Alkyl and Aryl Halides Exercise 1

1 ALKYL AND ARYL HALIDES
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 an
2. Which of the following species is an electrophile? 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) H3O
(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. The species which can donate electrons are known as Sol. leaving ability 
Basic strength
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) Nucleophilicity and its variation
ALKYL AND ARYL HALIDES 22
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 Ans. (a)
phase? Sol. DMF is a polar aprotic solvent. The given options belong
CH 3 , NH 2 , OH  ,F - to the same group and nucleophilicity decreases down
   - the group in polar aprotic solvents.
(a) CH 3 >NH 2 >OH >F
(b) F   OH   NH 2  CH 3 Θ Θ Θ Θ
  -  12. F,Cl,Br, I
(c) OH >NH >F >CH 2 3
Among these nucleophiles, which of the following
(d) none of these orders is correct for their nucleophilicity order in
Ans. (a) 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 (a) F>Cl >Br>I (b) I >Br >Cl>F
is inversely proportional to the electronegativity of the Θ Θ Θ Θ
electron donation atom. Thus, the higher the (c) I >Br >F>Cl (d) none of these
electronegativity of the atom, the lower is the Ans. (b)
nucleophilicity.
Sol. Water is a protic polar solvent. The given options
Given anions are:
belong to the same group and nucleophilicity increases
Θ Θ Θ Θ
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–
(c) I–< Cl–< Br– (d) Br–< Cl–< I–
Θ Θ Θ Θ Ans. (b)
10. C H 3 , N H 2 , O H, F
Sol. The given options belong to the same group and
Among these nucleophiles, which of the following 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 solvent which means that there is a leaving group. Also, the halide is more
large dipole moment of the molecule due to difference in electronegative compared to carbon. So, it creates a
electronegativities of oxygen and hydrogen atoms. So, as partial positive charge on the carbon it is attached.
the electronegativity of the central atom increases the So, this halide leaves which makes a way for other
nucleophilicity decreases. nucleophiles to attack its position.
The OH- group can act as a nucleophile and attack
Θ  Θ Θ that position. So, the halide in alkyl halide can be
11. F, Cl , Br, I
substituted by the OH- group to form alcohols.
Among these nucleophiles, which of the following orders
CH 3 CH  Cl  CH 2 CH 3   CH 3 CH  OH  CH 2 CH 3
-
OH
is correct for their nucleophilicity order in DMF?
Θ  Θ Θ Θ Θ Θ Θ Hence, this is a substitution reaction which is option
(a) F> Cl >Br > I (b) I >Br > Cl >F (b).
18. Which of the following two reactions would be

15. C3 H8  Cl2 
 C3 H7 Cl  HCl is an example of
Light faster?
Θ Θ
(a) Substitution (b) Elimination (a) CH 3 -I+ O H  CH 3 -OH+ I
(c) Addition (d) Rearrangement reaction Θ Θ
Ans. (a) (b) CH 3 -Cl+ OH  CH 3 -OH+ Cl

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

17. Isopropyl chloride undergoes hydrolysis by: nucleophilic substitution?
(a) SN1 mechanism
(a) H 2 C=CH-Cl (b) C6 H5Cl
(b) SN2 mechanism
(c) SN1 and SN2 mechanism (c) CH3 -CH=CH-Cl (d) ClCH 2 -CH=CH 2
(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- tendency for nucleophilic substitution.
HC CH3 HC CH3
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
secondary carbon, it has the tendency to go for both (c) inversion of configuration
mechanisms. (d) both (b) & (c)
Ans. (d)
Sol. There are two steps in SN1 reaction, in the first step, there (b) p-chlorobenzyl bromide
is the removal of an atom or molecule from compound (c) p-methoxybenzyl bromide
leads to the formation of a carbocation. We know that the (d) p-methylbenzyl bromide
central carbon atom of the carbocation is sp 2 Ans. (c)
hybridized, and the structure of sp 2 hybridized carbon Sol. Ethanolysis or alcoholysis or solvolysis is an SN 1
atom is planar. Now, in the next step, the nucleophile mechanism (to a large extent) involving rate-
will attack the carbocation, since the structure is planar, determining step of carbocation formation. The p-
the nucleophile can attack from any face, there will be methoxybenzyl bromide will be more stable due to the
formation of two enantiomers in equal amount. So, +R effect.
overall the mixture will be optically inactive.
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.
24. The reaction described is
The mechanism of SN 1 is shown below:
The is a stepwise mechanism
(a) SE2 (b) SN1

(c) SN2 (d) SN0
Ans. (c)
Sol. The given reaction is:
As we can see in this reaction an intermediate In this reaction inversion of configuration taking place
carbocation is formed which is planer in structure. So, the reaction will be Nucleophilic substitution Bi-
The planar structure allows the attack of nucleophile molecular or SN2.
possible from any direction. So, we can see an Hence, option (c) is the correct one.
equimolar mixture of both configurations which may
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 
concentration of O H is reduced to half, the rate of SN2
they cancel the effect on each other. This mixture is reaction increased by:
known as a racemic mixture and the process is known
as racemisation. (a) 3 times (b) 1.5 times
Hence, option (b) is the correct one. (c) 2 times (d) 6 times
Ans. (b)
23. Among the following, the one which reacts most
readily with ethanol is
(a) p-nitrobenzyl bromide
Sol. For S N 2 reaction,

∴If concentration of R – X is tripled and  OH -  is
halved, rate will become 1.5 times. Ans. (d)
26. C3H8 + Cl2 C3H7Cl + HCl is an example of Sol.
which of the following types of reactions
(a) Substitution (b) Elimination
(c) Addition (d) Rearrangement
Ans. (a)
Sol. This is an example of free radical substitution reaction
Stability of free radical is 3o >2o >1o.
hydrogen atom of alkane is replace by halogen atom.
29. Following reaction

27. 2, 6 - Dimethylheptane on monochlorination
produces……. derivatives (CH3)3CBr + H2O  (CH3)3COH + HBr is an example
(a) 5 (b) 6 of
(c) 3 (d) 4 (a) elimination reaction
Ans. (b) (b) free radical substitution
Sol. 2,6 - Dimethylheptane is a disubstituted alkane. Two (c) nucleophilic substitution
methyl groups are attached to the second and sixth (d) electrophilic substitution
carbon atoms on the chain, there are four free terminal Ans. (c)
methyl groups. Monochlorination can occur on all of Sol. So in this reaction bromine is replaced with hydroxyl ion,
them. The products formed after mono chlorination will so this reaction is a substitution reaction. And we know
be that the hydroxyl ion has a negative charge so it is a
nucleophile. So, the reaction is a Nucleophilic
substitution reaction.
30. The increasing order of reactivity of the following

bromides in SN1 reaction is
(I) (II)
Br
28. Formation of free radical takes place with absorption of

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

(d) reactivity in SN1 reaction
(S)
(a) S > Q > R > P (b) S > R > P > Q

(I) (II) (c) P > Q > R > S (d) S > R > Q > P
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,
C H 3 X  10  2 0  3 0
(III) (IV)
Here, molecule (S) is a secondary alkyl halide
(a) II > III > IV > I (b) IV > III > II > I carbocation is stabilized by an aromatic ring and a
(c) III > IV > II > I (d) I > II > III > IV methyl group. Hence it has a greater reactivity towards
S N 1 reaction. (Q) and (R) are primary alkyl halides.
Ans. (a)
Since the aromatic ring stabilizes the positive charge
Sol. S N 1 reactivity increases for stable carbocation. When (Q) is more reactive than (R) followed by (P). So, the
bromine will be eliminated there will be formation of
carbocation, this carbocation is stabilized by order of reactivity is written as, S  Q  R  P
hyperconjugation of the substituents attached at the para- Thus, (a) is the correct option.
position. In compound (II) there are three hydrogen
atoms present, in (III) there are two hydrogen atoms, 33. The rate of SN1 reaction is fastest with:
(IV) there is one hydrogen atom, and in (I) there is no
hydrogen atom. As the number of hydrogen atoms
increases, the stability due to hyperconjugation
increases.
(a)
32. Rate of SN1 reaction is:
(P)
CH
(Q) Br
(b)
CH NO2
(R)
Br
(c)
less stable compared to option (A) and (B).

