1 HALOALKANES AND HALOARENES

Exercise – 1: Basic Objective Questions

Nucleophiles And Electrophiles 6. Which of the following species is a nucleophile?
(a) CN  (b) CH3
1. Which of the following species is an electrophile? (c) Br (d) all of these
 
(a) H (b) H Ans. (d)
(c) both (a) and (b) (d) none of these Sol. The species which can donate electrons are known as
Ans. (a) nucleophiles. A nucleophile can either be negatively
Sol. H+ has the tendency to accept electrons whereas H- has charge or it can have excess electrons. In the given
no tendency. question all of the species given are nucleophiles. In the
given options every species carries a negative charge
and can donate an electron. Hence, the correct answer is
2. Which of the following species is an electrophile? an option (d)
(a) BH3 (b) NO2 7. The decreasing order of nucleophilicity among the
 nucleophiles
(c) Br (d) all of these (A) CH3C – O- (B) CH3O-
Ans. (d) O
Sol. All these species are electron deficient and have (C) CN-
tendency to accept electrons. So, these are
electrophiles.

3. Which of the following species is a nucleophile? (D)

 (a) C > B > A > D (b) B > C > A> D
(a) H2O (b) H3 O
(c) D > C > B > A (d) A > B > C > D
(c) both (a) and (b) (d) none of these Ans. (a)
Ans. (a) Sol. Bulkier the nucleophile lesser will be nucleophilicity.
Sol. H 2 O has a tendency to attack +ve charge due to lone The negative charge or lone pair should be on less
pairs. electronegative atom of nucleophile. So, the order of
nucleophilicity is C > B > A > D.
4. Which of the following species is a nucleophile?

(a) C H 2 O (b) CH3OH Solvent and leaving group
(c) both (a) and (b) (d) none of these
Ans. (c) 8. Consider the following groups
Sol. Both have a nucleophilic tendencies. In (a) the oxygen
(I) — OCOCH3 (II) — OCH3
has a negative charge and in (b) the oxygen has lone
pairs. Both are the characteristics of nucleophiles. (III) — OSO2CH3 (IV) — OSO2CF3
The decreasing order of their leaving ability is
5. Which of the following species is a nucleophile?
(a) I > II > III > IV (b) IV > III > I > II
(a) NH3 (b) NH2 (c) III> II > I > IV (d) II > III > IV > I
(c) OH  (d) all of these Ans. (b)
Ans. (d) 1
Sol. leaving ability 
Sol. The species which can donate electrons are known as Basicstrength
nucleophiles. A nucleophile can either be negatively
charge or it can have excess electrons. In the given  delocalisation of -ve charge  stability of anion
question all of the species given are nucleophiles.
Hence, the correct answer is an option (d)
HALOALKANES AND HALOARENES 2

Nucleophilicity and its variation Θ  Θ Θ Θ Θ Θ Θ

(a) F> Cl >Br > I (b) I >Br > Cl >F
Θ Θ Θ Θ
9. Among these nucleophiles, which of the following
(c) I >Br >F>Cl (d) none of these
orders is correct for their nucleophilicity order in gas
phase? Ans. (a)
Sol. DMF is a polar aprotic solvent. The given options
CH 3 , NH 2 , OH  ,F -
belong to the same group and nucleophilicity decreases
   -
(a) CH 3 >NH 2 >OH >F down the group in polar aprotic solvents.
(b) F   OH   NH 2  CH 3
Θ Θ Θ Θ
  - 
(c) OH >NH 2 >F >CH 3 12. F,Cl,Br, I
(d) none of these Among these nucleophiles, which of the following
Ans. (a) orders is correct for their nucleophilicity order in
water?
Sol. Nucleophilicity is the ability of a group to donate
Θ Θ Θ Θ Θ Θ Θ Θ
electron pairs. Along the same period the
nucleophilicity is inversely proportional to the (a) F>Cl >Br>I (b) I >Br >Cl>F
Θ Θ Θ Θ
electronegativity of the electron donation atom. Thus,
the higher the electronegativity of the atom, the lower (c) I >Br >F>Cl (d) none of these
is the nucleophilicity. Ans. (b)
Given anions are: Sol. Water is a polar protic solvent. The given options
Θ Θ Θ Θ belong to the same group and nucleophilicity increases
C H 3 , N H 2 , O H, F . down the group in polar protic solvents.
The order of the electronegativity of atoms are:
F>O>N>C 13. For the following:
Hence the order of nucleophilicity will be in the (1) I– (2) Cl– (3) Br–
Θ Θ Θ Θ
the increasing order of nucleophilicity in polar protic
reverse order i.e. C H 3 > N H 2 > O H> F which is the
solvent would be
option (a).
(a) I–< Br–< Cl– (b) Cl–< Br–< I–
– – –
Θ Θ Θ Θ
(c) I < Cl < Br (d) Br–< Cl–< I–
10. C H 3 , N H 2 , O H, F Ans. (b)
Among these nucleophiles, which of the following Sol. The given options belong to the same group and
nucleophilicity increases down the group in polar protic
orders is correct for their nucleophilicity in acetone?
solvents.
Θ Θ Θ Θ

(a) C H 3  N H 2  O H> F
Mechanisms of substitution reactions
(b) F  OH  NH2  CH3
14. The alkyl halide is converted into an alcohol by
Θ Θ Θ Θ
(a) Addition (b) Substitution
(c) O H> N H 2  F  C H 3
(c) Dehydrohalogenation (d) Elimination
(d) none of these
Ans. (b)
Ans. (a)
Sol. In the alkyl halides, the halide group is a good
Sol. Acetone is a polar aprotic solvent which means that leaving group. Also, the halide is more
there is a large dipole moment of the molecule due to electronegative compared to carbon. So, it creates a
difference in electronegativities of oxygen and partial positive charge on the carbon it is attached.
hydrogen atoms. So, as the electronegativity of the So, this halide leaves which makes a way for other
central atom increases the nucleophilicity decreases. nucleophiles to attack its position.

Θ  Θ Θ
The OH- group can act as a nucleophile and attack
11. F, Cl , Br, I that position. So, the halide in alkyl halide can be
Among these nucleophiles, which of the following substituted by the OH- group to form alcohols.
CH 3CH  Cl  CH 2 CH3   CH3 CH  OH  CH 2 CH 3
-
orders is correct for their nucleophilicity order in DMF? OH
3 HALOALKANES AND HALOARENES

Hence, this is a substitution reaction which is option secondary carbon, it has the tendency to go for both
(b). mechanisms.

15. C3 H8  Cl2 

Light
 C3 H7Cl  HCl is an example of 18. Which of the following two reactions would be
faster?
(a) Substitution (b) Elimination Θ Θ
(c) Addition (d) Rearrangement reaction (a) CH 3 -I+ O H  CH 3 -OH+ I
Ans. (a) Θ Θ

Sol. The given reaction is: (b) CH 3 -Cl+ OH  CH 3 -OH+ Cl

C3 H 8 +Cl 2 
Light
 C 3 H 7 Cl+HCl (c) both have similar rates
Here, we can see that one of the hydrogens in the (d) rates cannot be predicted
alkane is replaced by chlorine. This means that the Ans. (a)
hydrogen is substituted by chlorine. Sol. Bond-breaking is easier with iodine because the
Hence, this reaction is a substitution reaction which is electronegativity of iodine is lesser than the
option (a). electronegativity of chlorine atom. So, as the
electronegativity decreases the reactivity increases.
16. R -X +N aO H  R O H +N aX
The above reaction is classified as 19. The less reactivity of chlorine atom in CH 2 =CH-Cl
(a) Nucleophilic substitution is due to
(b) Electrophilic substitution (a) Inductive effect
(c) Reduction (b) Resonance stabilization
(d) Oxidation (c) Electromeric effect
Ans. (a) (d) Electronegativity
Sol. The given reaction is: R -X +N aO H  R O H +N aX Ans. (b)
Here, we can see that the –OH group is being Sol. Due to the resonance the partial double bond is formed
substituted with the –X group in the compound RX. between the carbon and chlorine atom which is stronger
So, it’s a substitution reaction. than the sigma or single bond.

Now, the oxygen in the O H group has negative charge
which can easily be donated to the R of RX. This
means that the group acts as a nucleophile and the
reaction is a nucleophilic substitution reaction.
Hence option (a) is the correct one.

20. Which one of the following is most reactive towards

17. Isopropyl chloride undergoes hydrolysis by:
nucleophilic substitution?
(a) SN1 mechanism
(a) H2 C=CH-Cl (b) C6 H5Cl
(b) SN2 mechanism
(c) SN1 and SN2 mechanism (c) CH3 -CH=CH-Cl (d) ClCH2 -CH=CH2
(d) Neither SN1 nor SN2 mechanism Ans. (d)
Ans. (c) Sol. In options (a), (b), and (c) molecules the chlorine atom
Sol. is attached with sp 2 hybridized carbon atom and in
Cl option (d) the chlorine atom is attached with sp 3
+ hybridized carbon atom. The others have a very less
- Cl-
HC CH3 HC CH3 tendency for nucleophilic substitution.

