCl
(B) 
NaNO 2
(C)   p-flouro

HCl, 0 5 C 
character due to resonance. Whereas in benzyl toluene
chloride the C - Cl bond is pure single covalent Sol. A= Toulene, B = p-toluidine, C = p-toluene
bond . diazonium chloride, D = HBF4
 Thus out of four isomers the C - Cl bond is
weakest in benzyl chloride. W.E-22: Which of the following derivatives of
Electrophilic substitution reactions of benzene would undergo hydrolysis most
Halo Benzene: Halo benzene undergoes readily with aq. KOH
Cl Cl
usual electrophilic substitution reactions.
 Halogen atom being deactivating in nature, but O2N NO 2

activates the benzene ring by increasing electron

(A) (B)
density at ortho and para position.
 Therefore, during the electrophilic substitution NO 2 NO 2
reaction, electrophile will occupy ortho and para Cl
Cl
position.
 As halogen atom in halo benzene has -I effect NO 2

hence its electrophilic substitution reactions (C) (D)

occur slowly under more drastic conditions as NO 2
N
compared to benzene. NO 2 H3C CH3
 Chlorine withdraws electrons through inductive Sol. B. – NO group increases reactivity because of
2
effect and releases electrons through resonance. –R and –I effect.
W.E-23:When all cis isomers of C6H6 Cl6 (1,2,3,4,5,6- 8. In the preparation of alkyl halide from alkene
Hexachlorocyclohexane) is heated with alc. KOH, and halogen which of the following reaction
the most probable product is is involved
Cl
1) Electrophilic addition 2) Nucleophilic addition
Cl
3) Electrophilic substitution
Cl 4) Nucleophilic substitution
(A) (B) 9. In the preparation of alkyl halide from alkane
and halogen which of the following reaction
Cl Cl Cl is involved
1) Free radical substitution
Cl 2) Nucleophilic addition
3) Electrophilic substitution
4) Nucleophilic substitution
(C) (D) Properties:-
10. Grignard reagent is formed when alkyl halide
reacts with which one of the following
Cl
1) Mg in alcohol 2) Mg in acid
Sol. B. It is an example of E2 elimination. 3) Mg in dry ether 4) MgO
11. When alkyl halide reacts with moist Ag 2O
C.U.Q gives
1) alcohol 2) ether 3) alkane 4) alkene
INTRODUCTION 12. Alkyl halide on reduction with Zn + HCl gives
1. Which of the following is 10 alkyl halide 1) alcohol 2) alkene 3) alkane 4) ether
1) R  CH 2  X 2) R2CHX 13. Isocyanide is formed as the major product
of the reaction when alkyl halide is treated
3) R3C  X 4) R – H with one of the following
2. 2o halide among the following 1) AgNO2 2) KNO2 3) AgCN 4) KCN
1) isopropyl chloride 2) isobutyl chloride 14. Which of the reactions are most common in
3) n-propyl chloride 4) n-butyl chloride alkyl halides
3. Ethylidene bromide is 1) Nucleophilic addition
1) CH 3CH 2 Br 2) Br  CH 2  CH 2  Br 2) Electrophilic addition
3) CH 3  CHBr2 4) CH 2  CHBr 3) Nucleophilic substitution
4) Electrophilic substittuion
4. Which of the following is gemdihalide? 15. Treatment of ammonia with excess of ethyl
1) CH3CHBrCH2Br 2) CH3CHBr2 chloride will yield
3) CH3CHBrCH2CH2Br 4) BrCH2CH2Br 1) Diethyl amine 2) Ethane
5. Vicinal dihalide is 3) Tetra ethyl ammonium chloride
1) CH 3CH 2 Br 2) Br  CH 2  CH 2  Br 4) methyl amine
3) CH 3  CHBr2 4) CH 2  CHBr 16. In chloro ethane the carbon bearing halogen
is bonded to -------hydrogens and nature of
ALKYL & ARYL HALIDES alkyl halide is
Preparation:- 1) three, primary 2) two, secondary
6. The reagent used to get alkyl halide from 3) one, tertiary 4) two, primary
alcohol Uses:
1) PCl5 2) SOCl2 3) both 1 & 2 4) Cl2 17. Which of the following alkyl halide is used
7. For the preparation of alkyl halides from as a ethylating agent?
alcohols which among the following cannot 1) CH3I 2) C2H5Cl 3) C2H4Br2 4) C2H5OH
be used 18. Which of the following is used as refrigerant?
1) CH3COCH3 2) CCl4
1) PCl5 2) SOCl2 3) PCl3 4) NaCl 3) C H Cl 4) CF
2 5 4
19. Ethyl chloride is not useful in preparing 29. The raw material for raschig process is
1) PVC 2) TEL 1) chloro benzene 2) phenol
3) Grignard reagent 4) Diethyl ether 3) benzene 4) anisol
30. Chloro benzene on treatment with sodium in
SN1 and SN2 Reactions dry ether gives diphenyl. The name of the
20. SN 1 reaction occurs through the reaction is
intermediate formation of 1) Fittig reaction 2) Wurtz fittig reaction
1) carbocation 2) carbanion 3) Wurtz reaction 4) Sandmeyer reaction
3) free radicals 4) transition 31. An organic compound which produces a
21. The rate of SN 2 reaction is maximum when bluish green coloured flame on heating in the
presence of copper is
the solvent is
1) chloro benzene 2) benzaldehyde
1) Methyl alcohol 2) Water 3) aniline 4) benzoic acid
3) Dimethyl sulphoxide 4) Benzene 32. The raw materials for the commercial
22. The most reactive nucleophile among the manufacture of DDT are
following is 1) chloro benzene and chloroform
1) CH 3O  2) C6 H 5O  2) chloro benzene and chloro methane
3) chloro benzene and chloral
3)  CH 3 2 CHO  4)  CH 3 3 CO  4) chloro benzene and iodoform
23. The correct order of reactivity towards POLY HALOGEN COMPOUNDS
nucleophilic substitution reaction is 33. Iodoform is used as
1) CH 3 F  CH 3Cl  CH 3 Br  CH 3 I 1) anaesthetic 2) antiseptic
3) analgesic 4) anti febrin
2) CH 3 I  CH 3 Br  CH 3Cl  CH 3 F 34. The following is used in paint removing
3) CH 3 I  CH 3Cl  CH 3 Br  CH 3 F 1) CHCl3 2) CH 2Cl2 3) CCl4 4) C H 3 C l
4) CH 3 I  CH 3 Br  CH 3 F  CH 3Cl 35. In fire extinguishers, following is used
1) CHCl3 2) CS 2 3) CCl4 4) CH 2Cl2
24. In SN 2 reactions the order of reactivity of the
36. The following is used for metal cleaning and
halides. CH 3 X , C2 H 5 X , n  C3 H 7 X , n  C4 H 9 X is finishing
1) CH 3 X  C2 H 5 X  n  C3 H 7 X  n  C4 H 9 X 1) CHCl3 2) CHI 3 3) CH 2Cl2 4) C6 H 6
2) C2 H 5 X  n  C3 H 7 X  n  C4 H 9 X  CH 3 X 37. First chlorinated insecticide
3) C2 H 5 X  n  C3 H 7 X  n  C4 H 9 X  CH 3 X 1) DDT 2) Gammaxene 3) Iodoform 4) Freon
4) n  C4 H 9 X  n  C3 H 7 X  C2 H 5 X  CH 3 X 38. The following is used as anaesthetic
25. SN 2 mechanism proceeds through the 1) C2 H 4 2) CHCl3 3) CH 2Cl2 4) DDT
formation of a 39. Freon - 12 is
1) carbocation 2) transition state 1) CF3Cl 2) CHCl2 F 3) CF2Cl2 4) CFCl3
3) free radical 4) carbanion 40. The name of DDT
ALKYL & ARYL HALIDES 1) p, p’- dichloro diphenyl trichloro ethane
2) p, p’- dichloro diphenyl trichloro ethene
26. In Dow’s process the starting raw material 3) p, p’- dichloro diphenyl trichloro benzene
is 4) p, p’- tetra chloro ethane