Option D:
CH2 Br
(d) 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.
the carbocation destabilises.
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 Sol. Greater the stability of carbocation, more it favors S N 1 .
formed on the carbon is highly stable due to the The stability of tertiary carbocation will be the most
delocalization of the positive charge by the two stable and the primary carbocation will the least stable.
phenyl groups adjacent to it.
Option B: 35. Which of the following compounds will undergo SN1

reaction?
CH
Br
Here, after the bromine leaves, the carbocation (a) (b)

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
option (A) since it has two phenyl groups but this
compound has one phenyl group.
Option C:
CH NO2
(c) (d)
Ans. (a)
Br
Sol. The compound a is a tertiary alkyl halide and there is
Here, after the bromine leaves, the carbocation formation of the carbocation intermediate formed by
formed on that carbon on which bromine was the loss of the chlorine ion which stabilized by the
attached. Here phenyl ring is present but the presence resonance with the benzene ring. Hence, the correct
of electron-withdrawing group destabilizes it. So it is answer is option (a)
rate of SN2 reaction.

36. Which one of the following will give racemised
product in C2H5OH? (P) (Q)
(R) H 3 C-Br (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)
(a) (b)
Sol. Allylic halides highly favor SN2 reaction. So (Q) must be
first but vinylic halides hardly go for SN2 reaction.
Thus, it must be last. The other two are decided on
basis of crowding.
39. Arrange the following in the deceasing order of their

(c) (d)
rate of SN2 reaction.
Ans. (c)
Sol. The chiral center is present in (c) only. For the reactant
to give a racemic mixture the compound must have at
least one chiral carbon atom. The reaction of formation
of a racemic mixture of option (c) is given below:
(P) (Q)
37. Which of the following reactions follows SN2

mechanism
(a) CH 3 Br + OH -  CH 3 OH + Br -
(b)
Θ Θ
CH 3  CH(Br) - CH 3 + O H  CH 3 CH(OH) - CH 3 + Br (R) (S)
(c) C H 3 C H 2 O H  -HO
2
 CH 2 =CH 2 (a) Q > R > P > S (b) R > Q > S > P
(c) P > Q > R > S (d) S > P > R > Q
(d)
CH3 CH3 Ans. (d)
Br -
Sol. EWG shall increase the rate of nucleophilic
H3C CH3 + OH- H3C CH3 +
substitution. NO2 is the electron withdrawing group so,
Br OH
it will be most reactive. Both OCH3 and CH3 both are
Ans. (a) electron donating group so, both will decrease the rate
Sol. The order for the SN 2 reaction is 1  2  3 . The
   of Nucleophilic substitution. The Nucleophilic
substitution ability will be more decreased by OCH 3
first option represents the best conditions to proceed by
SN 2 mechanism because there will be the formation of group than the CH3 group.
a primary carbocation.
40. Predict the major product of the reaction
38. Arrange the following in the deceasing order of their
(c) RCl > RBr > RF > RI

(d) RI > RBr > RCl > RF
Ans. (d)
Sol. SN 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.
Now, the strength of the bond between the carbon
Sol. EtO - K + + PhOH 
 EtOH + PhO - K +
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.
Now, the larger the size of the halogen, larger will be
the bond length and weaker will be the bond and
thus, in turn, the halogen will be a better leaving
41. group. So, the order of the size of halogens is I > Br >
This reaction would follow which of the following Cl > F.
pathway predominantly? Hence the order of reactivity of the alkyl halides
(a) SN1 (b) SN2 towards SN 2 reaction will be: R – I > R – Br > R –
(c) E1 (d) E2 Cl > R – F, which is option (d).
Ans. (b)
Sol. HI is very strong acid consequently, by Bronsted Mechanisms of elimination reactions
Lowry, I  is very weak base. Thus elimination is out
44. 1-Chlorobutane on reaction with alcoholic potash
of question. Similarly, the halide being primary, S N 2
gives
takes place. (a) 1-Butene (b) 1-Butanol
(c) 2-Butene (d) 2-Butanol
42. Which among MeX, RCH2X, R2CHX, R3CX is most Ans. (a)
reactive towards SN2reaction? Sol. The treatment of alcoholic potash or potassium
hydroxide with 1-chlorobutane leads to an
(a) MeX (b) RCH2X elimination reaction. In the elimination reaction,
(c) R2CHX (d) R3CX unsaturated compounds are produced by the
elimination of a leaving group.
Ans. (a) Let us see the reaction:
Sol. SN 2 reaction means nucleophilic substitution bi- 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
molecular reaction. This reaction takes place when
the leaving group is attached to the primary carbon Hence, we can see that 1-butene is produced and thus
atom. As the number of substituents on the carbon atom option (a) is the correct answer.
carrying halogen increases, steric hindrance increases
and hence the rate of SN2 reaction decreases. 45. Major product of the following reaction is:
Hence, option (a) is the correct one.
43. The order of reactivities of the following alkyl halides

for a SN2 reaction is
(a) RF > RCl > RBr > RI
(b) RF > RBr > RCl > RI
Sol. E2 elimination
(a) (b)
48.
(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 a
hydrogen atom from the beta carbon atom. The This reaction would follow which of the following
mechanism is given below: pathway predominantly?
(a) SN1 (b) SN2
(c) E1 (d)E2
Ans. (d)
Sol. Tert-butoxide being a very strong base, elimination
must take place.
46. n-Propyl bromide on treatment with ethanolic
potassium hydroxide produces
49. When CH3CHClCH2CH3 is treated with alcoholic
(a) Propane (b) Propene
(c) Propyne (d) Propanol KOH, the major product is
Ans. (b) (a) CH3 – CH = CH – CH3
Sol. The treatment of ethanolic potassium hydroxide with n- (b) CH2 = CH – CH2 – CH3
propyl bromide leads to an elimination reaction. In the (c) CH3 – CHOH – CH2 – CH3
elimination reaction, unsaturated compounds are
produced by the elimination of a leaving group. (d) CH3 – CH2 – CH2 – CH3
Let us see the reaction: Ans. (a)
CH3CH2CH2Br + KOH  CH3CH=CH2 + KBr +H2O Sol. When CH3 CHClCH 2 CH3 is treated with
n-Propyl Bromide Ethanolic Potassium Hydroxide Propene Potassium Bromide Water
Hence, we can see that option (b) is the correct answer. alcoholic KOH, elimination reaction takes place.
Chloride along with hydrogen is eliminated. Now, the
elimination of the particular hydrogen is decided by
the Saytzeff’s rule.
47. It says that the hydrogen is eliminated from the beta
carbon which has less number of hydrogen.
Now, let us look at the compound.
Major product :
1 2 3 4
C H3 C H  Cl  C H 2 C H3
β α β γ
From this, we can see that the chlorine is attached to

(a) (b) 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
hydrogen will be eliminated form C – 3. Hence the
(c) (d)
overall reaction will be:
Ans. (b)
CH3 CHClCH 2 CH3 