21. In SN1 reaction, the racemization takes place. It is due

CH3 CH3
to
The order for the SN 1 reaction is 3  2   1 and the (a) conversion of configuration
order for the SN 2 reaction is 1  2  3 . Since, its (b) retention of configuration
(c) inversion of configuration
HALOALKANES AND HALOARENES 4

(d) both (b) & (c)

Ans. (d) 23. Among the following, the one which reacts most
Sol. There are two steps in SN1 reaction, in the first step, readily with ethanol is
there is the removal of an atom or molecule from (a) p-nitrobenzyl bromide
compound leads to the formation of a carbocation. We (b) p-chlorobenzyl bromide
know that the central carbon atom of the carbocation is (c) p-methoxybenzyl bromide
sp 2 hybridized, and the structure of sp 2 hybridized (d) p-methylbenzyl bromide
carbon atom is planar. Now, in the next step, the Ans. (c)
nucleophile will attack the carbocation, since the
Sol. Ethanolysis or alcoholysis or solvolysis is an SN 1
structure is planar, the nucleophile can attack from any
face, there will be formation of two enantiomers in mechanism (to a large extent) involving rate-
equal amount. So, overall the mixture will be optically determining step of carbocation formation. The p-
inactive. methoxybenzyl bromide will be more stable due to the
+R effect.
22. SN1 reaction of alkyl halides leads to
(a) retention of configuration
(b) racemisation
(c) inversion of configuration
(d) none of these
Ans. (b)
Sol. The SN 1 reaction works with the formation of a
carbocation. The fastest rate of this reaction depends
on the stability of the carbocation.
The mechanism of SN 1 is shown below:
24. The reaction described is
The is a stepwise mechanism

(a) SE2 (b) SN1

(c) SN2 (d) SNi
Ans. (c)
Sol. The given reaction is:

As we can see in this reaction an intermediate

carbocation is formed which is planar in structure. In this reaction inversion of configuration taking place
The planar structure allows the attack of nucleophile So, the reaction will be Nucleophilic substitution Bi-
possible from any direction. So, we can see an molecular or SN2.
equimolar mixture of both configurations which may Hence, option (c) is the correct one.
be optically active and mirror images of each other.
But due to the presence of an equal amount of these
25. When the concentration of alkyl halide is tripled and
isomers, the entire mixture is optically inactive since 
they cancel the effect on each other. This mixture is concentration of O H is reduced to half, the rate of SN2
known as a racemic mixture and the process is known reaction increased by:
as racemisation. (a) 3 times (b) 1.5 times
Hence, option (b) is the correct one. (c) 2 times (d) 6 times
5 HALOALKANES AND HALOARENES

Ans. (b)
Sol. For S N 2 reaction, Rate [Alkyl halide] [Nucleophile]
∴If concentration of R – X is tripled and OH -  is
 
halved, rate will become 1.5 times.

26. Which reagent will you use for the following reaction?
CH 3CH 2CH 2CH 3  CH 3CH 2CH 2CH 2Cl  CH 3CH 2CHClCH 3
(a) Cl2/UV light
(b) NaCl + H2SO4
(c) Cl2 gas in dark
(d)Cl2 gas in the presence of iron in dark
Ans. (a)
Sol. The given reaction is a substitution reaction. It involves 28. Formation of free radical takes place with absorption of
the replacement of 1° and 2° hydrogen atoms of alkanes minimum energy in the formation of :
by chlorine. It occurs in presence of ultraviolet light or (a)
at high temperature. The chlorination does not occur at
room temperature in absence of light. In this reaction,
light is absorbed by the chlorine molecule and activated
(b)
chlorine initiates the reaction as follows

(c)

(d)

Ans. (d)
27. 2, 6 - Dimethylheptane on monochlorination Sol.
produces……. derivatives (including stereoisomers)
(a) 5 (b) 6
(c) 3 (d) 4
Ans. (b)
Sol. 2,6 - Dimethylheptane is a disubstituted alkane. Two
Stability of free radical is 3o >2o >1o.
methyl groups are attached to the second and sixth
carbon atoms on the chain, there are four free terminal
methyl groups. Monochlorination can occur on all of 29. Following reaction
them. The products formed after mono chlorination (CH3)3CBr + H2O  (CH3)3COH + HBr is an example
will be of
(a) elimination reaction
(b) free radical substitution
(c) nucleophilic substitution
(d) electrophilic substitution
Ans. (c)
Sol. So in this reaction bromine is replaced with hydroxyl
group, so this reaction is a substitution reaction. And
HALOALKANES AND HALOARENES 6

we know that H2O has lone pair so it is a nucleophile.

So, the reaction is a Nucleophilic substitution reaction. (a) II > III > IV > I (b) IV > III > II > I
(c) III > IV > II > I (d) I > II > III > IV
30. The increasing order of reactivity of the following Ans. (a)
bromides in SN1 reaction is Sol. S N 1 reactivity increases for stable carbocation. When
bromine will be eliminated there will be formation of
carbocation, this carbocation is stabilized by
hyperconjugation of the substituents attached at the
para-position. In compound (II) there are three
hydrogen atoms present, in (III) there are two hydrogen
(I) (II) atoms, (IV) there is one hydrogen atom, and in (I) there
Br is no hydrogen atom. As the number of hydrogen atoms
increases, the stability due to hyperconjugation
increases.

(III) (IV)
32. Rate of SN1 reaction is:
Br Br
(a) III > I > II > IV (b) III > II > I > IV (P)
(c) II > III > I > IV (d) II > I > IV > III
Ans. (d)
Sol. It depends on the carbocation stability. In (II), the (Q)
carbocation formed will be an aromatic carbocation so,
it will be the most stable. (III) will form anti-aromatic
carbocation while (I) is resonance stabilized
carbocation, and (IV) is secondary carbocation.
(R)
31. Arrange the following halides in decreasing order of
reactivity in SN1 reaction

(S)

(a) S > Q > R > P (b) S > R > P > Q

(c) P > Q > R > S (d) S > R > Q > P
(I) (II) Ans. (a)
Sol. SN 1 reaction proceeds via carbocation intermediate. The
reactivity of a substrate depends on the stability of
carbocation. The greater the stability of carbocation, the
greater will be its ease of formation from an alkyl
halide, and hence faster will be the rate of the reaction.
As we know tertiary carbocation is most stable (due to
the +I effect of substituents) therefore, the tert-alkyl
halides will undergo S N 1 reaction very fast. The
order of reactivity is as follows,
CH 3 X  10  2 0  3 0
(III) (IV)
Here, molecule (S) is a secondary alkyl halide
carbocation is stabilized by an aromatic ring and a
methyl group. Hence it has a greater reactivity towards
7 HALOALKANES AND HALOARENES

S N 1 reaction. (Q) and (R) are primary alkyl halides. delocalization of the positive charge by the two
Since the aromatic ring stabilizes the positive charge phenyl groups adjacent to it. Also, –CH3 group has +I
(Q) is more reactive than (R) followed by (P). So, the effect
order of reactivity is written as, S  Q  R  P
Option B:
Thus, (a) is the correct option.

33. The rate of SN1 reaction is fastest with:

(a)

Here, after the bromine leaves, the carbocation

formed on the carbon is also stable due to the
delocalization of the positive charge by the phenyl
group adjacent to it, but it is less stable compared to
(b)
option (A) since it has two phenyl groups but this
compound has one phenyl group.

Option C:

(c)

Here, after the bromine leaves, the carbocation

formed on that carbon on which bromine was
attached. Here phenyl ring is present but the presence
of electron-withdrawing group destabilizes it. So it is
(d) less stable compared to option (A) and (B).
Option D:
CH2 Br
CH2 Br
Ans. (a)
Sol. The SN 1 reaction works with the formation of a
Here, after the bromine leaves, the carbocation
carbocation. The fastest rate of this reaction depends
formed on that carbon on which bromine was
on the stability of the carbocation. The stability of the
attached. We can see that the carbocation formed is
carbocation increases with the delocalization of the
attached to a phenyl ring and it is stable. But it is less
positive charge. Also, the presence of the electron-
stable compared to option (A).
donating group increases the stability of carbocation
Hence, the most stable carbocation is formed in
whereas the presence of electron-withdrawing group
option (A) and it undergoes the fastest S N 1 reaction.
destabilise the carbocation.
When there is a phenyl group present adjacent to the 34. Arrange the following in decreasing order of
carbocation, the positive charge delocalizes and it reactivity towards SN1 reaction
becomes stable.
Let us look at the options: (P) CH 3 -Cl (Q)
Option A:

(R) (S)
(a) S > R > Q > P (b) S > Q > R > P
(c) R > S > Q > P (d) P > Q > R > S
Ans. (a)
Here, after the bromine leaves, the carbocation
formed on the carbon is highly stable due to the
HALOALKANES AND HALOARENES 8

Sol. Greater the stability of carbocation, more it favors S N 1 .

The stability of tertiary carbocation will be the most
stable and the primary carbocation will the least stable.

35. Which of the following compounds will undergo SN1

reaction?

37. Which of the following reactions follows SN2

mechanism
(a) C H 3 Br + O H -  C H 3 O H + Br -
(a) (b)
(b)
Θ Θ
CH 3  CH(Br) - CH 3 + O H  CH 3 CH(OH) - CH 3 + Br

(c) C H 3 C H 2 O H  -H
2 O
 CH 2 =CH 2

(d)
CH3 CH3
(c) (d)
Ans. (a) H3C CH3 + OH- H3C CH3 + Br -

Sol. The compound a is a tertiary alkyl halide and there is Br OH

formation of the carbocation intermediate formed by
the loss of the chlorine ion which stabilized by the Ans. (a)
resonance with the benzene ring. Hence, the correct  
Sol. The order for the SN 2 reaction is 1  2  3 . The


answer is option (a)

first option represents the best conditions to proceed by
S N 2 mechanism because it is a primary alkyl halide.
36. Which one of the following will give racemised
product in C2H5OH?
38. Arrange the following in the decreasing order of their
rate of SN2 reaction.

(P) (Q)
(a) (b) (R) H 3 C -B r (S) H 3 C=CH-Br
(a) S > P > Q > R (b) Q > S > R > P
(c) Q > R > P > S (d) R > Q > P > S
Ans. (c)
Sol. Allylic halides highly favor SN2 reaction. So (Q) must be
first but vinylic halides hardly go for SN2 reaction.
(c) (d) Thus, it must be last. The other two are decided on
Ans. (c) basis of crowding.
Sol. The chiral center is present in (c) only. For the reactant
to give a racemic mixture the compound must have at 39. Arrange the following in the decreasing order of their
least one chiral carbon atom. The reaction of formation rate of SN2 reaction.
of a racemic mixture of option (c) is given below:
9 HALOALKANES AND HALOARENES

41.
This reaction would follow which of the following
pathway predominantly?
(a) SN1 (b) SN2
(c) E1 (d) E2
(P) (Q) Ans. (b)
Sol. HI is very strong acid consequently, by Bronsted
Lowry,I- is very weak base. Thus elimination is out
of question. Similarly, the halide being primary, S N 2
takes place.