1) Phenol 2) Chloro benzene 41. Freon R - 22 is
3) Aniline 4) Diazobenzene
27. Chloro benzene is prepared commercially by 1) CHClF2 2) CCl2 F2 3) CH 3Cl 4) CH 2Cl2
1) Dow’s process 2) Decon’s process 42. Molecular formula of DDT has
3) Raschig process 4) Etard’s process 1) 5 Cl atoms 2) 4 Cl atoms
28. Chloro benzene is ........ reactive than benzene 3) 3 Cl atoms 4) 2 Cl atoms
towards electrophilic substitution and directs 43. What is DDT among the following
incoming electrophile to the ....... position. 1) Green house gas 2) A fertilizer
1) more, ortho & para 2) less, ortho & para 3) Bio degradable pollutant
3) more, meta 4) less, meta 4) Non - Bio degradable pollutant
 C.U.Q - KEY Physical properties:-
8. Which one of the following has the lowest
1) 1 2) 1 3) 3 4) 2 5) 2 6) 3 7) 4
boiling point ?
8) 1 9) 1 10) 3 11) 1 12) 3 13) 3 14) 3
1) CH 3Cl 2) C2 H 5Cl 3) C2 H 5 Br 4) C2 H 5 I
15) 3 16) 4 17) 2 18) 3 19) 1 20) 1 21) 3
Chemical properties:-
22) 1 23) 2 24) 1 25) 2 26) 2 27) 3 28) 2 9. Chloroethane is reacted with alcoholic
29) 3 30) 1 31) 1 32) 3 33) 2 34) 2 35) 3 potassium hydroxide. The product formed is
36) 3 37) 1 38) 2 39) 3 40) 1 41) 1 42) 1 1) C2H6O 2) C2H6 3) C2H4 4) C2H4O
10. What is X in the following reaction?
43) 4
C2 H 5Cl  X  C2 H 5OH  KCl
LEVEL-I (C.W) 1) KHCO3 2) alc. KOH 3) aq. KOH 4) K 2CO3
11. Which of the following acids will give
INTRODUCTION maximum yield of alkyl chloride in Huns
diecker reaction
1. The IUPAC name of (CH3)2CHCH2Br is
1) 1-bromo-2-methylpropane 1) CH 3CH 2CH 2COOH 2)  CH 3 2 CHCOOH
2) 2-bromo-2-methylpropane 3)  CH 3 3 CCOOH 4) C6 H 5CH  CH 3  COOH
3) 1-bromo-1-methylpropane 12. In the reaction sequence
4) 2-bromo-1-methylpropane
2. IUPAC name of allyl chloride is C 2 H 5 C l  K C N  C 
2 H 5O H
 X
1) 1-chloro ethane 2) 3-chloro-1-propyne what is the molecular formula of X is
3) 3-chloro-1-propene 4) 1-chloropropene 1) C H CN 2) C2H5NC 3) C2 H5OH 4) C2 H 8O
2 5
13. Ethyl chloride on heating with silver cyanide
3. IUPAC name of forms a compound X. The functional isomer
of X is
1) 2-bromo-3-methyl pentane 1) C2H5NC 2) C2H5CN
2) 2-bromo-3,3-dimethyl butane 3) H3C-NH-CH3 4) C2H5NH2
3) 4-bromo-3,3-dimethyl butane 14. With Zn-Cu couple and C 2H5OH, ethyl
4) 2-bromo-3,3-dimethyl pentane Iodide reacts to give
ALKYL & ARYL HALIDES 1) ethers 2) diethyl ether
Preparation:- 3) Iodoform 4) Ethane
15. In the dehydrohalogenation of ethyl chloride
4. C2H5OH  PCl5
 X. In this reaction 'X' is the following change occurs.
1) Ethanol 2) Ethylene chloride 1) sp2 carbon converts to sp3 carbon
3) ethylidene chloride 4) ethyl chloride 2) sp2 carbon converts to sp carbon
5. Thionyl chloride is preferred in the 3) sp3 carbon converts sp carbon
preparation of chloro compound from 4) sp3 carbon converts to sp2 carbon
alcohol since SN1 and SN2 Reactions
1) Both the byproducts are gases and they escape 16. The reaction
out leaving product in pure state
2) It is a chlorinating agent C2 H 5Cl  OH   C2 H 5OH  Cl  is
3) It is a oxidising agent 1) S N 1 2) S N 2 3) S E 1 4) S E 2
4) All other reagent are unstable 17. (R)-2 octyl tosylate is solvolyzed in water
6. The only alkene which gives primary alkyl
halides on hydrohalogenation under ideal S N 1 conditions. The product (s)
will
1) C2 H 4 2) C3 H 6 3) C4 H 8 4) C5 H10
1) R-2-octanol and S-2-octanol in a 1:1 ratio
7. -OH cannot be replaced by -Cl if we use 2) R-2-octanol and S-2-octanol in 1.5:1 ratio
1) PCl5 2) PCl3 3) S2Cl2 4) SOCl2 3) R-2-octanol only 4) S-2-octanol only
18. The absolute configuration of a molecule 28. The following is an example of Sandmeyer
changes during the reaction reaction
1) S N 1 2) S N 2 1) C6 H 5 N 2  Cl  
CuCl / HCl
 C6 H 5Cl
3) free radical substitution 4) S E 2 H2O/ 
2) C6 H5 N2Cl   C6 H5OH
19. For a nucleophillic substitution reaction the
rate was found in the order RI > RBr > RCl 3) C 6 H 5 N 2  C l   H 
B F4
 C6H 5F
> RF then the reaction could be
1) S N 1 Only 2) S N 2 Only 4) C6 H 5 N 2  Cl  
KI / warm
 C6 H 5 I
3) Either S N 1 or S N 2 4) Neither S N 1 nor S N 2 Properties of haloarenes
20. S N 2 reaction leads to 29. Chlorobenzene on reaction with CH 3Cl in
1) inversion of configuration presence of AlCl3 gives
2) retention of configuration 1) toulene 2) m-chloro toulene
3) partial racemisation 4) no racemisation 3) only o-chloro toulene
21. Which of thefollowing alkyl halide is 4) mixture of o- and p-chlorotoulene
hydrolysed by S N 1 mechanism 30. 2C6 H 5Cl  2 Na  X , X is
1) CH 3Cl 2) CH 3  CH 2  Cl 1) toulene 2) biphenyl
3) CH 3  CH 2  CH 2  Cl 4) CH3 3 C Cl
3) phenyl ethane 4)1-chloro-2-phenyl ethane
31. Chlorobenzene on fusing with solid NaOH
Nomenclature and natureof C-X bond gives
22. C-Cl bond of chlorobenzene in comparision 1) benzene 2) benzoic acid
to C-Cl bond of methyl chloride is 3) phenol 4) benzene chloride
1) Longer and weaker 2) Shorter and weaker 32. Chlorobenzene on nitration gives major
3) Shorter and stronger 4) Longer and stronger product of
1) 1-chloro - 4 - nitro benzene
2) 1- chloro - 3 nitro benzene
23. IUPAC name of is 3) 1, 4 - dinitro benzene
4) 2, 4, 6 - tri nitro benzene
1) 1, 2 - dichloro benzene 2) m-dichloro benzene 33. The reaction
3) 1, 6- dichloro benzene 4) o- dichloro benzene C6 H 5 I  2 Na  CH 3 I  C6 H 5CH 3  2 NaI is
24. In aryl halides carbon atom holding halogen 1) Wurtz reaction 2) Fittig reaction
is 3) Wurtz - Fittig reaction 4) Sandmeyer reaction
1) sp 2 hybridised 2) sp hybridised
LEVEL-I (C.W) - KEY
3 3
3) sp hybridised 4) sp d hybridised 1) 1 2) 3 3) 4 4) 4 5) 1 6) 1 7) 3
25. The following is aryl alkyl halide
1) o-chloro toulene 2) o-bromo chloro benzene 8) 1 9) 3 10) 3 11) 1 12) 1 13) 2 14) 4
3) 1-chloro - 2-phenyl ethane 4) toulene 15) 4 16) 2 17) 1 18) 2 19) 3 20) 1 21) 4
Preparation of haloarenes 22) 3 23) 1 24) 1 25) 3 26) 2 27) 1 28) 1
26. Chloro benzene can be prepared by reacting 29) 4 30)2 31) 3 32) 1 33) 3
benzene diazonium chloride with
1) HCl 2) Cu2Cl2 / HCl LEVEL-I (C.W) - HINTS
3) Cl2 / AlCl3 4) HNO2 CH 3  CH  CH 2  Br
|
1.
27. , X is CH 3
1-bromo 2-methyl propane
1) chlorobenzene 2) m-dichloro benzene
2. Allyl chloride is CH 2  CH  CH 2Cl
3) benzene hexachloride 4) p- dichlorobenzene
3.
25.
4. C2 H 5  OH  PCl5 
C2 H 5  Cl  POCl3  HCl Halogen is attached to carbon present on
5. Both byproducts are gases. aromatic ring.
6. C2 H 4  HCl  C2 H 5  Cl 26. C H N Cl