KOH
 alc.
 CH3CH=CHCH3 (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 Sol. For 1 π bond formation, 1 H and 1 Cl will be eliminated
CH3CH2CH(F)CH3 with CH3O–/ CH3OH is
∴ Equal no. of H and Cl will be eliminated. So, the
(a) CH3CH2CH(OCH3) CH3
product will be 1, 3, 5-chlorobenzene. The reaction is
(b) CH3 CH  CHCH3 given below:
(c) CH3 CH 2 CH  CH 2 Cl Cl
(d) CH3 CH 2 CH 2 CH 2 OCH3 Cl Cl
Ans. (c) alc.
Sol. Here, the leaving group is fluorine and when it is KOH
treated with alcohol and alkoxide then there will be the Cl -3HCl Cl
Cl Cl
formation of least substituted alkene.
Cl
51. What alkyl halide would give the following alkene as 53. 1-pentene will be formed as major product when
the only product in an elimination reaction methoxide reacts with
(a) 2-iodopentane
(b) 3-iodopentane
(c) 2-fluoropentane
(d) 3-fluoropentae
Ans. (c)
Sol. 1-pentene will be formed as major product when
methoxide reacts with 2-fluoropentane. In this case
fluoride ion is leaving group so major product is least
substituted alkene.
(a) (b)
(c) (d) Both (a) and (b)

Ans. (b)
Sol. Only the option (b) can give the specified product because
the rearrangement cannot be done. The chlorine atom is 54. What is true about the following reaction?
eliminated and the hydrogen atom removed from the
alpha-carbon atom. The reaction is given below:
H
- HCl
(a)Only substitution product is formed.

Cl (b)Only elimination product is formed.
(c)Both substitution and elimination products are
52. C6H6Cl6 is six membered cyclic compound in which formed and substitution dominates.
each carbon carry one chlorine atom, on treatment with (d)Both substitution and elimination products are
alcoholic KOH yields formed and elimination dominates.
CH3
-I
CH3 C CH CH3
CH3 I CH3

Ans. (d) CH3 C CH CH3
Sol.
CH3
CH3 CH3
CH3 C C CH3

CH3 CH3
C C
CH3 CH3
55.
The major alkene obtained when this alkyl halide is 56.
subjected to E1 reaction will be The major product obtained when this substrate is
subjected to E1 reaction will
(a)
(a) (b)
(b)
(c) (d) none of these

Ans. (b)
Sol. In E-1 reaction, the major product is always satyzeff
(c) product. [Note: In E-1 reaction, the hydrogen need
(d) All in equal proportions not be anti to the leaving group.
Ans. (a)
Sol. Since the reaction is E-1, the carbocation can rearrange
to form a more stable 3 o -carbocation to give the more
stable (saytzeff) product. The reaction is given below:
57. Find the major product of the following reaction
(b) CH3
(c) CH2
(a) (b)
(d) all three in equal proportions.
Ans. (b)
Sol. The E1 elimination of 1-Bromo-1methylcyclohexnae is
a two-step reaction. In the first step, the bromine atom
(c) (d) takes its bonding electron pair and forms a tertiary
Ans. (d) carbocation.
Sol. E1-elimination, so rearrangement is possible. When the In the next step, the base abstracts the beta-hydrogen
iodine is removed there is the formation of secondary atom and forms a 1-methyl-cyclohexene as a product.
carbocation, then the rearrangement takes for the The reaction is as shown below:
formation tertiary carbocation and the hydroxyl group
will attack the carbocation. The reaction is given below:
Br CH3 CH3
CH3 CH3 -Br 
CH3
H

I
CH3 CH3 H
I 
59. 2-bromopentane is heated with potassium ethoxide in
ethanol. The major product obtained is
CH3 (a) Pent-1-ene (b) cis pent-2-ene
 (c) trans pent-2-ene (d) 2-ethoxypentane
H
Ans. (c)
CH3 Sol. This is an E 2 elimination, where trans-alkene is more
favoured in which the same groups are on the opposite
side. The reaction is given below in which there is
elimination of HBr molecule.
Br
CH3
58.
The major product obtained when this substrate is
subjected to E1 reaction will be
60. The major product formed in the following reaction is
(a) CH3
(a)
62. Find the major product of the reaction:
(b) (a) (b)
(c) (d) Both (a) and (b)

Ans. (b)
(c)
Sol. Me3CO is very bulky base. So, Hoffman elimination
takes place. The chlorine atom will be eliminated and
the hydrogen will be eliminated from the alpha-carbon
atom. The major product is the one which has less
(d) substituted carbon atoms. The reaction is given below:
H Cl
Me3CO K 
H Major
+
Ans. (c)
Sol. E 2 elimination. The reactant is alcohol and alkoxide
which is used for the elimination of HBr molecule from
the reactant and this is will form an alkene. The Minor
reaction is given below:
CH3 CH3
CH3O
CH3 C CH2Br CH3 C CH2
CH3OH, Product :
H
63.
61.
In the above reaction, maximum Saytzeff product will
be obtained where X is: (a) (b)
(a) I (b) Cl
(c) Br (d)F
Ans. (a)
Sol. I is best leaving group and hence favours E2
mechanism. Since, I is a halogen and has least (c) (d) No reaction
electronegativity, will favor the E2 mechanism. Ans. (d)
Sol. There is no α - H which is anti to leaving group.
64. An 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)
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
Thus, (a) is the correct option.
CH3 CH CH CH2 CH3
2 - pentene
66.
65. The major product obtained when this alkyl halide is

The major product obtained when this alkyl halide is subjected to E2 reaction will be
subjected to E2 – reaction will be
(a)
(a)
(b)
(b)
68.
(c)
(d) all in equal proportion
Ans. (a)
Sol. The saytzeff product is major product in E2 elimination.
The bromine will be eliminated and the hydrogen will be
eliminated alpha-carbon atom. The more substituted
carbon atoms will be the major product. The reaction is
given below: (a) (b)
(c) (d) none of these

Ans. (b)
Sol. Even though, a more stable product is possible at the
methyl end, the H there is not anti to Br. (E-2) Thus,
less stable product is formed.
69.
67. The major product obtained when this alkyl halide is
The major product obtained when this substrate is subjected to E2 reaction under the treatment of
subjected to E2 reaction will be potassium tert-butoxide will be
(a)
(a) (b)
(b)
(c) both (a) and (b) (d) none of these
(c) (d) none of these Ans. (b)
Ans. (a) Sol. Tert-butoxide is a bulky base, hence, less stable
Sol. Saytzeff product. (At the same time, H is anti to Br) (Hoffman) product is formed. The bromine atom will
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,
70. only product a is possible for the given reaction.
Which of the following products will be major if this
substrate is subjected to E2 reaction?
72. If tert-butyl bromide and NaNH2 reacts, the product
formed is
(a) tert-butylamine
(a) (b) (b) tert-butylammonium bromide
(c) both in equal proportion (c) a mixture of butyl amines
(d) not predictable (d) iso butylenes
Ans. (b) Ans. (d)
Sol. E2 reaction gives Saytzeff product. The bromine will be Sol. This is an E2 -mechanism. The bromine atom will be
eliminated from   carbon and the hydrogen will be removed from alpha-carbon atom and the hydrogen
eliminated from Beta-carbon atom. Major product is atom will removed from the beta-carbon atom. Since
resonance stabilised alkene all the methyl group are alpha-methyl group, all the
methyl group will give same product. The reaction
given below:
CH3 CH3
CH3 C CH2 NaNH2

CH3 C CH2
- HBr
Br H
73. Choose the correct major product of the reaction:
71.
The products obtained when this substrate is

(a) (b)
76. What is the major product of the following reaction?
(c) (d)
Ans. (a)
Sol.
(a)
(b)
74. What is the product of the reaction of the following
compound with alcoholic potassium hydroxide?
(c)
(d) None of these
Ans. (a)
(a) 1-methylcyclohexane only Sol. The reagent used in the reaction is a strong base. So,
(b) 1-Methylcyclohexane only there will a formation of alkene which is less
substituted by the elimination of HBr by the process of
(c) 3-methylcyclohexene (major product),
Hofmann Elimination. The reaction is given below:
1-methylcyclohexene (minor product)
(d) 3-methylcyclohexene only CH3 CH3
Ans. (d)
H2C CH CH CH C CH3 Me3CO K 
Sol. For E 2 elimination (via anti periplanar arrangement) -HBr
leaving group (-Br) and β – Hydrogen should be in H Br CH3
opposite or anti position.