42. Which among MeX, RCH2X, R2CHX, R3CX is most

reactive towards SN2 reaction?
(R) (S) (a) MeX (b) RCH2X
(c) R2CHX (d) R3CX
(a) Q > R > P > S (b) R > Q > S > P
Ans. (a)
(c) P > Q > R > S (d) S > P > R > Q
Sol. S N 2 reaction means nucleophilic substitution bi-
Ans. (d)
molecular reaction. This reaction takes place when
Sol. EWG shall increase the rate of bimolecular the leaving group is attached to the primary carbon
nucleophilic substitution. NO2 is the electron atom. As the number of substituents on the carbon atom
withdrawing group so, it will be most reactive. Both carrying halogen increases, steric hindrance increases
OCH 3 and CH 3 both are electron donating group so, and hence the rate of SN2 reaction decreases.
both will decrease the rate of bimolecular Nucleophilic Hence, option (a) is the correct one.
substitution. The bimolecular Nucleophilic substitution
ability will be more decreased by OCH 3 group than the 43. The order of reactivities of the following alkyl halides
CH3 group. for a SN2 reaction is
(a) RF > RCl > RBr > RI
40. Predict the major product of the reaction (b) RF > RBr > RCl > RI
(c) RCl > RBr > RF > RI
(d) RI > RBr > RCl > RF
Ans. (d)
Sol. S N 2 reaction is the nucleophilic substitution bi-
(a) (b) molecular reaction in which the leaving group is
substituted by a nucleophile.
The reactivity of the alkyl halides towards SN 2
reaction depends on the quality of the leaving group.
(c) (d) If the halide is a good leaving group, then the
Ans. (c) reactivity increases.
Sol. EtO - K + + PhOH 
 EtOH + PhO - K +
Now, the strength of the bond between the carbon
atom and the halogen decides the quality of the
Now, here PhO - , where is in excess, will attack as a leaving group. If the bond strength is weak then the
nucleophile. Since the halide is a terminal bromide, the halogen will be a good leaving group because it can
reactions is S N 2 (even though PhO - is weak easily break the C – X bond.
nucleophile than ethoxide)
HALOALKANES AND HALOARENES 10

Now, the larger the size of the halogen, larger will be deprotanation of hydrogen atom from the beta carbon
the bond length and weaker will be the bond and atom. The mechanism is given below:
thus, in turn, the halogen will be a better leaving
group. So, the order of the size of halogens is I > Br >
Cl > F.
Hence the order of reactivity of the alkyl halides
towards S N 2 reaction will be: R – I > R – Br > R –
Cl > R – F, which is option (d).
46. n-Propyl bromide on treatment with ethanolic
Mechanisms of elimination reactions potassium hydroxide produces
(a) Propane (b) Propene
44. 1-Chlorobutane on reaction with alcoholic potash (c) Propyne (d) Propanol
gives Ans. (b)
(a) 1-Butene (b) 1-Butanol Sol. The treatment of ethanolic potassium hydroxide with n-
(c) 2-Butene (d) 2-Butanol propyl bromide leads to an elimination reaction. In the
elimination reaction, unsaturated compounds are
Ans. (a)
produced by the elimination of a leaving group.
Sol. The treatment of alcoholic potash or potassium Let us see the reaction:
hydroxide with 1-chlorobutane leads to an
elimination reaction. In the elimination reaction, CH3CH2CH2Br+ KOH  alc.  CH3CH=CH2 + KBr +H2O
n-Propyl Bromide Propene Potassium Bromide Water
Ethanolic Potassium Hydroxide
unsaturated compounds are produced by the
elimination of a leaving group.
Hence, we can see that option (b) is the correct answer.
Let us see the reaction:
CH 3 CH 2 CH 2 CH 2 Cl + KOH  CH 3 CH 2 CH=CH 2 + KBr + H 2 O
1-Chlorobutane 1-Butene 47.
Hence, we can see that 1-butene is produced and thus
option (a) is the correct answer.
Major product :
45. Major product of the following reaction is:

(a) (b)

(c) (d)
Ans. (b)
Sol. E2 elimination

(a) (b)

(c) (d)

Ans. (b)
Sol. CH 3 NH 2 is a weak agent. Thus, the elimination is E 1 -
Type. The bromine atom will be eliminated and
11 HALOALKANES AND HALOARENES

48. Ans. (c)

Sol. Here, the leaving group is fluorine and when it is
treated with alcohol and alkoxide then there will be the
formation of least substituted alkene.

51. What alkyl halide would give the following alkene as

This reaction would follow which of the following the only product in an elimination reaction
pathway predominantly?
(a) SN1 (b) SN2
(c) E1 (d)E2
Ans. (d)
Sol. Tert-butoxide being a very strong base, elimination
must take place and bulky base favours E2 over E1

49. When CH3CHClCH2CH3 is treated with alcoholic

KOH, the major product is (a) (b)
(a) CH3 – CH = CH – CH3
(b) CH2 = CH – CH2 – CH3
(c) CH3 – CHOH – CH2 – CH3
(d) CH3 – CH2 – CH2 – CH3 (c) (d) Both (a) and (b)
Ans. (b)
Ans. (a)
Sol. When CH 3 CHClCH 2 CH 3 is treated with Sol. Only the option (b) can give the specified product
because the rearrangement cannot be done. The
alcoholic KOH, elimination reaction takes place. chlorine atom is eliminated and the hydrogen atom
Chloride along with hydrogen is eliminated. Now, the removed from the β-carbon atom. The reaction is given
elimination of the particular hydrogen is decided by below:
the Saytzeff’s rule.
It says that the hydrogen is eliminated from the beta
carbon which has less number of hydrogen.
Now, let us look at the compound.
1 2 3 4
C H3 CH  Cl  C H 2 C H3
β α β γ

From this, we can see that the chlorine is attached to

the second carbon which is the alpha carbon. Now
there are two beta carbons, C – 3 and C – 1. But, C –
3 has two hydrogens while C – 1 has three
hydrogens. Thus, according to the Saytzeff’s rule, the 52. C6H6Cl6 is six membered cyclic compound in which
hydrogen will be eliminated form C – 3. Hence the each carbon carry one chlorine atom, on treatment with
overall reaction will be: alcoholic KOH yields
KOH
CH 3 CHClCH 2 CH3   alc.
 CH 3 CH=CHCH 3 (a) C6H6 (b) C6H3Cl3
Hence, this is the major product which is option (a). (c) (C6H6) OH (d) C6H6Cl4
Ans. (b)
50. The major product obtained on treatment of
CH3CH2CH(F)CH3 with CH3O–/ CH3OH is Sol. For 1 π bond formation, 1 H and 1 Cl will be eliminated
(a) CH3CH2CH(OCH3) CH3 ∴ Equal no. of H and Cl will be eliminated. So, the
product will be 1, 3, 5-trichlorobenzene. The reaction is
(b) CH3 CH  CHCH3
given below:
(c) CH 3CH 2 CH  CH 2
(d) CH3 CH 2 CH 2 CH 2 OCH3
HALOALKANES AND HALOARENES 12

Cl Cl

Cl Cl
alc.
KOH
-3HCl 55.
Cl Cl Cl Cl
The major alkene obtained when this alkyl halide is
Cl subjected to E1 reaction will be
53. 1-pentene will be formed as major product when
methoxide reacts with
(a) 2-iodopentane
(b) 3-iodopentane (a)
(c) 2-fluoropentane
(d) 3-fluoropentane
Ans. (c)
Sol. 1-pentene will be formed as major product when
methoxide reacts with 2-fluoropentane. In this case (b)
fluoride ion is leaving group so major product is least
substituted alkene.
54. What is true about the following reaction?

(c)
(d) All in equal proportions
Ans. (a)
Sol. Since the reaction is E1, the carbocation can rearrange
to form a more stable 3 o -carbocation to give the more
(a)Only substitution product is formed. stable (saytzeff) product. The reaction is given below:
(b)Only elimination product is formed. CH3
(c)Both substitution and elimination products are -I
CH3 C CH CH3
formed and substitution dominates.
(d)Both substitution and elimination products are CH3 I CH3
formed and elimination dominates. 
CH3 C CH CH3
Ans. (d)
Sol. CH3

CH3 CH3

CH3 C C CH3


CH3 CH3

C C

CH3 CH3
13 HALOALKANES AND HALOARENES

CH3 CH3

I
CH3 CH3
I 
56.
The major product obtained when this substrate is
CH3
subjected to E1 reaction will

H

CH3

(a) (b)

Br

CH3
(c) (d) none of these 58.
Ans. (b) The major product obtained when this substrate is
Sol. In E1 reaction, the major product is always saytzeff’s subjected to E1 reaction will be
product. [Note: In E1 reaction, the hydrogen need
not be anti to the leaving group.

57. Find the major product of the following reaction (a) CH3

(b) CH3

(a) (b)
(c) CH2
(d) all three in equal proportions.
Ans. (b)
(c) (d) Sol. The E1 elimination of 1-Bromo-1-methylcyclohexane is
a two-step reaction. In the first step, the bromine atom
Ans. (d)
takes its bonding electron pair and forms a tertiary
Sol. E1-elimination, so rearrangement is possible. When the carbocation.
iodine is removed there is the formation of secondary
In the next step, the base abstracts the beta-hydrogen
carbocation, then the rearrangement takes for the
formation of tertiary carbocation and and deprotonation atom and forms a 1-methyl-cyclohexene as a product.
of H-atom form the adjacent carbon leading to the The reaction is as shown below:
formation of a more substituted alkene.The reaction is
given below:
HALOALKANES AND HALOARENES 14

Br CH3 CH3
-Br 
CH3
H

Ans. (c)
59. 2-bromopentane is heated with potassium ethoxide in Sol. E 2 elimination. The reactant is alcohol and alkoxide
ethanol. The major product obtained is which is used for the elimination of HBr molecule from
(a) Pent-1-ene (b) cis pent-2-ene the reactant and this is will form an alkene. The
(c) trans pent-2-ene (d) 2-ethoxypentane reaction is given below:
Ans. (c)
CH3 CH3
Sol. This is an E 2 elimination, where trans-alkene is more
favoured in which the same groups are on the opposite CH3O
CH3 C CH2Br CH3 C CH2
side. The reaction is given below in which there is CH3OH,
elimination of HBr molecule.
H

61.
In the above reaction, maximum Saytzeff product will
60. The major product formed in the following reaction is
be obtained where X is:
(a) I (b) Cl
(c) Br (d)F
Ans. (a)
Sol. I is best leaving group and hence favours E2
(a) mechanism. Since, I is a halogen and has least
electronegativity, will favor the E2 mechanism.