Cu Cl
 C6 H 5Cl  N 2
2 2
6 5 2

7. R  OH  S2Cl2  No reaction 27. C6 H 6  Cl2 

FeCl
 C6 H 5Cl  HCl
3

8. Order of B.P.’s : 28. Sandmeyer reaction

 
R - F < R - Cl < R - Br < R - I is C6 H 5 N 2 Cl 
CuCl / HCl or
 C6 H 5Cl  N 2
Cu Cl
If M.wt. increases, molecular attractions also 2 2

increases 29. Cl group on benzene is ortho, para directing

group hence gives mixture of O-and P-chloro
9. C2 H 5Cl alc . KOH
 C2 H 4  HCl toulene
10. C2 H 5  Cl  KOH  C2 H 5  OH  KCl 30. Fittig reaction
aqueous 31. C6 H 5Cl  NaOH  C6 H 5OH  NaCl
C H  OH 32. Cl group on benzene is ortho, para directing
12. C2 H 5  Cl  KCN 
2 5
 C2 H 5  CN  KCl
group and major product is para product.
13. Functional Isomer of - Isocyanide is -cyanide 33. It is Wurtz-Fittig reaction
14. C2H5  I  2H  ZnCu, C2H5 OH
C2H6  HI
LEVEL-I (H.W)
C2 H 5  Cl 
 C2 H 4  HCl
alc . KOH

1. The number of structural isomers possible

15.
  with the formula C4H9Cl are
1) 5 2) 4 3) 3 4) 2
SP 3 SP 2 2. Density is highest for
16. rate   CH 3Cl   OH   SN 2

1) CH 3Cl 2) CH 2Cl2 3) CHCl3 4) CCl4
18. In S N 2 mechanism nucleophile attacks from ALKYL & ARYL HALIDES
backside. 3. In the preparation of ethyl chloride from
19. In both SN 1 & SN 2 rate order for different ethyl alcohol with thionyl chloride is carried
in the presence of pyridine, here pyridine is
halides is RI  RBr  RCl  RF used because
20. In S N 2 mechanism nucleophile attacks from 1) Facilitates the reaction
backside. 2) C2H5OH is soluble in pyridine
3) Pyridine absorbs HCl 4) Pyridine absorbs SO2
21. 3o alkyl halide is hydrolysed by S N 1 mechanism
4. In the hydrohalogenation of ethylene for
22. C-Cl bond lenth of chlorobenzene is shorter than adding HCl, the catalyst used is
that in alkyl halide & so bond energy is more in 1) Anhydrous AlCl3 2) Conc. Sulphuric acid
chlorobenzene 3) Dilute Sulphuric acid 4) Anhydrous ZnCl2
5. Ethyl bromide on boiling with alcoholic
solutions of sodium hydroxide forms
1) ethane 2) ethylene
23. 3) ethyl alcohol 4) all of these
6. Following major compound is formed when
24. In aromatic (or) aryl halide, halogen is attached ethyl chloride reacts with silver nitrite
1) Nitro ethane 2) Ethyl nitrite
to sp 2 carbon 3) Ethylene 4) Acetaldehyde
7. Which of the following represents 17. The order of reactivity of various alkyl
Williamson's synthesis halides towards S N 1 reaction is
1) CH3COOH + PCl3  1) 30  20  10 2) 10  20  30 3) 3  20  10 4) 10  30  20
2) CH3-CH2-Cl+CH3COOH  18. ‘Achiral’ molecule among the following is
1) Propan-2-ol 2) butan-2-ol
3) CH3—CH2—ONa+CH3—CH2—Cl  3) 2-chlorobutane 4) 2-bromopropanoic acid
4) CH3—CH2—OH + Na  LEVEL-I (H.W) - KEY
8. What is the product of the following reaction 1) 2 2) 4 3) 3 4) 1 5) 2 6) 2 7) 3
Cl Br
+KCN  ? 8) 1 9) 1 10) 2 11) 2 12) 3 13) 2 14) 2
Cl CN Cl Br 15) 1 16) 3 17) 1 18) 1
1) 2)
Cl
LEVEL-I (H.W) - HINTS
Br
3) 4) C
|
9. The reaction of alkyl halide with benzene in Cl C
C C C
presence of anhydrous AlCl 3 gives alkyl 1. C C C C Cl ; | |
|
benzene the reaction is known as C C C C C  C  C  Cl
Cl
1) Friedel-craft's reaction 2) Carbylamine reaction
3) Gattermann reaction 4) Wurtz reaction 2. As molecular weight increases density increases.
10. Which of the following can give a grignard
reagent when reacted with magnesium in dry
ether ?
1) C2 H 6 2) C2 H 5Cl 3) C2 H 5OH 4) C2 H 5CN 3.
11. A Grignard's reagent reacts with water to
give
1) ether 2) alkanes 3) amine 4) Alcohol 4. AlCl3 Ionises HCl
 
12. C2H5Cl + Mg —> C2H5 MgCl in this reaction C2 H 5  Br    C2 H 4  HBr
NaOH , alc .
5.
the solvent is
1) C2H5OH 2) Water 3) Dry ether 4) Acetone 6. C2 H5  Cl  KNO2 
DMF
C2 H5  NO2  KCl
13. R  X  NaI dry acetone
 R  I  NaX . The re- CH 3  CH 2  ONa  CH 3  CH 2  Cl 
action is known as 7.
C2 H 5  O  C2 H 5  NaCl
1) Swarts reaction 2) Finkelstein reaction
3) Wurtz-Fittig reaction 4) Friedel-Craft’s reaction 8. Order of reactivity C-I>C-Br>C-Cl>C-F

SN1 and SN2 Reactions

14. S N 1 reaction is favoured by
1) Non-polar solvents 9.
2) Bulky group on the carbon atom attached to
the halogen atom
10 & 12. C2 H 5  Cl  Mg   C2 H 5  MgCl
Dry ether
3) Small groups on the carbon atom attached to  Grignard's reagent 
halogen atom 4) All the above 11. RMgX  H 2O  R  H
15. Which of the following is not stereospecific
14. S N 1 reaction is favoured by bulky group
1) S N 1 2) S N 2 3) E2
on the carbon attached to the halogen atom
4) Addition of Br2 to ethylene in CCl4 15. S N 1 is not stereo specific
16. Which of the following factors does not
16. S N 1 mechanism is not favoured by
favour S N 1 mechanism concentration of nucleophile
1) Strong base 2) Polar solvent 17. Order of reactivity of various alkylhalides
3) Low conc. of nucleophile 4) 30 halide towards S N 1 reaction is 3o  2o  1o
 1. HALOALKANES AND ARENES
OH
LEVEL-II (C.W) 9. + SOCl2  X . X is