CH3 CH3
CH2 CH CH C CH3
CH3
77. Choose the 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)
(a) (b)
Sol. Alcoholic KOH favors E 2
CH3  CH  Br 
alc.KOH
 CH3  CH  CH 2  HBr
|
(c) (d)
CH3
Ans. (b)
Sol. There will be elimination of HCl molecule which leads 
OH
to the formation of cycloalkene. The double bond will 
be made in such a way that it has more substituents. N Me3 NMe3OH
The reaction is given below:
CH3 ONa CH3 H
Cl

78. What is the major product of the following reaction?
Major product:
80.
(a) (b)
(a) (b)
(c) (d)
Ans. (a)
Sol.
C 2 H5 ONa, +
Br 
C 2 H5 OH

Major Minor
(c) (d)
Ans. (d)
Sol. Since the leaving group is highly withdrawing but
strongly bonded, the eliminations is E1 -CB . Thus, the
79. Major product: alkene obtained is least substituted, i.e. ethene from the
ethyl group attached to N.
81. What is the major product of the reaction sequence?

(a) (b)
(c) (d)
Ans. (a)
 (a) (b)
Sol. Here, the LG is - N Me3 , which is highly with drawing
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
(c) (d)
broken and will form a double bond as in option (a).
The diagram is given below: Ans. (a)
Sol. Addition of C H 3 I (excess) methylates the amino (a) both SN1 and E1 have same rate-determining-step.
group. Next addition of Ag2O , H 2 O/Δ represents Therefore, E1 competes with SN1.
E 1 -cb mechanism, giving Hoffman product. In the first (b) a base is a nucleophile and a nucleophile is a base,
Therefore, SN2 competes with E2.
step the amine group will be replaced with iodine and in
the second step there is the formation of alkene. The (c) both a and b
reaction is given below: (d) none of these
Ans. (c)
Sol. Alkyl halide undergoes both substitution reaction and
elimination reaction. In a nucleophilic substitution
reaction, the one-step reaction is called the SN 2 reaction.
It is a bimolecular nucleophilic substitution reaction
where the rate of reaction depends on the concentration
of nucleophile and substrate. Here base can act as a
nucleophile. For example, the hydroxide ion is a good
82. Among the following the most reactive towards nucleophile. In E2 the elimination reaction, the
alcoholic KOH is nucleophile that the hydroxide ion acts as a base and
(a) CH2 = CHBr (b) H3CCOCH2CH2Br abstracts a proton and favors the reaction.
Therefore, SN 2 and E2 are compatible. Similarly, the
(c) CH3CH2Br (d) CH3CH2CH2Br
SN 1 reaction proceeds via the intermediate formation.
Ans. (b) The reaction forms carbocations as an intermediate. It is
Sol. a rate-determining step. The rate of reaction depends on
the concentration of substrate. It is as follows,
O
rate = k Substrate
E1 is elimination reaction proceeds via the carbocation
generation. It is a rate-determining step.
CH3 CH 2  CH 2  Br
The rate of reaction depends on the substrate. Thus
β α SN 1 and E1 are compatible.
β-Hydrogen is acidic due to EWG Therefore, both (a) and (b) options are correct.
Thus, (c) is the correct option.
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
between the alpha and beta carbon. This forms a
conjugated system. The reaction is given below:
84.
O
This reaction would follow which of the following
pathway predominantly?
alcoholic KOH (a) SN1 (b) SN2
CH3 CH2 CH2 Br
-HBr (c) SN1/E1 (d) SN2/E2
Ans. (d)
O
Sol. Here, there is equal probability. If there is SN 2 the
bromine nucleophile is replaced with methoxide ion.
CH3 C CH CH2 Since, methoxide ion is a weak base the elimination
Substitution vs Elimination reaction can also take place which leads to the formation
of cycloalkene.
83. SN1 competes with E1 and SN2 competes with E2.

General methods of preparation of alkyl halides
This is because
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)
Sol. In the given reactions alcohol to be protonated first…
HI being a strong acid among the given hydrogen
halides, readily gives the proton. Ans. (d)
The order is : HI >HBr>HCl> HF Sol. Peroxide effect- Bro goes to less substituted carbon in an
unsymmetrical alkene.
86. The following reaction is known as
C2H5OH+SOCl2  Pyridine
C2H5Cl+SO2+HCl
(a) Kharasch effect
(b) Darzen’s process
(c) Williamson’s synthesis 89. Which of the following organic compounds will give a
(d) Hunsdiecker synthesis reaction mixture of 1-chlorobutane and 2-chlorobutane on
Ans. (b) hydrochlorination (HCl)
Sol. The reaction is Darzen’s process. In the presence if (a) CH 3  CH  CH  CH
2
pyridine – in this inversion of configuration occurs |
(SN2). CH 3
(b)
87. Which of the following reagents could be used to convert
cyclohexanol to chlorocyclohexane? H
|
(a) Cl2, light (b) SOCl2 HC  C  CH  CH 2
(c) PBr3 (d) none of these (c) CH2=CH–CH=CH2
Ans. (b) (d) CH3  CH 2  CH  CH 2
Sol. It is an SN1 type reaction. Ans. (d)
Sol.
88.
(A) is :
(a)
(b) 90. What will be the product in the following reaction
(a)
(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
by following the Markovnikov rule.
(b) According to the Markovnikov rule, when HCl is added
to any alkene, the Cl  is added to the carbon atom
containing least number hydrogen atom or is added to the
carbon atom after the formation of the most stable
carbocation from the given alkene in the reaction.
The reaction takes place as follows,
(c) CH 3CHCH 2  HCl 
benzoyl peroxide
CH 3CH (Cl )CH 3
The most stable carbocation formed during the reaction
is CH3  CH ()  CH3 .
Hence, option (a) is the correct answer.
(d) 93. Which of the following reactions will yield 2,

2-dibromopropane?
(a) CH3 –C  CH +2HBr 
(b) CH3CH = CHBr +HBr 
(c) CH = CH +2HBr 
(d) CH3 – CH= CH2 + HBr 
Ans. (a)
Ans. (a) Sol. When propyne is treated with 2 moles of hydrogen
Sol. NBS (N - Bromosuccinimide) – substitute at Allylic bromide, the product is 2, 2-Dibromopropane, if the
position reaction is not in the presence of peroxide. This reaction
AllylicBromination takes place takes place as first the HBr reacts with propyne to form
CH2 Br 2-Bromopropene and then this reacts with HBr to form
NBS CH2 2, 2-Dibromopropane. The reaction is given below:
CH 3C  CH  HBr  CH 3C ( Br )  CH 2
CH 3C ( Br )  CH 2  HBr  CH 3  CBr2  CH 3
91. Preparation of alkyl halides in laboratory is least preferred
by Physical properties of alkyl and aryl halides
(a) Treatment of alcohols
(b) Addition of hydrogen halides to alkenes
94. Correct order of B.P. for the alkyl halide is
(c) Halide exchange
(a) C2H5Cl > C2H5Br > C2H5I
(d) Direct halogenation of alkanes
Ans. (d) (b) C2H5I > C2H5Br > C2H5Cl
Sol. In Direct halogenation alkanes via free radical (c) C2H5I > C2H5Cl > C2H5Br
mechanism.
(d) C2H5Br > C2H5I > C2H5Cl
A mixture of mono substituted, di substituted and tri
substituted alkyl halide derivatives are formed as Ans. (b)
byproduct which are not desired. Sol. For the same alkyl group : B.P. of alkyl halide increases
with the size of the halogen atom
92. When hydrochloric acid gas is treated with propene in  C2 H5 I > C2 H5 Br > C2 H5 Cl
presence of benzoyl peroxide, it gives
(a) 2-Chloropropane (b) Allyl chloride
95. In CH3CH2Br, % of Br is Ans. (a)