62. Find the major product of the reaction:

(b)

(a) (b)

(c)
(c) (d) Both (a) and (b)
Ans. (b)
Sol. Me3CO is very bulky base. So, Hoffman elimination
(d) takes place. The chlorine atom will be eliminated and
the hydrogen will be eliminated from the β-carbon
atom. The major product is the one which has less
substituted carbon atoms. The reaction is given below:
15 HALOALKANES AND HALOARENES

Sol. Both the products obtained by elimination on 3-

bromopentare is 2-pentene (right and left products). The
reaction is given below:

alc. KOH
CH3 CH2 CH CH2 CH3
- HBr

Br

CH3 CH CH CH2 CH3

2 - pentene

Product :

65.
63.
The major product obtained when this alkyl halide is
subjected to E2 – reaction will be

(a) (b)
(a)

(c) (d) No reaction

Ans. (d)
Sol. There is no β-H which is anti to leaving group. (b)

64. A halide C5H11Br on treatment with alc. KOH give 2-

pentene only. The halide will be:
(a)

(c)
(b) (d)All three products in equal proportions
Ans. (a)
Sol. In E2 elimination, saytzeff product is the major
(c) product, the hydrogen atom will be eliminated from
beta carbon atom along with the bromine atom and the
more substituted carbon atom will the major product.

(d)
Ans. (c)
HALOALKANES AND HALOARENES 16

Thus, (a) is the correct option.

66.

The major product obtained when this alkyl halide is

67.
subjected to E2 reaction will be
The major product obtained when this substrate is
subjected to E2 reaction will be

(a)

(a) (b)

(b)
(c) (d) none of these
Ans. (a)
Sol. Saytzeff product. (At the same time, H is anti to Br)

(c)
(d) all in equal proportion
Ans. (a)
Sol. The saytzeff product is major product in E2 elimination. 68.
The bromine will be eliminated and the hydrogen will The major product obtained when this substrate is
be eliminated β-carbon atom. The more substituted
subjected to E2 reaction will be
carbon atoms will be the major product. The reaction is
given below:

(a) (b)
17 HALOALKANES AND HALOARENES

(a) (b)
(c) (d) none of these
(c) both in equal proportion
Ans. (b)
(d) not predictable
Sol. Even though, a more stable product is possible at the
Ans. (b)
methyl end, the H there is not anti to Br. (E2) Thus, less
stable product is formed. Sol. E2 reaction gives Saytzeff product. The bromine will be
eliminated from   carbon and the hydrogen will be
eliminated from Beta-carbon atom. Major product is
resonance stabilised alkene

69.
The major product obtained when this alkyl halide is
subjected to E2 reaction under the treatment of
potassium tert-butoxide will be

(a)
71.

(b)
(c) both (a) and (b) (d) none of these
Ans. (b)
Sol. Tert-butoxide is a bulky base, hence, less stable The products obtained when this substrate is
(Hoffman) product is formed. The bromine atom will subjected to E2 reaction will be
be eliminated and the hydrogen will be eliminated from
beta-carbon atom. The major product is the one which
has less substituted carbon atoms. The reaction is given
below:
(a) (b)

(c) (d) all of these

Ans. (a)
Sol. No rearrangement is possible in E2 mechanism. So,
only product a is possible for the given reaction.

72. If tert-butyl bromide and NaNH2 reacts, the product

70. formed is
Which of the following products will be major if this (a) tert-butylamine
substrate is subjected to E2 reaction? (b) tert-butylammonium bromide
HALOALKANES AND HALOARENES 18

(c) a mixture of butyl amines

(d) iso butylenes
Ans. (d)
Sol. This is an E2 -mechanism. The bromine atom will be
(a) 1-methylcyclohexane only
removed from alpha-carbon atom and the hydrogen
atom will removed from the beta-carbon atom. Since (b) 1-Methylcyclohexene only
all the methyl group are alpha-methyl group, all the (c) 3-methylcyclohexene (major product),
methyl group will give same product. The reaction 1-methylcyclohexene (minor product)
given below:
(d) 3-methylcyclohexene only
Ans. (d)
CH3 CH3
Sol. For E 2 elimination (via anti periplanar arrangement)
CH3 C CH2 NaNH2
CH3 C CH2 leaving group (-Br) and β – Hydrogen should be in
- HBr
Br H opposite or anti position.

73. Choose the correct major product of the reaction:

75. Isopropyl bromide on heating with a concentrated

solution of alcoholic (ethanolic) KOH predominantly
gives
(a) Propene (b) Propan-2-ol
(c) Propan-1-ol (d) Isopropyl ethyl ether
Ans. (a)
Sol. Alcoholic KOH favors E 2

(a) (b) CH3  CH  Br 

alc.KOH
 CH3  CH  CH2  HBr
|
CH3

76. What is the major product of the following reaction?

(c) (d)
Ans. (a)
Sol.

(a)

74. What is the product of the reaction of the following

compound with alcoholic potassium hydroxide?
(b)
19 HALOALKANES AND HALOARENES

(a) (b)
(c)
(d) None of these
Ans. (a)
(c) (d)
Sol. The reagent used in the reaction is a strong base. So,
there will a formation of alkene which is less Ans. (a)
substituted by the elimination of HBr by the process of Sol.
Hofmann Elimination. The reaction is given below:
C2 H5 ONa, +
CH3 CH3 Br 
C2 H5 OH

Major Minor

H2C CH CH CH C CH3 Me3CO K 

-HBr
H Br CH3

CH3 CH3

79. Major product:

CH2 CH CH C CH3

CH3

(a) (b)
77. Choose the major product of the reaction.

(c) (d)
Ans. (a)

Sol. Here, the LG is - N Me3 , which is highly with drawing
(a) (b) and hence elimination takes place with less substituted
alkene. This reaction occurs as when the hydroxyl ion
reacts with positive part of the reactant, the bond is
broken and will form a double bond as in option (a).
(c) (d) The diagram is given below:
Ans. (b)
Sol. There will be elimination of HCl molecule which leads
to the formation of cycloalkene. The double bond will
be made in such a way that it has more substituents.
The reaction is given below:

CH3 ONa CH3

Cl

78. What is the major product of the following reaction?

HALOALKANES AND HALOARENES 20

Major product:
80.

82. Among the following the most reactive towards

alcoholic KOH is
(a) (b) (a) CH2 = CHBr (b) H3CCOCH2CH2Br
(c) CH3CH2Br (d) CH3CH2CH2Br
Ans. (b)
Sol.

(c) (d)
Ans. (d) CH3 CH 2  CH 2  Br
Sol. Since the leaving group is highly withdrawing but β α
strongly bonded, the eliminations is E 1 -CB . Thus, the
alkene obtained is least substituted, i.e. ethene from the β-Hydrogen is acidic due to EWG
ethyl group attached to N. Formed double bond is conjugated also. When the
compound is treated with alcoholic KOH, there is the
elimination of HBr molecule and form a double bond
81. What is the major product of the reaction sequence?
between the alpha and beta carbon. This forms a
conjugated system. The reaction is given below:

alcoholic KOH
(a) (b) CH3 CH2 CH2 Br
-HBr

O
(c) (d)
Ans. (a) CH3 C CH CH2
Sol. Addition of C H 3 I (excess) methylates the amino
Substitution vs Elimination
group. Next addition of Ag2O , H 2 O/Δ represents
E 1 -c b mechanism, giving Hoffman product. First step
83. SN1 competes with E1 and SN2 competes with E2.
is the ammonolysis of alkyl halides in excess ammonia This is because
to form Quaternary ammonium salts and in the second
(a) both SN1 and E1 have same rate-determining-step.
step there is the formation of alkene. The reaction is
given below: Therefore, E1 competes with SN1.
(b) a base is a nucleophile and a nucleophile is a base,
Therefore, SN2 competes with E2.
(c) both a and b
(d) none of these
Ans. (c)
21 HALOALKANES AND HALOARENES

Sol. Alkyl halide undergoes both substitution reaction and Sol. In the given reactions alcohol to be protonated first…
elimination reaction. In a nucleophilic substitution HI being a strong acid among the given hydrogen
reaction, the one-step reaction is called the SN 2 halides, readily gives the proton.
reaction. It is a bimolecular nucleophilic substitution The order is : HI >HBr>HCl> HF
reaction where the rate of reaction depends on the
concentration of nucleophile and substrate. Here base 86. The following reaction is known as
can act as a nucleophile. For example, the hydroxide
ion is a good nucleophile. In E2 the elimination C2H5OH+SOCl2  Pyridine
C2H5Cl+SO2+HCl
reaction, the nucleophile that the hydroxide ion acts as a (a) Kharasch effect
base and abstracts a proton and favors the reaction. (b) Darzen’s process
Therefore, SN 2 and E2 are compatible. Similarly, the (c) Williamson’s synthesis
S N 1 reaction proceeds via the intermediate formation. (d) Hunsdiecker synthesis reaction
The reaction forms carbocations as an intermediate. It is Ans. (b)
a rate-determining step. The rate of reaction depends on Sol. The reaction is Darzen’s process. In the presence if
the concentration of substrate. It is as follows, pyridine – in this inversion of configuration occurs
(SN2).
rate = k Substrate
E1 is elimination reaction proceeds via the carbocation
generation. It is a rate-determining step. 87. Which of the following reagents could be used to
convert cyclohexanol to chlorocyclohexane?
The rate of reaction depends on the substrate. Thus
(a) Cl2, light (b) SOCl2
SN 1 and E1 are compatible.
Therefore, both (a) and (b) options are correct. (c) PBr3 (d) none of these
Thus, (c) is the correct option. Ans. (b)
Sol. It is an SN2 type reaction.