INTRODUCTION SO 3 H Cl
1. Isomerism shown by 2,3-dichlorobutane is
1) diastereomerism 2) optical isomerism 1) 2)
3) geometric isomerism 4) structural isomerism
2. The number of possible monochloro Cl
structural isomers formed on 3) 4)
monocholrination of  CH 3 2 CHCH 2CH 3 is
1) 2 2) 3 3) 4 4) 5 Chemical properties:-
3. Among the isomeric alkanes of molecular 10. Among the following, the compound with
highest density is
formula C5 H12 , which gives four isomeric
1) n  C3 H 7Cl 2) n  C3 H 7 Br
monochlorides on photochemical
chlorination is 3) n  C3 H 7 I 4) CHCl3
1) neo pentane 2) n-pentane 11. C2 H 5Cl  AgOH  A  AgCl .
3) iso pentane 4) 2-methyl propane
4. Secondary alkyl halide among the following A  CH 3COCl  C  HCl. “C” is
is 1) Ethyl acetate 2) Methyl acetate
1) 2-bromo-3-methyl butane 3) butanone - 2 4) propanone
2) 1-bromo-3-methyl butane 12. The compound(B) in the below reaction is:
H 3O 
3) 2-bromo-2-methyl butane C2 H 5Cl KCN
 A  B
4) 1-bromo-2-methyl butane 1) ethylene chloride 2) acetic acid
ALKYL & ARYL HALIDES 3) propionic acid 4) ethyl cyanide
Preperation:- 13. Chloro ethane reacts with X to form diethyl
ether. What is X ?
5.
R  Cl  NaI acetone
 R  I  NaCl 1) NaOH 2) H 2 SO4 3) C2 H 5ONa 4) Na2S2O3
This reaction is
1) Wurtz reaction 2) Fittig reaction 14. 1-chlorobutane on reaction with alcoholic
3) Finkelstein reaction 4) Frankland reaction potash gives
1) 1-butene 2) 1-butanol
6. C2 H 5OH  SOCl2  Pyridine
x  y  z in this 3) 1-butyne 4) 2-butanol
reaction x, y and z respectively are S 1 and S 2 reactions
N N
1) C2 H 4Cl2 , SO2 , HCl 2) C2 H 5Cl , SO2 , HCl 15. Which of the following is correct order of
reactivity
3) C2 H 5Cl , SOCl , HCl 4) C2 H 4 , SO2 , Cl2
1) Vinyl chloride > Allyl chloride > Propylchloride
7. 2-methyl butane on reaction with Br2 in the 2) Propylchloride > Vinyl chloride > Allyl chloride
3) Allyl chloride > Propylchloride > Vinyl chloride
presence of sunlight gives mainly
4) Allyl chloride < Vinyl chloride > Propylchloride
1) 1-bromo-3-methyl butane
16. Addition of ethanol to the aqueous hydrolysis
2) 2-bromo-3-methyl butane of benzyl chloride does not increase the rate
3) 2-bromo-2methyl-butane of the hydrolysis but changes only the
4) 1-bromo-2methyl butane composition of the final products. This
8. In Hunsdiecker reaction indicates that the reaction is proceeding
1) number of carbon atoms decrease through
2) number of carbon atoms increase
1) S N 1 mechanism 2) S N 2 mechanism
3) number of carbon atoms remains same
4) carboxylic acid is formed 3) S E 1 mechanism 4) S E 2 mechanism
17. The correct order of decreasing S N 2 Properties of haloarenes:-
reactivity (AIEEE-2007) 21. The correct order of increasing boiling points
is
1) RCH 2 X  R2CHX  R3CX 1) bromomethane < bromoform <
chloromethane < dibromomethane
2) RCH 2 X  R3CX  R2CHX
2) bromoform<dibromomethane<chloroform
3) R2CHX  R3CX  RCH 2 X < chloromethane
3) chloroform < bromoform < chloromethane
4) R3CX  R2CHX  RCH 2 X < dibromomethane
Preparation of haloarenes:- 4) chloromethane < bromomethane <
dibromomethane < bromoform
18. Direct iodination of benzene is not possible
because 22. Aryl halides are less reactive towards
nucleophilic substitution reactions as
1) iodine is oxidising agent compared to alkyl halides due to
2) the product C6 H 5 I is reduced to C6 H 6 by HI 1) the formation of less stable carbonium ion
3) HI is unstable 4) ring is deactivated 2) resonance stabilisation
3) inductive effect
19. On treatment of toulene with Cl2 in presence
4) larger carbon halogen bond
of Fe, dark the product formed is (AIEEE 2007)
23. Replacement of Cl of chloro benzene to give
1) o- and p-chloro toulene phenol requires drastic conditions but Cl of
2) benzyl chloride 2, 4, 6 - trinitro chloro benzene is readily
3) m-chloro toulene 4) only p-chloro toulene replaced because
20. The major mono halo product in the reaction 1) NO2 makes ring electrons rich at ortho and
para positions
is X. 
Br2 , heat or
U.V.light
X . 2) NO2 with draws electrons from meta
position
Identify the product X.
3) NO2 donates electrons at meta position
4) NO2 withdraws electrons from ortho, para
1) positions
24. Chloro atom in chlorobenzene is ortho para
director because
1) resonance effect predominates over inductive
effect
2) 2) inductive effect predominates over resonance
effect
3) both inductive effect and resonance effect are
evenly matched
3) 4) only resonance effect operates
25. When aryl halides are treated with sodium
in dry ether, it gives a product in which two
aryl groups are joined together. This reaction
is called
4) 1) Wurtz’s reaction 2) Fittig reaction
3) Wurtz-Fittig reaction 4) Swarts reaction
 33. Assertion (A) : Ethyl chloride with
26. . aq.ethanolic AgCN gives ethyl iso cyanide
as major product.
Identify ‘B’. Reason (R) : In ethyl cyanide, carbon of CN
group is sp hybridised
1) 34. Assertion (A): n-Butyl cloride has higher
boiling point than tert-butyl chloride.
2) Reason (R): C-Cl bond in n-butyl chloride is
more polar than in tert-butyl chloride.

3) LEVEL-II (C.W) - KEY

1) 2 2) 3 3) 3 4) 1 5) 3 6) 2 7) 3
4) 8) 1 9) 3 10) 3 11) 1 12) 3 13) 3 14) 1
15) 3 16) 1 17) 1 18) 2 19) 1 20) 1 21) 4
Poly halogen compounds:-
27. The compound used in the production of 22) 2 23) 4 24) 1 25) 2 26) 1 27) 2 28) 2
Freon refrigerant, R-22 is 29) 1 30) 1 31) 1 32) 2 33) 2 34) 3
1) methylene chloride 2) chloroform
3) iodoform 4) carbon tetra chloride LEVEL-II (C.W) - HINTS
28. The compound used as an anaesthetic during
surgeory is
1) chloroquine 2) halothane 1.
3) chloramphenicol 4) thyroxine
2nd and 3rd carbons are Chiral.
Assertion and Reasoning questions 5. Alkyl iodides are prepared by Finkelstein
1) Both A and R are true and R is the correct reaction.
explanation to A
2) Both A and R are true and R is not the correct 6. C2 H 5  OH  SOCl2 
P yridine

explanation to A C2 H 5  Cl  SO2  HCl
3) A is true but R is false
4) A is false but R is true 7. Reactivity order of hydrogens is 3o  2o  1o
29. Assertion (A) : Isopropyl chloride is a 8. RCOOAg  Br2  R  Br  CO2  AgBr
secondary alkylhalide
Reason (R) : Chlorine is present on secondary 9. The nucleophile Cl  replaces OH of alcohol
carbon 10. density increases with increase of molar mass.
30. Assertion (A) : 1,2- dichloro ethane is a vicinal C2 H 5Cl  AgOH   C2 H 5OH
 AgCl
dihalide 11.
Reason (R) : Two chlorine atoms present on ( A)
adjacent carbon atoms is known as vicinal

CH 3COCl
 HCl
 CH 3COOC2 H 5
dihalide.
31. Assertion (A) : Alkylhalides are polar in (C )
nature, but they are almost insoluble in water. 

Reason (R) : They can neither form Hydrogen C2 H 5  Cl 

KCN
 C2 H 5  CN 
H 3O

12. Acid
bond nor they can break hydrogen bond ( A)
between water molecules.
CH 3  CH 2  COOH  NH 3
32. Assertion (A) : Ethyl chloride gives ethyl
alcohol when treated with Ag2O in boiling ( B)
water. 13. C2 H 5ONa  C2 H 5  Cl 
Dry ether

Reason (R) : On boiling vapour presure of
water increases. C2 H 5  O  C2 H 5  NaCl
14. Alc.KOH is dehydrohalogenating agent.
15. Allyl chloride > vinyl chloride > propyl chloride
16. Rate is depenending only on one reactant. 4. , Y is
17. Iodination of benezene is a reversible reaction.
19. CH 3 group on benzene ring is ortho, para
directing group.
18. Aryl halides are less reactive towards 1) 2)
nucleophilic substitution than alkyl halides due
to partial double bond charecter obtained by
resonance.
20. NO2 group at ortho and para position with draws 3) 4)
electronsfrom the ring and makes to attack of
nucleophile easy. 5. The correct order of increasing boiling points
21. b.p. increases with increase in molecular mass. is
1) 1-chloropropane < isopropylchloride
29. C H 3  C H  C l
| < 1-chlorobutane
CH 3 2) isopropylchloride < 1-chloropropane
< 1-chlorobutane
30. Cl Cl
3) 1-chlorobutane < isopropylchloride
| |
< 1-chloropropane
CH 2  CH 2 Vic 
4) 1-chlorobutane < 1-chloropropane
< isopropylchloride

LEVEL-II (H.W) SN1 and SN2 reactions

6. Consider the following bromides

INTRODUCTION
1. Propane nitrile may be prepared by heating
1) Propyl alcohol with KCN
2) ethyl alcohol with KCN
3) Propyl chloride with KCN
4) ethyl chloride with KCN
2. C 2 H 5 Cl  dry
 Ag2 O
 A  Al