(a) 80 (b) 73 Sol. There is an increase in boiling point as we move from
chloride to a bromide to an iodide (for a given number of
(c) 70 (d) 7
carbon atoms) is because of the increase in the number
Ans. (d) 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
80 molecule attains spherical shape with less surface area.
% of Br is = 100  73.3 As a result, interparticle forces become weaker.
109
Hence, the lowest boiling point will be of t-butyl
chloride.
96. Which of the following is liquid at room temperature?
(a) CH3I (b) CH3Br
Reaction of Alkyl Halides
(c) C2H5Cl (d) CH3F
Ans. (a) 100. Benzene reacts with n-propyl chloride in the presence of
Sol. CH3 F,CH3Cl,CH3 Br and C 2 H 5 Cl are gases at room anhydrous AlCl3 to give
temperature. CH3I is liquid at room temperature and (a) 3-Propyl-1-chlorobenzene
solidifies at -66.5oC.
(b) n-Propylbenzene
(c) No reaction
97. Which of the following represents the correct order of
(d) Isopropylbenzene
densities?
Ans. (d)
(a) CCl4>CHCl3> CH2Cl2> CH3Cl > H2O
Sol. Benzene reacts with n-propyl chloride in the presence of
(b) CCl4>CHCl3> CH2Cl2> H2O > CH3Cl anhydrous aluminium chloride to give predominantly
(c) H2O > CH3Cl > CH2Cl2>CHCl3>CCl4 isopropylbenzene which is also called cumene.
Here, the carbocation so formed from n-propyl undergo
(d) CCl4>CHCl3> H2O > CH2Cl2> CH3Cl rearrangement to form more stable secondary
Ans. (b) carbocation which results in the formation of
Sol. CCl4 >CHCl3 >CH 2Cl 2 >H 2O>CH 3Cl isopropylbenzene or cumene.
Bromo, iodo and polychloro derivatives of hydrocarbons

are heavier than water. The density increases with
increase in number of chlorine atom, halogen atom but Anhyd. AlCl3
monochloro derivatives are lighter than water. + CH3CH2CH2Cl
98. Which of the following has the highest normal boiling

Benzene Cumene
point?
(a) iodobenzene (b) bromobenzene The carbocation formed during the reaction is
(c) chlorobenzene (d) fluorobenzene CH3CH 2 CH 2  which rearranges to more stable
Ans. (a) secondary carbocation CH3  CH()  CH3 .
Sol. There is an increase in boiling point as we move from
chloride to a bromide to an iodide (for a given number of Hence, option (d) is the correct answer.
carbon atoms) is because of the increase in the number
of electrons leading to larger dispersion forces. 101. Ethylene dichloride and ethylidene dichloride are
Hence, the maximum boiling point will be of isomeric compounds. Identify the statement which is not
iodobenzene. applicable to both of them
(a) react with alcoholic potash
99. Among the following alkyl halides, choose the one with (b) react with aqueous potash and give the same product
the lowest boiling point. (c) are dihalides
(a) t-butyl chloride (b) n-butyl chloride (d) Beilstein’s test
(c) t-butyl bromide (d) n-butyl iodide Ans. (b)
Sol. Here, according to the question ethylene dichloride and (a)

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)
Ethylene dichloride vicinal diol
(b)
(2)CH3  CH(Cl) 2 
Aq.KOH
 CH3  CHO
Ethylidene chloride acetaldehyde
Now, for option (a)

CH 2 (Cl)  CH 2 (Cl) 
Alc.KOH
 CH 2  CHCl
CH3 CH(Cl) 2 
Alc.KOH
 CH 2  CHCl (c)
For options (c), both the given compounds are
dihalides as both of them contain 2 chlorine atom and
hence, are dichlorides.
For option (d), Beilstein test is an organic test which is
used for qualitative test for halides.
So, this is also applicable to the given compounds as
both of them contain chlorine atoms (d)
Hence, option (b) is not applicable to the given and
compounds and therefore, is the correct answer.
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 Ans. (c)
(c) C – Br > C – Cl > C – I (d) C – I > C – Br > C – Cl Sol. Finkelstein reaction – involves the preparation of alkyl
Ans. (a) iodine from remaining alkyl halides by SN 2 mechanism.
Sol. Bond energy is directly proportional to the difference in R F  NaF 
electronegativity between the 2 atoms. 
R  Cl   NaI  R  l + NaCl 
Acetone
Since, the order of electronegativity: Cl  Br  I

R  Br  NaBr 
So, the order of the bond energy is
C  Cl  C  Br  C  I
104. Corey-House synthesis is a much more convenient
Hence, option (a) is the correct answer.
method for making odd no. alkanes for which of the
following reasons?
103. In the following reaction find the correct product : (a) Two different alkyl halides can be use. From one
alkyl halide, R2 CuLi is prepared and then this is reacted
with another alkyl halide.
(b) The reagent R2 CuLi can be prepared from 1°, 2° or
3° alkyl halide as well as from halobenzenes
(c) both (a) and (b)
NaI/Acetone (d) none of these
Ans. (c)
Sol. The scope of corey-House synthesis is exceptionally
broad and a range of lithium diorganylcuprates
(R2CuLi, R=1o, 2o, 3o alkyl, aryl or alkenyl) and (c) Ethyl nitrite (d) Ethane
Ans. (a)
organyl halide will undergo coupling.
Sol. CH3CH 2 Br + AgNO2  C2 H5 NO2 + AgBr
RX  2Li  RLi  LiX  
2RLi  CuI  R 2 CuLi  Li covalent Nitro ethane
R 2 CuLi  R 'X  R  R ' RCu  LiX

109. What is the major product of the reaction?
105. Which of the following combinations of reactants is
better for making propane?
(a) (CH3)2CuLi+CH3CH2Br  CH3CH2CH3
(b) Et2CuLi+CH3 – Br  CH3 – CH2 – CH3
(c) both of these (a)
(d) none of these
Ans. (c)
Sol. Smaller R – X are preferred in Corey – House synthesis.
(b)
106. Which of the following combinations of reactants is
better for making neopentane?
(a)
(c)
(b)
(d)
(c) both (a) and (b)

(d) none of these
Ans. (b) Ans. (c)
Sol. In Corey-House reaction for a better yield of product, the Sol.
alkyl halide used should be primary whereas lithium
dialkyl copper may be 1o ,2o ,3o
107. Silver acetate + Br2 The main product of this reaction is

(a) CH3— Br (b) CH3COI
(c) CH3COOH (d) None of these
Ans. (a)
Sol.
O
110. Which of the following reactions is a good way to

CS prepare methyl tert–butyl ether?
CH 3  C  O Ag + Br2 
2
 CH 3  Br + AgBr + CO 2
(a) CH3O–Na+ + (CH3)3 CBr
Borodine – Hunsdiecker reaction.
(b) (CH3)3CO– K+ + CH3I
108. Ethyl bromide reacts with silver nitrite to form (c) (CH3)3COH + CH3OH
(a) Nitroethane
(d) CH3MgBr + (CH3)3COCl
(b) Nitroethane and ethyl nitrite
Ans. (b)
Sol. Moreover, the hydrogen atoms on nitrogen 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
111. Iodine from iodoethane can be substituted by cyanide can repeatedly react with a number of alkyl halide
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 major 
product. RNH 2  3CH3 I   RN  CH3 3  I
(b) With either KCN or AgCN, EtNC is formed as major
product.
114.
(c) With AgCN, EtCN and with KCN, EtNC is formed.
(d) With AgCN, EtNC while with KCN, EtCN is formed
as major product.
Ans. (d)
Sol. AgCN – covalent – connecting atom is N  EtNC
KCN  Ionic  Connecting atom  'C' (a)

Et  CN
112. CH3 – CH2 – CH2 – I 

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

(a) CH3 – CH2 – NH – CH3
(b)
115. What is the product of the following reaction?