84.
This reaction would follow which of the following 88.
pathway predominantly?
(a) SN1 (b) SN2
(c) SN1/E1 (d) SN2/E2 (A) is :
Ans. (d) (a)
Sol. Here, there is equal probability. If there is SN 2 the
bromine nucleophile is replaced with methoxide ion.
Since, methoxide ion is a weak base the elimination
reaction can also take place which leads to the formation (b)
of cycloalkene.

General methods of preparation of alkyl halides

85. Decreasing order of reactivity of HX in the reaction (c)

ROH + HX  RX + H2O
(a) HI > HBr > HCl > HF
(b) HBr > HCl > HI > HF
(c) HCl > HBr > HI > HF
(d) HF > HBr > HCl > HI (d)
Ans. (a)
HALOALKANES AND HALOARENES 22

(c)

Ans. (d)
Sol. Peroxide effect- Br o goes to less substituted carbon in an
unsymmetrical alkene.
(d)

89. Which of the following organic compounds will give a

mixture of 1-chlorobutane and 2-chlorobutane on
hydrochlorination (HCl)
Ans. (a)
(a) CH 3  CH  CH  CH
2 Sol. NBS (N - Bromosuccinimide) – substitute at Allylic
|
position
CH 3
AllylicBromination takes place
(b) H 2 C  HC  CH  CH 2
(c) CH3CH=CHCH3
(d) CH3  CH 2  CH  CH 2
Ans. (d)
Sol.
91. Preparation of alkyl halides in laboratory is least
preferred by
(a) Treatment of alcohols
(b) Addition of hydrogen halides to alkenes
(c) Halide exchange
(d) Direct halogenation of alkanes
Ans. (d)
Sol. In Direct halogenation alkanes via free radical
mechanism.
90. What will be the product in the following reaction A mixture of mono substituted, di substituted and tri
substituted alkyl halide derivatives are formed as
byproduct which are not desired.

92. When hydrochloric acid gas is treated with propene in

(a) presence of benzoyl peroxide, it gives
(a) 2-Chloropropane (b) Allyl chloride
(c) No reaction (d) n-Propyl chloride
Ans. (a)
Sol. When propene reacts with hydrochloric acid in the
presence of benzoyl peroxide, it gives 2-Chloropropane
(b) by following the Markovnikov rule.
According to the Markovnikov rule, when HCl is

added to any alkene, the Cl is added to the carbon
atom containing least number of hydrogen atom or is
added to the carbon atom after the formation of the
23 HALOALKANES AND HALOARENES

most stable carbocation from the given alkene in the

reaction. 96. Which of the following is liquid at room temperature?
The reaction takes place as follows, (a) CH3I (b) CH3Br
CH 3CH  CH 2  HCl 
benzoyl peroxide
CH 3 CH (Cl )CH 3 (c) C2H5Cl (d) CH3F
The most stable carbocation formed during the reaction Ans. (a)
is CH3  CH ()  CH 3 .
Sol. CH 3 F,CH3 Cl,CH 3 Br and C 2 H 5 Cl are gases at room
Hence, option (a) is the correct answer. temperature. CH3I is liquid at room temperature and
solidifies at -66.5oC.
93. Which of the following reactions will yield 2,
2-dibromopropane? 97. Which of the following represents the correct order of
(a) CH3 –C  CH +2HBr  densities?
(b) CH3CH = CHBr +HBr  (a) CCl4>CHCl3> CH2Cl2> CH3Cl > H2O
(c) CH ≡ CH +2HBr  (b) CCl4>CHCl3> CH2Cl2> H2O > CH3Cl
(d) CH3 – CH= CH2 + HBr 
(c) H2O > CH3Cl > CH2Cl2>CHCl3>CCl4
Ans. (a)
Sol. When propyne is treated with 2 moles of hydrogen (d) CCl4>CHCl3> H2O > CH2Cl2> CH3Cl
bromide, the product is 2, 2-Dibromopropane, if the Ans. (b)
reaction is not in the presence of peroxide. This reaction Sol. CCl 4 >CHCl 3 >CH 2Cl 2 >H 2O>CH 3Cl
takes place as first the HBr reacts with propyne to form Bromo, iodo and polychloro derivatives of
2-Bromopropene and then this reacts with HBr to form hydrocarbons are heavier than water. The density
2, 2-Dibromopropane. The reaction is given below: increases with increase in number of chlorine atom,
CH 3C  CH  HBr  CH 3C ( Br )  CH 2 halogen atom but monochloro derivatives are lighter
than water.
CH 3C ( Br )  CH 2  HBr  CH 3  CBr2  CH 3 98. Which of the following has the highest normal boiling
point?
Physical properties of alkyl and aryl halides (a) iodobenzene (b) bromobenzene
(c) chlorobenzene (d) fluorobenzene
Ans. (a)
94. Correct order of B.P. for the alkyl halide is
Sol. There is an increase in boiling point as we move from
(a) C2H5Cl > C2H5Br > C2H5I
chloride to a bromide to an iodide (for a given number
(b) C2H5I > C2H5Br > C2H5Cl of carbon atoms) because of the increase in the number
of electrons leading to larger dispersion forces.
(c) C2H5I > C2H5Cl > C2H5Br
Hence, the maximum boiling point will be of
(d) C2H5Br > C2H5I > C2H5Cl iodobenzene.
Ans. (b)
Sol. For the same alkyl group : B.P. of alkyl halide increases 99. Among the following alkyl halides, choose the one with
with the size of the halogen atom the lowest boiling point.
 C 2 H 5 I > C 2 H 5 Br > C 2 H 5 Cl (a) t-butyl chloride (b) n-butyl chloride
(c) t-butyl bromide (d) n-butyl iodide
95. In CH3CH2Br, % of Br is Ans. (a)
Sol. There is an increase in boiling point as we move from
(a) 80 (b) 73 chloride to a bromide to an iodide (for a given number
(c) 70 (d) 7 of carbon atoms) because of the increase in the number
Ans. (b) of electrons leading to larger dispersion forces.
Sol. Molecular mass of CH3CH2Br = 109 amu The boiling point decreases with the increase in
At Wt. of Br = 80 branching in the alkyl group, because with branching
the molecule attains spherical shape with less surface
80
% of Br is = 100  73.3 area. As a result, interparticle forces become weaker.
109
HALOALKANES AND HALOARENES 24

Hence, the lowest boiling point will be of t-butyl

chloride. Now, for option (a)
CH2 (Cl)  CH 2 (Cl) 
Alc.KOH
 CH 2  CHCl
Reaction of Alkyl Halides
CH3CH(Cl)2 
Alc.KOH
 CH 2  CHCl
For options (c), both the given compounds are
100. Benzene reacts with n-propyl chloride in the presence of dihalides as both of them contain 2 chlorine atom and
anhydrous AlCl3 to give hence, are dichlorides.
(a) 3-Propyl-1-chlorobenzene For option (d), Beilstein test is an organic test which is
(b) n-Propylbenzene used for qualitative test for halides.
(c) No reaction So, this is also applicable to the given compounds as
(d) Isopropylbenzene both of them contain chlorine atoms
Ans. (d) Hence, option (b) is not applicable to the given
Sol. Benzene reacts with n-propyl chloride in the presence compounds and therefore, is the correct answer.
of anhydrous aluminium chloride to give predominantly
isopropylbenzene which is also called cumene. 102. Amongst the C––X bond (where X = Cl, Br, I), the
correct bond energy order is
(a) C – Cl > C – Br > C – I (b) C – I > C – Cl > C – Br
(c) C – Br > C – Cl > C – I (d) C – I > C – Br > C – Cl
Anhyd. AlCl3 Ans. (a)
+ CH3CH2CH2Cl
Sol. Bond energy is directly proportional to the difference in
electronegativity between the 2 atoms.
Benzene Cumene Since, the order of electronegativity: Cl  Br  I
So, the order of the bond energy is
The carbocation formed during the reaction is
 C  Cl  C  Br  C  I
CH 3 CH 2 C H 2 which rearranges to more stable Hence, option (a) is the correct answer.

secondary carbocation CH 3 C HCH3 .
103. In the following reaction find the correct product :
Hence, option (d) is the correct answer.

101. Ethylene dichloride and ethylidene dichloride are

isomeric compounds. Identify the statement which is NaI/Acetone
not applicable to both of them
(a) react with alcoholic potash
(b) react with aqueous potash and give the same product
(c) are dihalides
(d) Beilstein’s test (a)
Ans. (b)
Sol. Here, according to the question ethylene dichloride and
ethylidene dichloride on reaction with aqueous
potassium hydroxide do not give same products,

1 CH 2 (Cl)  CH 2 (Cl) 

Aq.KOH
 CH 2 (OH)  CH 2 (OH)
(b)
Ethylene dichloride vicinal diol

(2)CH3  CH(Cl)2 

Aq.KOH
 CH3  CHO
Ethylidene chloride acetaldehyde
25 HALOALKANES AND HALOARENES

(c) Ans. (c)

Sol. Smaller R – X are preferred in Corey – House
synthesis.