360 0
  B  S 
2 Cl 2
C
2 O3

In the above sequence of reactions identify

‘C’ Reactivity order S N 1 will be
1) Chloretone 2) Chloropicrin 1) II > III > I 2) II > I > III
3) Mustard gas 4) Lewisite gas 3) III > II > I 4) I > II > III
3. CH 3CH  CH 2 
HBr
 A 
aq KOH
B , 7. Which of the following is likely to give a
peroxide
precipitate with AgNO3 solution
B is
1) propanol-2 2) propanal - 1 1) CCl4 2) CH 3  CH 2  Cl
3) propanol - 1 4) propanal - 2 3)  CH 3  3 CCl 4) CHCl3
8. Which compound among the following, 16. Reaction Product formed
undergoes faster S N 1 reaction? a) R-X+RCOOAg p) alkene
b) R-X+NaOR q) ester
c) R-X+Aq.NaOH r) ether
1) 2) d) R-X+KOH s) alcohol
t) isonitrile
1) a-r, b-s, c-t, d-t 2) a-s, b-r, c-t, d-q
3) a-q, b-r, c-s, d-p 4) a-s, b-p, c-t, d-q
3) 4)
LEVEL-II (H.W) - KEY
9. Assertion (A): iso-Butyl bromide is a 1) 4 2) 3 3) 3 4) 3 5) 2 6) 1 7) 3
secondary halide. 8) 1 9) 4 10) 1 11) 1 12) 1 13) 4 14) 1
Reason (R): neo-Pentyl chloride is a primary
15) 1 16) 3
halide.
10. Assertion (A): Alkyl halides undergo LEVEL-II (H.W) - HINTS
nucleophilic substitution reactions readily.
1. C2 H 5Cl  KCN  C2 H 5CN
Reason (R): Halide ion is a very weak base
and hence can be easily replaced by the
attacking nucleophilie. 2.
11. Assertion (A): C-X bond in aryl halides is less
polar than the C-X bond in alkyl halides.
Reason (R): sp2 hybridized carbon is more
electronegative than sp3 hybridized carbon
atom.
12. Assertion (A): Alkyl chlorides are more 3. Anti Markowinkoff rule
reactive than alkyl bromides.
Reason: C-Cl bond is more polar than C-Br
bond. 4.
13. Assertion (A): 30 butyl bromide reacts with
sodium metal in presence of dry ether to give 7. 3o alkyl halides give white ppt with AgNO3
2, 2, 3, 3 tetra methyl butane solution
Reason (R): 3 0 butyl bromide under go 8. tertiary halide reacts faster.
elimination during the reaction condition to 16. A) C2 H 5Cl - Anaesthetic
give alkene B) Mg + dry ether - Grignard reagent
14. Assertion (A) : H 2 SO4 is not used during C) C2 H 5Cl  C2 H 5ONa -Williamson’ssynthesis
the reaction of alcohols with KI. D) Na + dry ether - Wurtz reaction
Reason (R) : H 2 SO4 oxidises HI to I2 and
PREVIOUS EAMCET QUESTIONS
will prevent reaction of alcohol with KI. 1. Which of the following is more readily
15. List - I List - II
hydrolised by S N 1 mechanism? (EAM-2014)
A) C2 H 5Cl 1)Williamson synthesis
B) R-X +Mg + dry ether 2) Wurtz reaction 1) C6 H 5CH (CH 3 ) Br 2)  C6 H 5 2 CHBr
C)C2H5Cl + C2H5ONa 3) Anaesthetic 3)  C6 H 5 2 C  CH 3  Br 4) C6 H 5CHCH 2 Br
D) Na + dry ether 4) Antiseptic
5) Grignard reagent 2. With respect to chlorobenzene, which of the
The correct match is following is Not correct? (EAM-2012)
A B C D A B C D 1) Cl is ortho / para directing
1) 3 5 1 2 2) 5 3 1 2 2) Cl exhibits +M effect
3) 3 4 1 2 4) 3 5 1 4 3) Cl is ring deactivating 4) Cl is meta directing
3. Identify A, B and C in the following reactions 4. A + SOCl2  B + SO2 + HCl ,

CH3Cl 
KCN
 A 
HYDROLYSIS
H O
B 
C2H5OH / H

C A  Na  C  H 2 ,
3

(EAM-2010) B  C  (C 2 H 5 ) 2 O  NaCl
A B C Then A is
1) CH 3 NC CH 3 NHCH 3 CH 3CO2C2 H 5 1) C2H5Cl 2) C2H5ONa
3) C2H5OH 4) C H3OH
2) CH 3CN CH 3CONH 2 CH 3COOH 5. Correct order of Boiling point for
3) CH 3CN CH 3COOH CH 3CO2C2 H 5 a) 1-chloropropane
b) isopropyl chloride
4) CH 3CN CH 3COOH (CH 3CO) 2 O c) 1-chlorobutane
4. Consider the following reaction 1) a < b < c 2) b > a > c
C2 H 5Cl  AgCN  EtOH / H 2O
 X (major ) 3) b < a < c 4) a > b > c
which one of the following statements is true 6. CH3CH 2COOAg  Br2 
CCl4
 X 
aq KOH

for X? (EAM-2009) Y 

red P4 / Br2
 Z . Z is
1) It gives propionic acid on hydrolysis
2) It has an estar function 1) CH 3CH 2CH 2 Br 2) CH 3CH 2 Br
3) It has a nitrogen linked to ethyl carbon 3) CH 3 Br 4) CH 3CH 2CH 3
4) It has a cyanide group 7. An alkyl halide on reaction with sodium in
PREVIOUS EAMCET - KEY presence of ether gives 2,2,5,5-
tetramethylhexane. The alkyl halide is
1) 3 2) 4 3) 3 4) 1 1) 1-chloro pentane
2) 1-chloro-2,2-dimethyl propane
LEVEL-III 3) 3-chloro-2,2-dimethyl butane
4) 2-chloro-2-methyl-butane
Preparation & Properties of haloalkanes:
1. When a mixture containing PCl3 and PCl5 is
heated with ethyl alcohol total of 4 moles of 8. 
Br2 ,heat
or uvlight
 X . X is
ethyl chloride is formed. Mole ratio of PCl3
and PCl5 in the mixture is
CH 2 CH 2 Br
1) 3 : 1 2) 1 : 1 3) 1 : 3 4) 2 : 1 CH  CH 3
2. Compound ‘A’ reacts with PCl5 to give ‘B’ |
which on treatment with KCN followed by 1) 2)
Br
hydrolysis gave propionic acid. A & B are NO2 NO2
respectively
C H 2C H 3
1) C3H8 & C3H7Cl 2) C2H6 & C2H5Cl C H 2C H 3

3) C2H5Cl & C2H4Cl2 4) C2H5OH & C2H5Cl 3) NO2 4)

3. Electrolysis of aq.CH3COONa gives (B) at Br
Br

anode (B) when heated with Cl2 at 4000C

Br
gives (C).
(C) when reacts with alcoholic NH 3 gives
finally 9.  Mg 
dry ether
 A 
H 2O
 B ; B is
(D) . Then D is
1)  C2 H 5 3 N 2)  C2 H 5 4 N  Cl  1) cyclohexanol 2) cyclohexane
3)  C2 H 5 2 NH 4) C2 H 5 NH 2 3) cyclohexene 4) hexane
10. CH 3  CHBr  CH 3 
alc . KOH
A Properties of haloarenes:-
HBr

peroxide
 B NaI
acetone
 C . C is
16.
1) CH 3  CH 2CH 2 I 2)
1) toulene 2) biphenyl
3) 4-chlorotoulene 4) ethyl benzene
3) 4) CH 3  CH  CHI 17. Which of the following compound undergoes
replacement of Cl by OH by merely warming
11. On mixing ethyl acetate with aqueous sodium with aq NaOH
chloride, the composition of resulting solution
1) CH 3COOC2 H 5  NaCl
2) CH 3COONa  C2 H 5OH 1) 2)

3) CH 3COCl  C2 H 5OH  NaOH

4) CH 3Cl  C2 H 5COONa
12. CH 3  CH 3   A 
Br2 / hv
 B
LiAlH 4

3) 4)

Br2 / hv
C  
Na / dry ether
 D . D is
1) CH 3  CH 2  CH 2  CH 3
2) CH 3  CH 2  O  CH 2  CH 3
3) CH 3  CH (CH 3 )  CH (CH 3 )  CH 3
18.
4) CH 3  CH 2  CH 3
13. Identify X,Y,Z in the following series
1) C6 H 4Cl2 2) C6 H 3Cl3
C2 H 5 I   X   Y  Z 3) C6 H 5  C6 H 5 4) C6 H 5  C2 H 5
alc.KOH Br2 Excess of KCN

1) Br—CH2—CH2—CN 2) CH3 — CH2— CN 19. Fluorobenzene ( C6 H 5 F ) can be synthesized

3) NC—CH2—CH2—CN 4) Br—CH2—CH2—Br
in the laboratory
14. The number of possible monochloro
1) by heating phenol with HF and KF
structural isomers formed on free radical 2) from aniline by diazotisation followed by
monochlorination of  CH  CHCH CH
3 2 2 3 heating the diazonium salt with HBF4
1) 2 2) 3 3) 4 4) 5 3) by direct fluorination of benzene with F gas 2
CH 3 4) by reacting bromobenzene with NaF solution
20. Which of the folloiwng will best convert
15. + HI  X ; X is
nitrobenzene into 3-fluorobromobenzene?