(c) CH3 – CH2 – N+(CH3)3I-
(d) CH2 = CH2
Ans. (c)
Sol. primary amines react with excess methyl iodide to (a)
form quaternary ammonium salts. The nitrogen atom
of primary amines contains a lone pair of electron. So,
primary amines are strongly nucleophilic in nature.
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
(b) (c) Alkene (d) Alkyne
Ans. (b)
Sol. R  X + Mg 
dry
Ether
 R Mg X
119. CH3 – CH2 – CH2 – Br + CH3 – CH2 – Br  

Na/ether

(c) Both (a) and (b)
(d) Neither (a) nor (b) P is :
Ans. (d) (a) P is mixture of three alkanes (n–hexane, n–butane
and n–pentane); none is formed in good yield
Sol. The reaction follows SN2 (inversion)
(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)
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
116. The increasing order of reactivity of the following
halides for the SN1 reaction is
120. The major substitution product of the following
(I) CH3CH(Cl)CH2CH3 (II) CH3CH2CH2Cl
(III) p-H3CO–C6H4 – CH2Cl
(a) (III) < (II) < (I) (b) (II) < (I) < (III)
(c) (I) < (III) < (II) (d) (II) < (III) < (I) KSH
reaction is  
Ans. (b)
Sol. S N 1 means unimolecular nucleophilic substitution
reaction, and we know the reactivity order for this
reaction is tertiary carbocation > secondary carbocation
> primary carbocation > methyl halide. So the structure
(I) is a secondary molecule because the chlorine is
attached to the carbon atom which is further attached to (a) (b)
two carbon atoms. Structure (II) is a primary molecule.
Structure (III) is also a primary molecule but it is the
most stable because this molecule can show resonance.
The reactivity order is: (II) < (I) < (III).
117. When CH3CH2CHCl2is treated with NaNH2 the product (c) (d)
formed is Ans. (d)
(a)CH3 – CH = CH2 (b) CH 3  C  CH Sol. S N 2  inversion of configuration.
(c) CH3CH2CH(NH2)(Cl) (d) CH3CH2C(NH2)2
Ans. (b) 121.
Sol. De hydro halogenation reaction elimination
Θ 
123. H3C-S Na +CH3CH 2 -X 

The reaction is fastest when X is:
P should be
(a) – OH (b) – F
O O
(a) || ||
(c)  O  C  CF3 (d) O  C CH3
Ans. (c)
O
||
(b) Sol.  O  C  CF3 Has negative charge delocalized.
Over oxygen the negative charge is delocalized because
there are three fluorine atoms present on the carbon atom
as fluorine atom is electron withdrawing group.
(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
Sol. Alkyl halides (2o and 3o) are reduced by sodium (b) R–I > R–Br > R–Cl> R–F
borohydride
(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
122. Elimination of bromine from 2-bromobutane results in the depends on the quality of the leaving group. If the
formation of halide is a good leaving group, then the reactivity
(a) predominantly 2-butyne increases.
(b) predominantly 1-butene Dehydrohalogenation is the elimination of HX or
hydrogen halides from an alkyl halide.
(c) predominantly 2-butene
Now, the strength of the bond between the carbon
(d) equimolar mixture of 1 and 2-butene atom and the halogen decides the quality of the
Ans. (c) leaving group. If the bond strength is weak then the
Sol. If the bromine is attached to the terminal carbon atom, halogen will be a good leaving group because it can
then there is the formation of only one alkene. But if, the easily break the C – X bond.
bromine is attached at the carbon atom other than the Now, the larger the size of the halogen, larger will be
terminal carbon atom, then there will be the formation of the bond length and weaker will be the bond and
more than one alkene, so the major alkene will be the thus, in turn, the halogen will be a better leaving
group. So, the order of the size of halogens is I > Br >
alkene with more substitution or lesser number of Cl> F.
hydrogen. So, the major product for the elimination of the
Hence, the order of reactivity of the alkyl halides
bromine from 2-bromobutane, there will the formation of towards dehydrohalogenation reaction will be: R – I
2-butene as a major product. The reaction is given below: > R – Br > R – Cl> R – F, which is option (b).
- HBr
CH3 CH CH2 CH3 CH3 CH CH CH3
Polyhalogen Compounds
Br 2 – Butene (Major)
+ 125. Industrial preparation of chloroform employs acetone and

(a) Phosgene (b) Calcium hypochloride
CH2 CH CH2 CH3 (c) Chlorine gas (d) Sodium chloride
1 – Butene (Minor) Ans. (b)
Sol. Calcium hypochlorite  CaOCl 2  and acetone are used
for industrial preparation of chloroform.
So, option (b) is the correct answer. Ans. (c)

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 was in an ionizable form. But when the CCl4 is
(c) Propane (d) Benzene 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.
130. Chloroform for anesthetic purposes is tested for its purity

127. Number of –bonds present in B.H.C. (Benzene with the reagent
hexachloride) are
(a) Silver nitrate (b) Lead nitrate
(a) 6 (b) Zero
(c) Ammoniacal Cu2Cl2 (d) Fehling solution
(c) 3 (d) 12
Ans. (b) Ans. (a)
Sol. Sol. The impurity HCl reacts with AgN O 3 to give ppt 
AgCl
131. The use of the product obtained as a result of reaction

between acetone and chloroform is
(a) Hypnotic (b) Antiseptic
(c) Germicidal (d) Anaesthetic
Ans. (a)
Sol. Chloretone is formed
128. B.H.C. is used as
(a) Insecticide (b) Pesticide
(c) Herbicide (d) Weedicide
Ans. (a)
Sol. B.H.C stands for Benzene hexachloride.Benzene
hexachloride is an insecticide generally known as
gammaxene. It is obtained by the following reaction- 132. Which plastic is obtained from as follows
o
CHCl3 
HF
BF3
X 
800 C
 
Polymarisation
 Plastic
(a) Bakelite (b) Teflon
(c) Polythene (d) Perspex
Ans. (b)
Sol.
800 C
CHCl3 
HF
SbF3
 CHF2 Cl   CF2  CH 2