106. Which of the following combinations of reactants is

better for making neopentane?
(a)
(d)

(b)

Ans. (c)
Sol. Finkelstein reaction – involves the preparation of alkyl
iodine from remaining alkyl halides by SN 2
mechanism. (c) both (a) and (b)
R F  NaF  (d) none of these
 Ans. (b)
R  Cl   NaI  R  l + NaCl 
Acetone
Sol. In Corey-House reaction for a better yield of product,
R  Br  NaBr  the alkyl halide used should be primary whereas lithium
dialkyl copper may be 1o ,2o ,3o
104. Corey-House synthesis is a much more convenient
method for making odd no. alkanes for which of the 107. Silver acetate + Br2 The main product of this reaction is
following reasons? (a) CH3— Br (b) CH3COI
(a) Two different alkyl halides can be use. From one
alkyl halide, R2CuLi is prepared and then this is reacted (c) CH3COOH (d) None of these
with another alkyl halide. Ans. (a)
(b) The reagent R2CuLi can be prepared from 1°, 2° or Sol.
O
3° alkyl halide as well as from halobenzenes 
CS
(c) both (a) and (b) CH 3  C O Ag + Br2 
2
 CH 3  Br + AgBr + CO 2
(d) none of these Borodine – Hunsdiecker reaction.
Ans. (c)
Sol. The scope of corey-House synthesis is exceptionally 108. Ethyl bromide reacts with silver nitrite to form
broad and a range of lithium diorganylcuprates (a) Nitroethane
(R2CuLi, R=1o, 2o, 3o alkyl, aryl or alkenyl) and (b) Nitroethane and ethyl nitrite
(c) Ethyl nitrite (d) Ethane
organyl halide will undergo coupling.
Ans. (a)
RX  2Li  RLi  LiX
Sol. CH 3CH 2 Br + AgNO2  C2 H5 NO2 + AgBr
2RLi  CuI  R 2 CuLi  LiI  
R 2 CuLi  R ' X  R  R ' RCu  LiX covalent Nitro ethane

105. Which of the following combinations of reactants is 109. What is the major product of the reaction?
better for making propane?
(a) (CH3)2CuLi+CH3CH2Br  CH3CH2CH3
(b) Et2CuLi+CH3 – Br  CH3 – CH2 – CH3
(c) both of these
(d) none of these (a)
HALOALKANES AND HALOARENES 26

(d) With AgCN, EtNC while with KCN, EtCN is

formed as major product.
Ans. (d)
Sol. AgCN – covalent – connecting atom is N  EtNC
(b)
KCN  Ionic  Connecting atom  'C'

Et  CN

(c) 112. CH3 – CH2 – CH2 – I 

aq.KCN
P(major)
P should be
(a) CH3 – CH2 – CH2 – CN
(b) CH3 – CH = CH2
(d)
(c) both (a) and (b) in equal proportions
(d) none of these
Ans. (a)
Sol. Aq. KCN  Substitution takes place, alkyl nitrile
Ans. (c) formed, since KCN is ionic.
Sol.
113. CH 3 CH 2  NH 2  CH 3  I  P
(Excess)  Major 

P should be
(a) CH3 – CH2 – NH – CH3
(b)

110. Which of the following reactions is a good way to

prepare methyl tert–butyl ether? (c) CH3 – CH2 – N+(CH3)3I-
(d) CH2 = CH2
(a) CH3O–Na+ + (CH3)3 CBr
Ans. (c)
(b) (CH3)3CO– K+ + CH3I Sol. primary amines react with excess methyl iodide to
(c) (CH3)3COH + CH3OH form quaternary ammonium salts. The nitrogen atom
of primary amines contains a lone pair of electron.
(d) CH3MgBr + (CH3)3COCl
So, primary amines are strongly nucleophilic in
Ans. (b) nature. Moreover, the hydrogen atoms on nitrogen
Sol. are easily replaceable. So, primary amines can act as
nucleophiles and can react with alkyl halides. In the
presence of excess alkyl halides, one amine molecule
can repeatedly react with a number of alkyl halide
111. Iodine from iodoethane can be substituted by cyanide
group in a number of ways. Which of the following is molecules and result in the formation of a quaternary
true statement? ammonium salt. The reaction is as follows :

(a) With either KCN or AgCN, EtCN is formed as RNH 2  3CH 3 I   RN  CH 3 3  I
major product.
(b) With either KCN or AgCN, EtNC is formed as
major product.
(c) With AgCN, EtCN and with KCN, EtNC is formed.
27 HALOALKANES AND HALOARENES

114. (d) Neither (a) nor (b)

Ans. (d)
Sol. The reaction follows SN2 (inversion)

(a)

116. The catalyst used in the preparation of an alkyl chloride

by the action of dry HCl on an alcohol is
(a) anhy. AlCl3 (b) anhy. ZnCl2
(b) (c) FeCl3 (d) Cu
Ans. (b)
Sol. Solution of anhy. ZnCl2 in conc. HCl is known as Lucas
reagent. It is used to differentiate primary, secondary
and tertiary alcohols. In this anhydrous zinc chloride
acts as a catalyst.
117. When CH3CH2CHCl2is treated with NaNH2 the
product formed is
(c) both (a) and (b) in equal proportions
(a)CH3 – CH = CH2 (b) CH 3  C  CH
(d) None of these
Ans. (b) (c) CH3CH2CH(NH2)(Cl) (d) CH3CH2CH(NH2)2
Sol. The reaction follows SN2 pathways. Ans. (b)
Sol. Dehydrohalogenation reaction elimination
CH3  CH2 CH Cl2 
NaNH2
2HCl
CH3  C  CH
118. Alkyl halides react with Mg in dry ether to form
(a) Magnesium halide (b) Grignard’s reagent
(c) Alkene (d) Alkyne
115. What is the product of the following reaction? Ans. (b)
Sol. R  X + Mg 
dry
Ether
 R Mg X
119. CH3 – CH2 – CH2 – Br + CH3 – CH2 – Br  
Na/ether

P is :
(a) (a) P is mixture of three alkanes (n–hexane, n–butane
and n–pentane); none is formed in good yield
(b) P is a mixture of only two alkanes (n–hexane and
n–butane); both are formed in good yield.
(c) both (a) and (b) depending upon other conditions
(d) none of these
Ans. (a)
(b) Sol. If different R-X are taken in wurtz reaction 3 types of
alkanes will be obtained.

R 'X  R ''X  2Na 

dry ether
R 'R ' R ''R '' R 'R '' NaX

(c) Both (a) and (b)

HALOALKANES AND HALOARENES 28

120. The product ‘B’ is Sol. Alkyl halides (2o and 3o) are reduced by sodium
borohydride

122. Elimination of bromine from 2-bromobutane results in

the formation of
(a) predominantly 2-butyne
(b) predominantly 1-butene
(a)
(c) predominantly 2-butene
(d) equimolar mixture of 1 and 2-butene
Ans. (c)
Sol. If the bromine is attached to the terminal carbon atom,
(b)
then there is the formation of only one alkene. But if, the
bromine is attached at the carbon atom other than the
terminal carbon atom, then there will be the formation of
more than one alkene, so the major alkene will be the
(c) alkene with more substitution or lesser number of
hydrogen. So, the major product for the elimination of
the bromine from 2-bromobutane, there will the
formation of 2-butene as a major product. The reaction is
given below:
(d) CH3 CH CH2 CH3
- HBr
CH3 CH CH CH3
Ans. (d)
Sol. Br 2 – Butene (Major)

CH2 CH CH2 CH3

1 – Butene (Minor)
121.

123. Isopropyl bromide on Wurtz reaction give:

(a) hexane (b) propane
P should be (c) 2,3-dimethyl butane (d) neo-hexane
Ans. (c)
(a)

(b)

Sol.
(c) both of these in equal proportions 124. The reactivity order of halides for dehydrohalogenation
(d) none of these is
Ans. (a) (a) R–F > R–Cl> R–Br > R–I
(b) R–I > R–Br > R–Cl> R–F
29 HALOALKANES AND HALOARENES

(c) R–I > R–Cl> R–Br > R–F

(d) R–F > R–I > R–Br > R–Cl
Ans. (b)
Sol. The reactivity of halides for dehydrohalogenation
depends on the quality of the leaving group. If the
halide is a good leaving group, then the reactivity
increases.
Dehydrohalogenation is the elimination of HX or
hydrogen halides from an alkyl halide.
128. B.H.C. is used as
Now, the strength of the bond between the carbon
atom and the halogen decides the quality of the (a) Insecticide (b) Pesticide
leaving group. If the bond strength is weak then the (c) Herbicide (d) Weedicide
halogen will be a good leaving group because it can Ans. (a)
easily break the C – X bond. Sol. B.H.C stands for Benzene hexachloride.Benzene
Now, the larger the size of the halogen, larger will be hexachloride is an insecticide generally known as
the bond length and weaker will be the bond and gammaxene. It is obtained by the following reaction-
thus, in turn, the halogen will be a better leaving
group. So, the order of the size of halogens is I > Br >
Cl> F.
Hence, the order of reactivity of the alkyl halides
towards dehydrohalogenation reaction will be: R – I
> R – Br > R – Cl> R – F, which is option (b).

Polyhalogen Compounds

125. Industrial preparation of chloroform employs acetone 129. CCl4 cannot give precipitate with AgNO3 due to
and (a) Formation of complex with AgNO3
(a) Phosgene (b) Calcium hypochlorite
(b) Evolution of Cl2 gas
(c) Chlorine gas (d) Sodium chloride
Ans. (b) (c) Chloride ion is not formed
Sol. Calcium hypochlorite Ca (OCl ) 2 and acetone are used (d) AgNO3 does not give silver ion
for industrial preparation of chloroform. Ans. (c)
So, option (b) is the correct answer. Sol. If there is the formation of precipitate then there is the
126. Haloforms are trihalogen derivatives of formation of AgCl . So we can say that the chlorine
(a) Ethane (b) Methane atom must be in an ionizable form. But when the CCl4
(c) Propane (d) Benzene is treated with A gN O 3 , there is no formation of
Ans. (b) precipitate because in CCl4 , all the chlorine atoms are
Sol. CHX (X = F, Cl, Br, I) joined to carbon through a covalent and are not in
3
 ionizable form. so due to the absence of Cl  ion, no
Haloform
precipitate is formed.