CH 2 I CH 3

1) 2) I

CH 3
CH 3 1) F2 / AlCl3 , Zn / HCl , NaNO2 / HCl  0 0 C , CuBr
2) Br2 / FeBr3 , SnCl2 / HCl, NaNO2 / HBF4  00 C, Heat
3) 4)
I
3) SnCl2 / HCl, NaNO2 / HBF4  00 C, Heat, Br2 / FeBr3
I
4) SnCl2 / HCl , Br2 / FeBr3 , NaNO2 / HBF4  00 C , Heat
21. The structure of the major product formed
in the following reaction
26. , Y is

1) 2)

3) CH 3  C (CH 3 )  CH 2 4) CH 3  CH 2CH 2  CH 2 Br
27. Which of the following halides would
1) 2) undergo nucleophillic substitution more
readily
1) 1-Chloro-1-Butene 2) 2-Chloro-1-Butene
3) 3-Chloro-1-Butene 4) 4-Chloro-1-Butene
28. CH 3 Br  Nu  CH 3  Nu  Br the
3) 4)
decreasing order of the rate of above reaction

22. In SN 2 reactions the correct order of the with nucleophiles Nu A to D is

reactivity for the following compounds
 Nu  ( A) PhO , ( B ) AcO , (C ) HO , ( D )CH 3O 
    

CH 3Cl , CH 3CH 2Cl ,  CH 3 2 CHCl and  CH 3 3 CCl 1) D > C > A > B 2) D > C > B >A
1) CH3CH2Cl CH3Cl CH3 2 CHCl CH3 3 CCl 3) A > B>C > D 4) B > D > C > A
29. The correct order of rate of S N 2 reactivity
2) CH3 2 CHCl  CH3CH2Cl  CH3Cl  CH3 3 CCl
of H 2O, OCH 3 , OH , CH 3COO is
3) CH3Cl CH3 2 CHCl  CH3CH2Cl CH3 3 CCl
1) OH  OCH 3  CH 3COO  H 2 O
4) CH3Cl CH3CH2Cl  CH3 2 CHCl CH3 3 CCl 2) H 2 O  O H  OC H 3  C H 3 C O O
23. The alkane that gives one isomeric 3) OCH 3  OH  CH 3COO  H 2 O
alkylhalide on photo chemical chlorination
is 4) H 2 O  C H 3 C O O  O H  O C H 3
1) propane 2) 2-methyl butane 30. Which of the following is most reactive
3) neopentane 4) isopentane towards nucleophillic substitution
24. The alkane which gives two isomeric mono 1) Chlorobenzene
chlorides on photo chemical chlorination is 2) 2, 4, 6 - Trinitrochloro benzene
1) ethane 2) butane 3) pentane 4) propane 3) 2, 4 - Dinitro chlorobenzene
4) 2 - nitro chlorobenzene
31. Which one of the following compounds will
25. , give enantiomeric pair on treatment with
HOH
Z is

1) 2)
1) 2)

3) 4) 3) 4)
32. Following is the list of four halides.Select 37. Order of nucleophilicity in polar aprotic
correct sequence of decreasing order of solvent?
reactivity for S N 1 reaction using the codes 1) I   Br   Cl   F 
given below. 2) F   Cl   Br   I 
3) I   Cl   Br   F 
I) II) C6 H 5  CH 2  Br 4) F   I   Br   Cl 
38. Which one of the following compounds will
be most reactive for S N 1 reaction?
III) IV) C6 H 5  CH 2  I

Codes:
1) III > I > IV > II 2) III > I > II > IV
3) I > III > IV > II 4) I > III > II > IV
33. The correct order of reactivity of following
compounds in SN1 reaction is
a) C6 H 5CH 2 Br
b) C6 H 5CH  C6 H 5  Br
c) C6 H 5CH  CH 3  Br
d) C6 H 5C  CH 3  C6 H 5  Br LEVEL-III - KEY
1) d > b > c > a 2) d > c > b > a
1) 2 2) 4 3) 2 4) 3 5) 3 6) 2 7) 2
3) a > b > c > d 4) a > c > d > b
8) 2 9) 2 10) 1 11) 1 12) 1 13) 3 14) 3
34. Order of rate of reaction with AgNO3 or rate
15) 2 16) 1 17) 4 18) 3 19) 2 20) 2 21) 4
of S N 1
22) 4 23) 3 24) 4 25) 3 26) 1 27) 3 28) 1
29) 3 30) 2 31) 3 32) 1 33) 1 34)3 35) 3
36) 1 37) 2 38) 1

LEVEL-III - HINTS
3C2 H 5OH  PCl3  3C2 H 5Cl  H 3 PO3
1) I > III > II 2) II > III > I 1. 1 mole
3) I > II > III 4) III > I > II
35. Which of the following species is most C2 H 5OH  PCl5  C2 H 5Cl  POCl3  HCl
reactive in an S N 2 reaction? 1 mole
1) CH 3CH 2  Cl 2) CH 3CH 2  Br C 2 H 5 O H  PC
 l5
 C 2 H 5 C l  
KCN
  C 2 H 5C N
KCl

3) CH 3CH 2  I 4) CH 3CH 2  F 2. ( A) (B)  H 2O

36. Order of nucleophilicity in polar protic C 2 H 5C O O H
solvent?
CH 3COONa 
electrolysis
 CH 3  CH 3
1) I   Br   Cl   F  3.
( B)
2) F   Cl   Br   I 
3) I   Cl   Br   F  
Cl2
400o C
 C2 H 5Cl 
NH 3
  C2 H 5 4 N Cl 
4) F   I   Br   Cl  (C ) ( D)
 C 2 H 5 O H  SO C l 2  C 2 H 5 C l  SO 2  H C l 17. As No. of electron with drawing group increase,
4.  A B replacement of Cl group becomes easy..

C2 H 5OH  Na  C2 H 5ONa  H 2 
 A C  18.

C2 H 5Cl  C2 H 5ONa  C2 H 5  O  C2 H 5  NaCl

 B C  Fittig reaction
5. As branching increases B.P decreases among 21. Alkyl halides undergo substitution more easily
isomers & as mol.wt increases B.P increases. than Aryl halides.
6. CH 3COOAg  Br2 
CCl4
 CH 3CH 2 Br 
aq KOH

C2 H 5OH 
red P4 / Br2
 C2 H 5 Br
7. Wurtz reaction 23.
8. Free radical substitution & reactivity is
t-H > S-H>P-H
9. R  X  Mg  R  MgX 
H 2O
 RH  MgXOH
10. CH 3  CHBr  CH 3 
alc . KOH
 CH 3  CH  CH 2
HBr

peroxide
 CH 3CH 2CH 2 Br NaI
acetone
 CH 3CH 2CH 2 I
11. No reaction 24. Anti Markowinkoff rule
12. CH 3CH 3 
Br / hv
 CH 3CH 2 Br 
2 LiAlH
 CH 3CH 3 4
28. CH 3O   OH   PhO   AcO 

Br2 / hv
 CH 3CH 2 Br 
Na / dry ether
 CH 3  CH 2  CH 2  CH 3
29. OCH 3  OH   CH 3COO   H 2O
13.

C2 H 5 I 
alc . KOH
 C2 H 4 
Br2
 Br  CH 2  CH 2  Br
 x Y   KCN
CN  CH 2  CH 2  CN
 z 30.

14. CH3 2 CHCH2CH2Cl, CH3 2 CHCH Cl  CH3

 CH 3 2 C  Cl  CH 2CH 3 , CH 3CH  CH 2Cl  CH 2CH 3
15. Markownikov’s rule

31. It has chiral centre.

16. 32. R-I is more reactive than R-Br and 20 is more
reactive than 10 .
33. The order of reactivity depends on the stability
of the carbocation formed
 2
5. reactions are
LEVEL-IV
S