Polymerisation
 [CF2  CF2 ] n (teflon)
129. CCl4 cannot give precipitate with AgNO3 due to 133. When CHCl3is boiled with NaOH, It gives
(a) Formation of complex with AgNO3 (a) Formic acid
(b) Evolution of Cl2 gas (b) Trihydroxy methane
(c) Chloride ion is not formed (c) Acetylene
(d) AgNO3 does not give silver ion (d) Sodium formate
Ans. (d) Cl
Sol.
CuCl2
+ HCl + O2 H2O +
4000C
134. The commercial uses of DDT and benzene Hence, option (b) is the correct answer.
hexachloride are
(a) DDT is a herbicide, benzene hexachloride is a
fungicide
Reaction of Aryl Halides
(b) Both are insecticides
(c) Both are herbicides 137. Which chloro derivative of benzene among the following
would undergo hydrolysis most readily with aqueous
(d) DDT is a fungicide and benzene hexachloride is a
sodium hydroxide to furnish the corresponding hydroxy
herbicide
derivative?
Ans. (b)
(a) (b)
Sol. BHC is a highly toxic, non-specific
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 (c) (d) C6H5Cl
effect to combat malaria, typhus, and the other insect-
borne human diseases among both military and civilian
populations.
Hence, both are insecticides. Ans. (a)
Hence, the second option is correct. Sol. Aryl halides does not easily undergo nucleophilic
substitution reaction because of the double bond
135. The formula of freon-12 is : character between halogen atom and the carbon atom due
(a) CClF3 (b) CH2Cl2 to resonance, due to sp2 hybridization of carbon atom
which increases its electronegativity which increase the
(c) CCl2F2 (d) CH2F2 bond strength and due to the instability of phenyl cation
Ans. (c) so formed during the reaction.
Sol. CF2 Cl2 But as the number of electron withdrawing groups like
 NO 2 increases, the benzene becomes electron-
deficient and it undergo nucleophilic substitution.
Preparation of Aryl Halides
So, 2,4,6-trinitrochlrobenzene reacts easily with NaOH
and undergo nucleophilic substitution reaction to form
136. Chlorobenzene is prepared commercially by 2,4,6-trinitrophenol.
(a) Down’s process (b) Raschig’s process Cl OH
(c) Deacon’s process (d) Etard’s process
NO2 NO2 NO2
Ans. (b) NO2
Sol. Chlorobenzene is commercially produced by Raschig’s NaOH

process.
The reaction involved in Raschig’s process is as follows,
NO2 NO2
138. Which of the following reaction is called Wurtz-Fittig

reaction?
(a)
(b)
140. In addition-elimination pathway of nucleophilic

aromatic substitutions, which of the following
compounds is most reactive?
(a)
(c)
(b)
(d) both (b) and (c)

Ans. (b)
Sol. Aryl halide + Alkyl Halide
 Na/Ether (c)
Alkyl substituted benzene (Wurtz – Fittig)
139.
(d)
This reaction follows

(a) Elimination pathway
(b) Substitution pathway
(c) addition-elimination pathway
Ans. (a)
(d) none of these
Sol. Reactivity : F >Cl> Br > I on benzene ring.
Ans. (c)
-I effect applied.
Sol. Aryl halide with electron withdrawing groups involves
in Nucleophilic substitution Aromatic through addition
elimination pathway. 141. In addition-elimination pathway of nucleophilic
aromatic substitutions, which of the following
compounds is most reactive?
(a)

1. HO / 
  P
2. H  Major 
Based on the above reaction, the major product would be

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

(c)
Ans. (b)
Sol. NO 2 -Group directs the incoming nucleophile to ortho
and para positions through –M effect (facilitates Nu)
144. Which of the following has the fastest rate of the reaction
with NaOC2H5?
(d)
(a) p–fluoronitrobenzene (b) p–bromonitrobenzene
(c) p–chloronitrobenzene (d) p–iodonitrobenzene
Ans. (a)
Sol. I-effect
145.
Ans. (c) Cl
Sol. The reactivity of aryl halides towards nucleophilic
aromatic substitution reaction increase with increase in Cl
C2H5ONa
no. of electron withdrawing groups on benzene ring. P; P is:

142. In addition elimination pathway of nucleophilic aromatic

substitutions, a–NO2 groups is NO2
(a) o, p–directing and activating (a) (b)

OC2H5 Cl
(b) o, p–directing and deactivating
(c) m–directing and activating Cl OC2H5
(d) m–directing and deactivating
Ans. (a)
Sol. NO 2 - Group directs the incoming nucleophile to O and
P positions through –M (facilitates Nu) NO2 NO2
(b) (d)
143.
Cl
OC2H5
OC2H5 Cl
NO2 OC2H5
Ans. (a)
Sol. The presence of nitro group at ortho and para positions (c)
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
the reaction below? (d)
I. The intermediate is aromatic. Ans. (c)

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

Mg
C6H5MgCl (Grignard reagent) following would undergo hydrolysis, most readily with
Dry Ether aqueous NaOH?
(a)
O2N NO2
C6H5MgCl + C2H5OH C2H5OMgCl +

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

O2N
(b)
NO2
149. Which one of the following compounds undergoes
hydrolysis most readily by aq. NaOH to furnish
corresponding phenol? O2N Cl
Cl Cl
NO2
(c)
(a) (b) O2N
OCH3 O2N Cl
Cl Cl
O2N
NO2 (d)
(c) (d) O2N
Cl
NO2 NO2
Ans. (d)
O2N Cl
Sol. The presence of nitro group at ortho and para positions
withdraws electron density from the benzene ring and Ans. (b)

thus facilitate the attack of the nucleophile OH on the Sol. Aryl halide having EWG – in benzene ring is more
reactive.
given haloarene. The carbanion thus formed is stabilized
through resonance. -M effect can operate through ortho, para positions only.
Exercise – 2: Previous Year Questions

(c)
1. Which of the following reactions is an example of

nucleophilic substitution reaction? (AIPMT
2009)
(a) 2 RX  2 Na  R  R  2 NaX
(d)
(b) RX  H 2  RH  HX
(c) RX  Mg  RMgX
(d) RX  KOH  ROH  KX
Ans. (d)
Sol. Nucleophilic substitution reaction involves replacement Ans. (a)
of a group or atom by a nucleophile. Sol. S N 2 is an inversion reaction, so will be favoured by
Nucleophiles are either negative charge or a lone pair least sterically hindered carbon atom or a primary carbon
of e− bearing species, OH− etc.
atom. Hence, will be most reactive in SN2
2. CH 3  CH 2  Br on treatment with LiAlH4 gives ethane reaction.
gas while (CH3)3C-Br on same treatment gives H2 gas
because (OJEE 2009) 4. Consider the following reactions,
(a) the former is SN2 and latter is E2 C2 H5 Cl  AgCN 
EtOH/ H2 O
 X
(Major)
reaction
(b) the former is E2 and latter is SN2 reaction Which one of the following statements is true for X?
(c) the former is SN1 and latter is E2 reaction (EAMCET 2009)
(d) the former is E2 and latter is SN2 reaction I. It gives propanoic acid on hydrolysis.
Ans. (a) II. It has an ester functional group.
Sol. III. It has nitrogen linked to ethyl carbon.
IV. It has a cyanide group.
(a) IV
(b) III
(c) II
(d) I
Ans. (b)
EtOH/
Sol. C2 H 5  Cl  AgCN 
H O
C2 H 5  NC  AgCl
2
3. Which one of the following species will be most reactive
in SN2 reaction? (AMU 2009) Nitrogen linked to ethyl carbon.
(a)
5. The correct order of increasing reactivity of C – X bond
towards nucleophile in the following compounds is
(AIPMT 2010)
(b)
(a) I < II < IV < III

(b) II < III < I < IV
(c) IV < III < I < II
(d) III < II < I < IV 8. The reaction,
Ans. (a) RX  2Na  RX 
Dry ether
 R  R  2NaX
Sol. The order of reactivity is dependent on the stability of
the intermediate carbocation formed by cleavage of C– is called (Hayana PMT 2010)
X bond. The 3o carbocation (formed from III) will be (a) Sandmeyer’s reaction
more stable than its 2o counterpart (formed from IV) (b) Wurtz reaction
which in turn will be more stable than the arenium ion
(c) Fittig reaction
(formed from I). Also, the aryl halide has a double bond
character in the C–X bond which makes the cleavage (d) Williamson’s synthesis
more difficult. However, inspite of all the stated factors, Ans. (b)
II will be more reactive than I due to the presence of the Sol. When two molecules of alkyl halides (same or different)
electron withdrawing –NO2 group. react with metallic sodium in the presence of ether to
C – X bond becomes weak and undergoes nucleophilic form alkane, this reaction is called Wurtz reaction.
6. In the following reaction