127. Number of –bonds present in B.H.C. (Benzene

130. Chloroform for anesthetic purposes is tested for its
hexachloride) are
purity with the reagent
(a) 6 (b) Zero
(a) Silver nitrate (b) Lead nitrate
(c) 3 (d) 12
(c) Ammoniacal Cu2Cl2 (d) Fehling solution
Ans. (b)
Ans. (a)
Sol.
Sol. The impurity HCl reacts with AgN O 3 to give ppt 
AgCl
HALOALKANES AND HALOARENES 30

131. The use of the product obtained as a result of reaction Hence, both are insecticides.
between acetone and chloroform is Hence, the second option is correct.
(a) Hypnotic (b) Antiseptic
(c) Germicidal (d) Anaesthetic 135. The formula of freon-12 is :
Ans. (a) (a) CClF3 (b) CH2Cl2
Sol. Chloretone is formed
(c) CCl2F2 (d) CH2F2
Ans. (c)
Sol. CF2 Cl2

132. Which plastic is obtained from as follows Preparation of Aryl Halides

o
CHCl3 
HF
BF3
X 
800 C
 
Polymerisation
 Plastic
136. Chlorobenzene is prepared commercially by
(a) Bakelite (b) Teflon
(a) Down’s process (b) Raschig’s process
(c) Polythene (d) Perspex
(c) Deacon’s process (d) Etard’s process
Ans. (b)
Ans. (b)
Sol.
Sol. Chlorobenzene is commercially produced by Raschig’s
800 C
CHCl3 
HF
SbF3
 CHF2 Cl   CF2  CF2 process.

Polymerisation
 [CF2  CF2 ] n (teflon) The reaction involved in Raschig’s process is as
follows,
133. When CHCl3is boiled with NaOH, It gives
Cl
(a) Formic acid
(b) Trihydroxy methane
(c) Acetylene CuCl2
+ HCl + O2 H2O +
(d) Sodium formate 4000C
Ans. (d)
Sol. Hence, option (b) is the correct answer.

Reaction of Aryl Halides

134. The commercial uses of DDT and benzene
137. Which chloro derivative of benzene among the
hexachloride are
following would undergo hydrolysis most readily with
(a) DDT is a herbicide, benzene hexachloride is a aqueous sodium hydroxide to furnish the corresponding
fungicide hydroxy derivative?
(b) Both are insecticides (a) (b)
(c) Both are herbicides
(d) DDT is a fungicide and benzene hexachloride is a
herbicide
Ans. (b)
Sol. BHC is a highly toxic, non-specific
(c) (d) C6H5Cl
organochlorine insecticide used mostly for a wide
variety of agricultural applications.
DDT (dichloro-diphenyl-trichloroethane) was
developed as the first of the modern synthetic
insecticides in the 1940s. It was initially used with great Ans. (a)
effect to combat malaria, typhus, and the other insect- Sol. Aryl halides does not easily undergo nucleophilic
borne human diseases among both military and civilian substitution reaction because of the double bond
populations. character between halogen atom and the carbon atom
31 HALOALKANES AND HALOARENES

due to resonance, due to sp2 hybridization of carbon 139.

atom which increases its electronegativity which
increase the bond strength and due to the instability of
phenyl cation so formed during the reaction.
But as the number of electron withdrawing groups like
 NO2 increases, the benzene becomes electron-
This reaction follows
deficient and it undergo nucleophilic substitution.
(a) Elimination pathway
So, 2,4,6-trinitrochlrobenzene reacts easily with NaOH
(b) Substitution pathway
and undergo nucleophilic substitution reaction to
form 2,4,6-trinitrophenol. (c) addition-elimination pathway
Cl
(d) none of these
OH
Ans. (c)
NO2 NO2 NO2 NO2 Sol. Aryl halide with electron withdrawing groups involves
NaOH in Nucleophilic substitution Aromatic through addition
elimination pathway.

NO2 NO2

138. Which of the following reaction is called Wurtz-Fittig

reaction?
(a)
140. Select the product of the reaction

(b)

(a)

(c)
(b)

(d) both (b) and (c)

Ans. (b) (c)
Sol. Aryl halide + Alkyl Halide
 Na/Ether
Alkyl substituted benzene (Wurtz – Fittig)

(d) Both (a) and (c)

HALOALKANES AND HALOARENES 32

Ans. (d)
Sol Both (a) and (c) 143.
Cl group is -o and -p directing.
141. In addition-elimination pathway of nucleophilic 
1. HO / 
aromatic substitutions, which of the following   P
2. H  Major 
compounds is most reactive?
(a)

Based on the above reaction, the major product would

be
(a) (b)

(b)

(c) both in equal proportions (d) none of these

Ans. (b)
Sol. NO2 -Group directs the incoming nucleophile to ortho
and para positions through –M effect (facilitates Nu)
(c)
144. Which of the following has the fastest rate of the
reaction with NaOC2H5?
(a) p–fluoronitrobenzene (b) p–bromonitrobenzene
(c) p–chloronitrobenzene (d) p–iodonitrobenzene
Ans. (a)
(d) Sol. I-effect, ease of nucleophilic aromatic substitution
directly proportional to number of EWG group.

145.
Ans. (c) (a) (b)
Sol. The reactivity of aryl halides towards nucleophilic
aromatic substitution reaction increase with increase in
no. of electron withdrawing groups on benzene ring.
142. In addition elimination pathway of nucleophilic
aromatic substitutions, NO2 group is
(a) o, p–directing and activating
(b) o, p–directing and deactivating (c) (d)
(c) m–directing and activating
(d) m–directing and deactivating
Ans. (a)
Sol. NO 2 - Group directs the incoming nucleophile to O and
P positions through –M (facilitates Nu)
33 HALOALKANES AND HALOARENES

Ans. (a) (c)

Sol. The presence of nitro group at ortho and para positions
withdraws electron density from the benzene ring and
thus facilitate the attack of the nucleophile C 2 H 5O  on
the given haloarene. The carbanion thus formed is
stabilized through resonance.

146. Which of the following is (are) true regarding

intermediate in the addition-elimination mechanism of (d)
the reaction below?

Ans. (c)
I. The intermediate is aromatic. Sol. Replacement of Cl of chlorobenzene to give phenol
II. The intermediate is resonance stabilized anion. requires drastic conditions but chlorine of 2, 4-
dinitrochlorobenzene is readily replaced because the
III. Electron withdrawing group on the benzene ring
presence of nitro group at ortho and para positions
stabilize the intermediate
withdraws electron density from the benzene ring and
(a) I only (b) II only thus facilitate the attack of the nucleophile CH 3 NH 
(c) I and III (d) I, II and III
on the given haloarene. The carbanion thus formed is
Ans. (d) stabilized through resonance.
Sol. Addition – elimination reaction proceeds through a Hence, the third option is correct.
carbanion formation. Electron withdrawing group on
the benzene ring when attached at the para or ortho
positions will increase the rate of reaction as they will 148. Chlorobenzene reacts with Mg in dry ether to give a
stabilize the intermediate. compound (A) which further reacts with ethanol to
yield
Hence, the 4th option is correct.
(a) Phenol (b) Benzene
(c) Ethylbenzene (d) Phenyl ether
147. Which is the major product of the reaction of 2, 4–
dinitrochlorobenzene with methylamine? Ans. (b)
(a) Sol. When chlorobenzene reacts with Mg in the presence of
dry ether it forms benzene magnesium chloride.
Now, the so formed benzene magnesium chloride when
reacts with ethanol, it forms benzene.

(b)
HALOALKANES AND HALOARENES 34

Cl (b)
NO2

Mg
C6H5MgCl (Grignard reagent) O2N Cl
Dry Ether

NO2
(c)
C6H5MgCl + C2H5OH C2H5OMgCl + O2N

Hence, option (b) is the correct answer. O2N Cl

149. Which one of the following compounds undergoes
hydrolysis most readily by aq. NaOH to furnish
O2N
corresponding phenol?

Cl Cl (d)
O2N

(a) (b)
Cl

OCH3 O2N Cl

Cl Ans. (b)
Cl
Sol. Aryl halide having EWG – in benzene ring is more
NO2 reactive.
-M effect can operate through ortho, para positions only.
(c) (d)
Assertion Reason and Statement Type
NO2 NO2 Questions
Ans. (d)
151. Given below are two statements:
Sol. The presence of nitro group at ortho and para positions
Statement-I: 2-Bromo pentane on reaction with
withdraws electron density from the benzene ring and
 alcoholic KOH gives 1-pentene as a major product.
thus facilitates the attack of the nucleophile OH on the
Statement-II: In dehydrohalogenation reactions the
given haloarene. The carbanion thus formed is
stabilized through resonance. preferred product is always that alkene which has lesser
Hence, the fourth option is correct. number of alkyl groups attached to the doubly bonded
c-atoms.
150. Which chloroderivative of nitrobenzenes among the In the light of the above statements, choose the most
following would undergo hydrolysis, most readily with appropriate answer from the options given below:
aqueous NaOH? (a) Both statements-I and II are correct.
(a) (b) Statement-I is correct but Statement-II is incorrect.
O2N NO2 (c) Both Statement-I and II are incorrect
(d) Statement-I is incorrect but Statement-II is correct.
Cl Ans. (c)
Sol. The major product formed from the reaction of 2-
bromopentane with alcoholic KOH is 2-pentene, and
O2N the name of the reaction is dehydrohalogenation.
According to Zaitsev's rule (or Saytzeff's rule), the
35 HALOALKANES AND HALOARENES

more substituted alkene is favored as the major product.