N
1) Stereospecific but not stereoselective
1. Arrange the following compounds in 2) Stereoselective but not stereospecific
increasing order of rate of reaction towards 3) Stereoselective as well as stereospecific
nucleophilic substitution. 4) Neither stereoselective nor stereospecific
Cl 6. Consider the follwong bromides
Cl Cl
a) Me Br
CH 3
a) b) c)
Me
CH 3
b)
1) a < b < c 2) a < c < b Br
3) c < b < a 4) b < c < a
2. Arrange the following compounds in Me Me
increasing order or rate of reaction towards c)
nucleophilic substitution. Br
Cl Cl The correct order of SN1 reactivity is
Cl
O2 N 1) a > b > c 2) b > c > a
NO2
3) b > a > c 4) c > b > a
a) b) c) Note: In the following questions two or more
options may be correct Consider the
NO2 NO2
following reaction and answer the questions
1) c < b < a 2) b < c < a no 26-28
3) a < c < b 4) a < b < c
H
3. Pick up the correct order of reactivity of the H H H
H
following compounds in SN1 reactions HO -+ C Cl HO C Cl HO C + Cl-
CH3 H H
Cl
CH3 CH3
(a)
H H (d) (e)
(b) (c)
Cl
1) < < <
Br I
7. Whihc of the statements are correct about
above reaction?
Cl
CH3
CH3 CH3 1) (a) and (e) both are nucleophiles
2) <
Br
< Cl I
2) in (c) carbon atom is sp3 hybridised
<
3) in (c) carbon atom is sp hybridised
Cl CH3
CH3
4) (a) and (e) both are electrophiles
CH3
Cl 8. Arrange the following compounds in the
3) >
> >
Br I
increasing order of their densities
Cl CH3
CH3 CH3 Cl
Cl
4) >
> >
Br I

a) b)
4. Which of the following will be the least
reactive towards nucleophilic substitution?
Cl
Cl Br

1) C2 H 5Cl 2)
c) d)
CH2Cl
Cl Cl Cl

3) 4) 1) a < b < c < d 2) a < c < d < b

CH3 3) d < c < b <a 4) b < d < c <a
9. Match the reactions given in Column-I with
the types of reactions given in Column-II + -
N2X X
Column-I Cu2X2
3) + N2
Cl Cl Cl
Cl Cl
Cl2 / Fe
+ 4) C2 H 5Cl  NaI dry acetone
C2 H 5 I  NaCl
1)
Column-II
Cl a) Fittig reaction
CH 3  CH  CH 2  HBr  CH 3  CH  CH 3 b) Wurtz fittig reaction
2) c) Finkelstein reaction
Br
d) Sandmeyer reaction
CH 3  CH  I CH 3  CH  OH 1) 1-b, 2-a, 3-d, 4-c 2) 1-a, 2-b, 3-d, 4-c
3) OH  3) 1-a, 2-b, 3-c, 4-d 4) 1-b, 2-a, 3-c, 4-d
11. Assertion (A) : Ary iodides can be prepared
by reaction of arenes with iodine in the
Cl OH presence of an oxidising agent.
Reason (R) : Oxidising agent oxidises I2 into
 NaOH Hl.
4)
NO2 NO2 12. Assertion (A) : it is difficult to replace
chlorine by -OH in chlorobenzene in
CH 3CH 2CH CH 3 
ale. KOH
 CH 3 CH  CH CH 3 comparison to that in chloroehane.
5)
Br Reason (R) : Chlorine-carbon (C-Cl) bond
in chlorobenzene has a partial double bond
Column-II character due to resaonance.
a) Nucleophilic aromatic substitution
13. Asseertion (A) : Nitration of chlorobenzene
b) Electrophilic aromatic substitution
leads to the formation of
c) Saytzeff elimination
d) Electrophilic addition m-nitrochlorobenzene
Reason (R) : NO 2 group is a m-directing
e) Nucleophilic substituion  S N 1 group.
1) 1-b, 2-d, 3-e, 4-a, 5-c
2) 1-b, 2-d, 3-a, 4-c, 5-e COMPREHENSION QUESTION
3) 1-b, 2-d, 3-c, 4-a, 5-e  Monohalo derivatives of alkanes are alkyl
4) 1-d, 2-b, 3-a, 4-c, 5-e halides. In alkyl halides, halogen atom is
10. Match the reaction given in Column-I with attached to sp3 carbon. As number of carbons
the names given in Column-II increases, density of alkyl halide increases. Alkyl
Column-I halides undergo substitution reaction
14. Tertiary alkyl halide is
X  RX 
Na

1) R 1) CH 3  CH (CH 3 )  Br

X 2) CH 3  C (CH 3 ) 2  CH 2 Br
3) CH 3  CH 2  CH 2  Br
2) 2 + 2Na Ether + 2NaX
4) CH 3  C (CH 3 ) 2  Br
15. Density is highest for
1) CH 3 F 2) CH 3Cl 3) CH 3 Br 4) CH 3 I
16. Order of reactivity of various alkyl halides
towards nucleophillic substitution follows the
order
1) R  I  R  Br  R  Cl  R  F
2) R  I  R  Br  R  Cl  R  F
3) R  Br  R  I  R  Cl  R  F
4) R  Cl  R  Br  R  I  R  F
 S N reaction is bimolecular reaction which
2
takes place by formation of transition state.
Velocity of the reaction depends on the
concentration of substrate as well as nucleophile.
The reaction is favorable by strong nucleophile
in the presence of polar aprotic solvent.
Optically active halides gives. Walden inversion
by S N 2 mechanism. Presence of hetero atom
at   carbon, unsaturation at   carbon and
carbonyl group at   carbon favours S N 2
mechanism.
17. Which of the following compound will follow
S N 2 mechanism
1) CH 3  Br 2) CH 2  CH 2  CH 2  Br
3) C6 H 5  CH 2  Br 4) all of these
18. Which of the following compound will give
Walden inversion
1) C4 H 9  CHD  Br 2)  C6 H 5 2 CHBr
3)  CH 3 3 CBr 4) All of these
19. Which of the following compounds favours
SN 2 mechanism
1) CH 3  CH 2  Br 2) CH 3  O  CH 2 Br
3) C6 H 5  CO  CH 2 Br 4) CH 3  C  CH 3 2 CH 2 Br
IDENTIFY THE CORRECT ANSWER 25. The structure of A is
1) Statement 1 and Statement 2 are correct
and Statement 2 is correct explanation for
Statement 1
2) Statement 1 and Statement 2 are correct and
Statement 2 is not correct explanation for
Statement 1
3) Statement 1 is correct and statement 2 is
wrong
4) Statement 1 is wrong and statement 2 is
correct
20. Statement-1 : S N 2 reaction is carried out in
the presence of polar aprotic solvents
Statement-2: Polar aprotic solvents does not
contain acidic hydrogen
21. Statement I : reacts faster than
by SN1 mechanism.
Statement 2 : 20 alkyl halide is more reactive
towards SN1 mechanism than 30.
22. Statement-1: S N 1 reaction is carried out in
the presence of polar protic solvents
Statement-2: Polar protic solvent increases
stability of carbocation due to the solvation
PASSAGE-II
. An organic compound with molecular formula
C5 H 9Cl exists in two optically active froms A
and B. A on hydrogenation in presence of a
catalyst gives an optically inactive compound
(C). While B gives an optically active compound
D.
23. Which of the following is the correct IUPAC
name of compound D
1) 1-chloro-2-methylpentane
2) 2-chloro-2-methylpentane
3) 1-chloro-3-methylbutane
4) 1-chloro-2.methybutane
24. Which of the following is the correct IUPAC
name of compound C.
1) 1-chloro-2-methylbutane
2) 2-chloropentane
3) 3-chloropentane
4) 2-chloro-2-methylbutane
1) 2)
3) 4)
 HALO ARENES LEVEL-IV - KEY
1) Statement 1 and Statement 2 are correct 1) 4 2) 4 3) 1 4) 4 5) 3 6) 2 7) 1
and Statement 2 is correct explanation for
Statement 1 8) 1 9) 1 10) 1 11) 3 12) 1 13) 4 14) 4
2) Statement 1 and Statement 2 are correct and 15) 4 16) 1 17) 4 18) 1 19) 3 20) 2 21) 3
Statement 2 is not correct explanation for 22) 1 23) 4 24) 3 25) 1 26) 4 27) 1 28) 4
Statement 1 29) 1 30) 4
3) Statement 1 is correct and statement 2 is
wrong LEVEL-IV - HINTS
4) Statement 1 is wrong and statement 2 is
01. CH 3 group is more donating at ortho position
correct
26. Statement 1 : Aryl halides undergo 03. For SN1, R - Cl < R < Br < R - I and 20 < 30
electrophilic substitution more readily than 04. Aryl halides are less reactive than alkyl halides
benzene for nucleophilic substitution
Statement 2 : Aryl halide gives a mixture of o 06. Stability of carbocation (allyl > 20 > 10)
-, p - products 08. As mol. wt increases, density increases
27. Statement 1 : paradichlorobenzene has 11. Oxidising agent oxidises HI into I2 and prevents
higher melting point and solubility than that the reverse reaction
of ortho meta forms 13. In chlorobenzene, Cl is weakly deactivating but
Statement 2 : para isomer has symmetrical O, P directing
structure and can easily pack closely in 14. Halogen is attached to 3o carbon
crystal structure. 15. As molecular weight increases density increases
16. Reactivity order is
COMPREHENSION QUESTION
When a monosubstituted benzene undergoes R  I  R  Br  R  Cl  R  F
an electrophilic substitution, the position 17. All compounds are primary.
taken up by the incoming group and the rate 18. Compound is chiral.
of the reaction are determined by the 19. Presence of carbonyl group at   carbon
substituent already present on the benzene favours S N 2 mechanism.
ring. On this basis various substituents can
be divided into three categories: ADDITIONAL QUESTIONS
1) o, p-directing and activating 1. The position of -Br in the compound in
2) m-directing and deactivating CH 3CH  CHC  Br  CH 3 2 can be
3) o, p-directing and deactivating
29. Which of these is o, p-directing and classified as
deactivating group 1) Allyl 2) Aryl 3) Vinyl 4) Secondary
2. What should be the correct IUPAC name for
1)  F 2) Cl 3)  Br 4) all of these
diethylbromomethane?
30. Which one of the following compounds is
1) 1-Bromo-1, 1-diethylmethane
most reactive for aromatic electrophilic
substitution reaction 2) 3-Bromopentane
3) 1-Bromo-1-ethylpropane
1) C6 H 5  F 2) C6 H 5  Cl 4) 1-Bromopentane
3) C6 H 5  I 4) C6 H 5  NO2 3. Which reagent will you use for the following
reaction?
CH 3CH 2CH 2CH 3 
31. . X is
CH 3CH 2CH 2CH 2Cl  CH 3CH 2CHClCH 3
1) Cl2 / UV light 2) NaCl  H 2 SO4
1) o-methylchlorobenzene
2) p-methylchlorobenzene 3) Cl2 gas in dark
3) m-methylchlorobenzene 4) Both 1 & 2 4) Cl2 gas in the presence of iron in dark
4. How many chiral compounds are possible on 9. The order of reactivity of following alcohols
momochlorination of 2-methyl butane? with halogen acids is_________
1) 8 2) 2 3) 4 4) 6 a) CH 3CH 2  CH 2  OH
5. Which branched chain isomer of the
hydrocarbon with molecular mass 72u gives CH 3CH 2  CH  OH
only one isomer of mono substituted
alkylhalide b)
CH 3
1) Tertiary butyl chloride 2) Neopentane
3) Isohexane 4) Neohexane
CH 3
6. Arrange the following compounds in
increasing order of their boiling points. CH 3CH 2 C OH
c)
CH 3
a) CH  CH 2 Br CH 3
CH 3
1) a > b > c 2) c > b > a
b) CH 3CH 2CH 2CH 2 Br 3) b > a > c 4) a > c > b
10. Which of the following alcohols will yield the
CH 3
corresponding alkyl chloride on reaction with
c) H 3C C CH 3 concentrated HCl and anh. ZnCl2 at room
temperature?
Br
1) CH 3CH 2  CH 2  OH
1) (b) < (a) < (c) 2) (a) < (b) < (c)
3) (c) < (a) < (b) 4) (c) < (b) < (a) CH 3CH 2  CH  OH
7. Which is the correct increasing order of 2)
CH 3
boiling points of the following compounds?
1- lodobutane, 1-Bromobutane, CH 3CH 2  CH  CH 2OH
1-Chlorobutane, Butane 3)
CH 3
1) Butane < 1-Chlorobutane < 1-Bromobutane
< 1-lodbutane CH 3
2) 1-lodobutane,< 1-Bromobutane< 1-
Chlorobutane< Butane CH 3CH 2 C OH
4)
3) 1-Bromopropane< 1-Bromobutane1- CH 3
Bromobutane< 1-Chlorobutane
4) Butane< 1-Chlorobutane< 1-lodobutane< 11. Which of the following haloalkanes react
1-Bromobutane with aqueous KOH most easily?
8. Which is the correct increasing order of 1) 1-Bromobutane
2) 2-Bromobutane
boiling points of the following compounds?
3) 2-Bromo-2-methylpropane
1-Bromoethane, 1- Bromopropane, 4) 2-Chlorobutane
1-Bromobutane, Bromobenzene 12. Match the compounds given in column-I with
1) Bromobenzene< 1-Bromobutane< 1- the effects given in Column-II
Bromopropane< 1-Bromoethane Colunm-I Column-II
2) Bromobenzene< 1-Bromoethane< 1- 1) Chloramphenicol a) Malaria
Bromopropane< 1-Bromobutane 2) Thyroxine b) Anaesthetia
3) 1-Bromopropane< 1-Bromobutane< 1- 3) Chloroquine c) Typhoid fever
Bromoethane< Bromobenzene 4) Chloroform d) Goiter
4) 1-Bromoethane< 1-Bromopropane< 1- 1) 1-c, 2-d, 3-a, 4-b 2) 1-d, 2-c, 3-a, 4-a
Bromobutane< Bromobenzene 3) 1-c, 2-d, 3-b, 4-a 4) 1-a, 2-b, 3-c, 4-d
13. Match the items of Column-I and Coumn-II 17. The reaction described is
Colunm-I Column-II CH3(CH2)5
(CH2)5CH3
1) SN1 reaction a) vic-dibromides Br OH -
H C HO C H
2) Chemicals in fire b) gem-dihalides
CH3 CH3
extinguisher
3) Bromination of c) Racemisation 1) SE2 2) SN1 3) SN2 4) SN0
alkenes 18. The organic chloro compound, which shows
4) Alkylidene halidesd) Saytzeff rule complete stereo chemcial inversion during
e)Chlorobromocarbons SN2 reaction is
1)  CH 3 3 CCl 2)  CH 3 2 CHCl 3) CH 3Cl 4)  C2 H 5 2 CHCl
5 ) e l i m i n a t i o n o f H X

from alkylhalide
1) 1-c, 2-e, 3-a, 4-b, 5-d 2) 1-c, 2-e, 3-b, 4-d, 5-a 19. Arrange the following compunds in
3) 1-b, 2-d, 3-c, 4-e, 5-a 4) 1-c, 2-e, 3-b, 4-d, 5-a increasing order of rate of reaction towards
14. Match the structures of compounds given in nucleo philic substitution.
Coumn-I with the classes of compounds given Cl
Cl
Cl
in Column-II NO 2
Colunm-I Column-II a) b) c)
CH 3  CH  CH 3 CH 3

1) a) Aryl halide 1) a < b < c 2) c < b <a 3) b < a < c 4) c < a < b
X
2) CH 2  CH  CH 2  X b) Alkyl halide
ADDITIONAL QUESTIONS - KEY
1) 1 2) 2 3) 1 4) 3 5) 2 6) 3 7) 1
X
8) 4 9) 2 10) 4 11) 3 12) 1 13) 1 14) 1
3) c) Vinyl halide 15) 1 16) 4 17) 3 18) 3 19) 3
ADDITIONAL QUESTIONS - HINTS
4) CH 2  CH  X d) Allyl halide 1. ‘Br’ is attached to carbon atom adjacent to the
double bonded carbon (allyl)
1) 1-b, 2-d, 3-a, 4-c 2) 1-b, 2-a, 3-d, 4-c 2 Longest carbon chain contains five carbon atoms
2) 1-a, 2-b, 3-d, 4-c 4) 1-a, 2-b, 3-c, 4-d 3. Free radical substitution
15. Match the structures given in Column-I with * *
the name in Column-II CH 3  CH  CH  CH 3
Colunm-I Column-II 4. | |
Br CH 2Cl
1) a) 4-Bromopent-2-ene 5. A hydrocarbon with molar mass 72 is
neopentane  C5 H12 
6. Among isomeric compounds, as the length of
2) b) 4-Bromo-3-methylpent-2-ene carbon chain increases, boiling point increases
7. As mol. wt increases b.p increases (if length of
carbon chain is same)
3) c) 1-Bromo-2methylbut-2e-ne 8. Based on above two concepts
9. Carbo cation stability order  30  20  10 
4) d)1-Bromo-2methylpent-2-ene 11. aq KOH favours SN1
15. Longest chain is to the considered ; Functional
1) 1-a, 2-c, 3-b, 4-d 2) 1-a, 2-b, 3-c, 4-d group (double bond) should be indicated with
3) 1-b, 2-d, 3-a, 4-c 4) 1-d, 2-b, 3-c, 4-a lowest number
16. A dextrorotatory optically active alkyl 16. Inversion in configuration is observed it does
halide undergoes hydrolysis by SN2 not mean that the configuration will change; it
mechanism. The resulting alcohol is depends on the nature of leaving group and the
1) Dextrorotatory 2) Laveorotatory nucleophile which enters
3) Optically inactive due to recemisation 17. Inversion in configuration - SN2
4) may be dextro (or) laevorotatory 19. In aromatic halides, Electron with drawing
groups favour nucleophilic substitution