In this case, 2-pentene (where the double bond is
between the second and third carbons) is more
substituted than 1-pentene (which has the double bond
Sodium chloride and sodium bromide being less
at the first carbon). Therefore, the major product is:
soluble in acetone get precipitated from the solution and
2-pentene
can be removed by filtration. This also prevents the
152. Given below are two statements:
backward reaction to occur according to Le Chatelier's
Statement I: Solubility of haloalkane in water is low.
principle.
Statement II: Energy required to overcome attractions
Swarts reaction
between haloalkane molecules & the energy raquired to
This reaction is used for the preparation of
break H-bonds in water are much higher than the new
fluoroalkanes by heating suitable chloroalkanes with
attractions developed between haloalkane and water.
inorganic fluorides such as AgF, Hg2F2, CoF2 or SbF3.
(a) Both statements I and II are correct
(b) Statement I is correct statement II is incorrect
(c) Statement I is incorrect statement II is correct
(d) Both statements I and II are incorrect 154. Given below are two statements:
Ans. (a) Statement-I : Aryl chlorides & bromides can be easily
Sol. (I) Intermolecular Attractions between haloalkanes - prepared by ESR of Arenes with Cl2 & Br2 respectively
dipole-dipole Intermolecular Attractions between water in the presence of lewis acid catalyst.
molecules - H-bonding Statement-II : Reactions With I2 are reversible &
(II) Attractions developed between R-X molecules and required the presence of an oxidising agent (HNO3,
water are weak HlO3) to oxidise HI formed during iodination.
Energy required to break the attractions in I case In the light of the above statements, choose the most
dominate II appropriate answer from the options given below:
∴alkyl halides are insoluble in water (I) Statement-I is correct but Statement-II incorrect.
153. Given below are two statements: (2) Statement-I is Incorrect but Statement-II is correct
Statement-I: Alkyl iodides are often prepared by the (3) Both Statement-I and II are incorrect
reaction of alkyl chlorides,/bromides with NaI in dry (4) Both statements-I and II are correct.
acetone. NaCl or NaBr formed is precipitated in dry Ans. (a)
acetone. It facilitates the reverse reaction according to Sol. Iodination reactions are reversible in nature. To carry
le-chatelier's principle. out reaction in the forward direction, HI formed during
Statement-II: The synthesis of alkyl flourides is best the reaction is removed by oxidation using HNO3 or
accomplished by heating an alkyl chloride/ bromide in HIO3
presence of metallic fluoride such as AgF, Hg2F2, CoF2
or SbF3.
In the light of the above statements, choose the most
appropriate answer from the options given below:
(a) Statement-I is correct but Statement-II is Incorrect.
(b) Both statements-I and II are correct. 155. Given below are two statements; one is labelled as
(c) Both Statement-I and II are incorrect Assertion (A) and the other is labelled as Reason(R).
(d) Statement-I is incorrect but Statement-II is correct. Assertion: Alkyl chlorides are best prepared from
Ans. (d) alcohols by reaction of SOCl2.
Sol. Finkelstein reaction: Reason : The other two products are easily escapable.
The iodoalkanes are obtained by heating chloro or So reaction gives pure Alkyl chlorides. In the light of
bromoalkanes with a concentrated solution of sodium the above statements, choose the most appropriate
iodide in dry acetone. answer from the options given below :
(a) Both (A) and (R) are correct and (R) is the correct
explanation of (A).
HALOALKANES AND HALOARENES 36

(b) Both (A) and (R) are correct but (R) is not the (d) (A) Is not correct but (R) is correct.
correct explanation of (A). Ans. (a)
(c) (A) is correct but (R) is not correct. Sol.
(d) (A) is not correct but (R) is correct. In chlorobenzene, the lone pair of electrons on the chlorine
Ans. (a) atom can participate in resonance with the pi electrons of the
Sol. Thionyl chloride is preferred for the preparation of benzene ring, giving the C-Cl bond a partial double bond
alkyl chlorides from alcohols because the gaseous by- character, making it more stable and less prone to nucleophilic
products (SO₂ and HCl) escape easily, leading to a attack.
higher yield of the alkyl chloride.
158. Assertion (A) Yield of an alkyl halide which is formed
by the free radical halogenation is low.
156. Given below are two statements; one is labelled as Reason (R) Free radical halogenation lead to formation
Assertion (A) and the other is labelled as Reason(R) of mixture of isomeric mono and polyhaloalkanes.
Assertion : For the same alkyl group, the boiling point (a) Both (A) and (R) are correct and (R) is the correct
of alkyl halides decrease in the order R-I > R-Br > R- explanation of (A).
Cl>R-F. (b) Both (A) and (R) are correct but (R) is not the
Reason : This is because with the decrease in size and correct explanation of (A).
mass of halogen atom, the magnitude of van der waal (c) (A) is correct but (R) is not correct.
forces increases. (d) (A) is not correct but (R) is correct.
In the light of the above statements, choose the most Ans. (a)
appropriate answer from the options given below : Sol. Free radical chlorination or bromination of alkanes
(a) Both (A) and (R) are correct and (R) is the correct gives a complex mixture of isomeric mono and
explanation of (A). polyhaloalkanes which is difficult to separate as pure
(b) Both (A) and (R) are correct but (R) is not the compounds.
correct explanation of (A). Cl /UV light
CH 3CH 2 CH 2CH 3 
2 CH 3CH 2CH 2 CH 2Cl
(c) (A) is correct but (R) is not correct. or heat
(d) (A) is not correct but (R) is correct.  CH 3CH 2  CH  CH 3
Ans. (c) |
Sol. Assertion (A) is correct, but reason (R) is incorrect Cl
statement. 159. Assertion (A) SN2 mechanism is accompanied by
The boiling points of alkyl halides decrease in the order racemisation.
RI>RBr>RCl>RF. This is because as the size of Reason (R) Nucleophile attaches itself on the side
halogen increases, the magnitude of van der Waals opposite to one where halogen atom is present.
forces increase, and hence the boiling point increase. (a) Both (A) and (R) are correct and (R) is the correct
157. Given below are two statements, one is labelled as explanation of (A).
Assertion (A) and the other is labelled as Reason(R). (b) Both (A) and (R) are correct but (R) is not the
Assertion : Chlorobenzene does not react with NaOH correct explanation of (A).
where as ethyl chloride reacts. (c) (A) is correct but (R) is not correct.
Reason : The partial double bond between carbon and (d) (A) is not correct but (R) is correct.
chlorine in chlorobenzene causes less reactivity towards Ans. (d)
Nucleophilic substitution reactions. Sol. In case of optically active alkyl halides, the product
In the light of the above statements, choose the most formed as a result of SN2 mechanism has inverted
appropriate answer from the options given below configuration as compared to the reactant. This is
(a) Both (A) and (R) are correct and (R) is the correct because the nucleophile attaches itself on the side
explanation of (A). opposite to the one where the halogen atom is present.
(b) Both (A) and (R) are correct but (R) is not the 160. Assertion (A) Electrophilic substitution reactions in
correct explanation of (A). haloarene occur slowly and under drastic conditions.
(c) (A) is correct but (R) is not correct.
37 HALOALKANES AND HALOARENES

Reason (R) Haloarene are activated as compared to (b) CH 3CH 2  Br (q) Ph-Ph
benzene. Zn  Cu / C H OH
 2 5

(a) Both (A) and (R) are correct and (R) is the correct
(c) CH 3CH 2 Br  PhBr (r) CH3CH2MgBr
explanation of (A).
Na
(b) Both (A) and (R) are correct but (R) is not the 

Dry Ether
correct explanation of (A).
(d) 2 PhBr 
Na
  (s)
(c) (A) is correct but (R) is not correct. Dry Ether
(d) (A) is not correct but (R) is correct.
(a) a-r, b-s, c-p, d-q
Ans. (c)
(b) a-r, b-p, c-s, d-q
Sol. Halogen atom due to —I - effect has some tendency to
(c) a-s, b-r, c-p, d-q
withdraw electron from benzene ring. So the ring gets
(d) a-q, b-s, c-r, d-p
deactivated as compared to benzene. Hence,
Ans. (b)
electrophilic substitution reactions in haloarene occur
Sol. (b) a-r, b-p, c-s, d-q
slowly and require more drastic conditions as compared
163. Match the following conditions given in Column I with
to those in benzene.
Column II and choose the correct option from the codes
given below.
Match the following Questions

161. Match the column :-

Column-I Column-II

(Reaction) (Reaction name)

(a) CH 3CH 2  Cl (p) Friedel craft
NaI
 reaction
Dry Acetone

(b) (q) Finkelstein

reaction
(c) CH 3  Br  AgF  (r) Sandmeyer's

reaction
(d) (s) Swart’s

Reaction

(a) a- p, b-r, c-s, d-q

(b) a-q, b-r, c-s, d-p Codes
(c) a-r, b-s, c-p, d-q A B C
(d) a-s, b-r, c-q, d-p (a) 3 1 2
Ans. (b) (b) 1 3 2
Sol. (b) a-q, b-r, c-s, d-p (c) 1 2 3
162. Match the column :- (d) 3 2 1
Column-I Column-II Ans. (c)
Sol. A  1, B  2, C  3 Presence of -NO2 group
(Reaction) (Product) activates chlorobenzene towards nucleophilic
(a) CH 3CH 2 Br (p) CH 3CH 2  H substitution,ease of nucleophilic substitution α no of

Mg E.W.G . More the no.of EWG , less T and harsh
dry Ether conditions are required for the nucleophilic substitution
reaction in halobenzene and derivatives
HALOALKANES AND HALOARENES 38

164. Match the reactions given in Column I with the types of B. Secondary alkyl 2. Prefer SN2 reaction
reactions given in Column II and choose the correct halide
option from the codes given below. C. Tertiary alkyl 3. SN1 or elimination
halide depending upon
stability of carbocation
Column I Column II or more substituted
A. 1 Electrophilic alkene.

addition Codes
A B C
B. CH 3  CH  CH 2  HBr  2 Electrophilic
CH 3  CH  CH 3 (a) 2 1 3
| aromatic (b) 1 2 3
Br
(c) 2 3 1
substitution
C. 3 (d) 1 3 2
Saytzeff
Ans. (a)
elimination Sol. Primary alkyl halide prefers SN2 reaction. Secondary
alkyl halide prefer SN2 or elimination depending upon
D. 4 Nucleophilic strength of base/nucleophile, tertiary halide prefers SN1
or elimination depending upon the stability of
aromatic carbocation or the more substituted alkene.

substitution

E. CH 3CH 2CHCH 3 

alc. KOH 5 Nucleophilic
|
Br substitution
CH 3CH  CHCH 3
(SN1)
Codes
A B C D E
(a) 2 1 5 4 3
(b) 4 1 5 2 3
(c) 2 5 1 4 3
(d) 2 1 4 5 3
Ans. (b)
Sol. A  4, B  1, C  5, D  2, E  3
165. Match the Column I representing alkyl halide with the
statement given in Column II and choose the correct
option from the codes given below.
Column I Column II
A. Primary alkyl 1. SN2 or elimination
halide depending upon
strength of
base/nucleophile