C6 H 5CH 2 Br   X , is CH3CH2 Br  A 

1. Mg, Ether aq.KOH KMnO4 / H
(AIPMT 9. 
2. H O +
3
2010) B 
NH 3

 C 
Br2
alkali
 D, D is (KCET 2010)
(a) C6H5CH2OCH2C6H5 (a) CH3 Br
(b) C6H5CH2OH
(b) CH3 CONH 2
(c) C6H5CH3
(d) C6H5CH2CH2C6H5 (c) CH 3 NH 2
Ans. (c) (d) CHBr2
Sol.
Ans. (c)
aq. KOH KMnO / H 
Sol. CH 3 CH 2 Br  
 CH 3 CH 2 OH 

4

 A
 
NH
CH 3 COOH 
3
 CH 3 CO O N H 4
Acetic acid  B 
 Br / alkali
  CH 3 CONH 2  2

 Hofmann bromamaide reaction 

7. iso-propyl bromide on Wurtz reaction gives Acetamide  C 
(RPMT 2010) CH 3 NH 2
(a) hexane Methyl amine  D 
(b) propane
(c) 2, 3-dimethylbutane 10. Reaction of methyl bromide with aqueous sodium
(d) neo-hexane hydroxide involves (KCET 2010)
Ans. (c) (a) racemisation
Sol. (b) SN1 mechanism
(c) retention of configuration
(d) SN2 mechanism
SOLID STATE 27
Ans. (d) Ans. (c)

Sol. Since the reaction depends upon the concentration of Sol. SN1 reactions proceed via the formation of a
both reactant and nucleophile, it follows SN2 mechanism. carbocation intermediate.
It involves inversion of configuration. More stable is the carbocation more reaction more
reactive is the alkyl/aryl halide towards SN1.
In C6H5C+(CH3)(C6H5) carbocation, the two phenyl
rings by their –R effect and –CH3 by its +I effect
diminish the positive charge and make it stable.
11. The reactivities of CH 3 Cl, CH 3 CH 2 CH 2 Cl and C6 H5 Cl

are in the order (CMC 2010)
14. Consider the reactions.
(a) CH 3 Cl  CH 3 CH 2 Cl  C 6 H 5 Cl
(i)
 CH3 2 CH  CH 2 Br 
C H OH
2 5
  CH3 2 CH  CH 2OC2 H5  HBr
(b) CH 3 CH 2 CH 2 Cl  CH 3 Cl  C6 H 5 Cl
(ii)
(c) C6 H 5 Cl  CH 3 CH 2 CH 2 Cl  CH 3 Cl  CH 3 2 CH  CH 2 Br 
C H O
2 5
 CH 3 2 CH  CH 2OC2 H 5  HBr

(d) CH 3 Cl  C6 H 5 Cl  CH 3 CH 2 CH 2 Cl The mechanisms of reactions (i) and (ii) are

Ans. (a) respectively (AIPMT
Sol. Bulky group causes steric hindrance in the formation of 2011)
transition state. Therefore, higher homologous are less (a) SN1 and SN2
reactive than lower homologous. (b) SN1 and SN1
∴ The correct order is (c) SN2 and SN2
CH 3 Cl  CH 3 CH 2 CH 2 Cl  C6 H 5 Cl (d) SN2 and SN1
Ans. (c)
Sol. If reaction is SN1, there will be the formation of
12. Identify Z, in the following series. carbocation and the rearrangement takes place. In these
C 2 H 5 I  
alc. KOH
 X 
Br2
Y 
KCN
Z reactions there is no rearrangement hence both are SN2
mechanism.
(VMMC 2010)
(a) CH3 CH 2 CN 15. Given reaction, ‘Y’ in the reaction is
(b) NCCH 2  CH 2 CN
(c) BrCH 2  CH 2 CN
(d) BrCH  CHCN
(DUMET 2011)
Ans. (b)
(a) hexane
Sol.
(b) cyclohexane
alc. KOH Br
C2 H 5 I  HI
 CH 2  CH 2 
2
 (c) cyclohexylcyclohexane
X 
(d) cyclohexyl ether
KCN
BrCH 2  CH 2 Br  NCCH 2  CH 2 CN Ans. (b)
Y  Z 
Sol.
13. Which one is most reactive towards SN1 reaction?

(AIPMT 2011)
(a) C6H5CH(C6H5)Br
(b) C6H5CH(CH3)Br
(c) C6H5C(CH3)(C6H5)Br
(d) C6H5CH2Br
(c) CH 2  CHCH 2 Br
(d)  CH 3 3 CBr
Ans. (b)
Sol. SN2 mechanism involves the back side attack and
formation of a transition state, thus less hindered alkyl
halide readily undergoes SN2 mechanism. Among the
given, CH 3 Br (methyl bromide) is less hindered, thus it
is hydrolysed by SN2 mechanism.
16. Which one of the following is not true for the hydrolysis 19. CH 3 CH 2 CH 2 Br 
KOH
alcohol
 CH 3 CH  CH 2
of t-butyl bromide with aqueous NaOH? The above reaction is an example of …… reaction.
(KCET 2011) (OJEE 2011)
(a) Reaction occurs through the SN1 (a) substitution
mechanism (b) elimination
(b) The intermediate formed is a carbocation (c) addition
(c) Rate of the reaction double when the concentration of (d) rearrangement
alkali is doubled
Ans. (b)
(d) Rate of the reaction double when the concentration
of t-butyl bromide is doubled Sol. The given reaction is an example of elimination reaction,
in which one molecule of HBr is eliminated from alkyl
Ans. (c) halide to give alkene.
Sol. Statement (c) is not true because hydrolysis of t-butyl
bromide takes place through SN1 mechanism, i.e. rate 20. In the replacement reaction
depends only upon the concentration of alkyl halide.
17. Following is the substitution reaction in which –CN The reaction will be most favourable if M happens to
replaced –Cl be (AIPMT

R  Cl  KCN   R  CN  KCl 2012)
(Alcoholic) (a) Na
To obtain propanenitrile, R-Cl should be (b) K
(KCET 2011) (c) Rb
(a) chloroethane (d) Li
(b) 1-chloropropane Ans. (c)
Sol. Tertiary halide shows SN1 mechanism i.e., ionic
(c) chloromethane mechanism. In the given reaction negative ion will
(d) 2-chloroproane attack on carbocation. Thus, greater the tendency of
Ans. (a) ionization (greater ionic character in M – F bond) more
Sol. Chloroethane reacts with KCN in the presence of heat to favourable will be reaction. The most ionic bond is Rb –
form propane nitrile. F in the given examples thus most favourable reaction
will be with Rb – F.

CH 3 CH 2 Cl  KCN   CH 3 CH 2 CN  KCl
Chloroethane Alcoholic Propane nitrile
21. In the following sequence of reaction,

18. Which of the following alkyl halides is hydrolysed by CH 3  Br 
KCN
 A 
H3 O 
 B 
LiAlH 4
 C, C is
SN2 mechanism? (BVP 2011)
(a) C6 H5 CH 2 Br (CBSE AIPMT 2012)
(a) acetone
(b) CH3 Br
(b) methane
SOLID STATE 29
(c) acetaldehyde (e) 3-bromo-2-methylpentane

(d) ethyl alcohol Ans. (e)
Ans. (d) Sol.
KCN H O
Sol. CH 3 Br 
 KBr
 CH 3CN 
3
 CH 3COOH
Methyl bromide Methyl cyanide(A) Ethanoic acid  B 
LiAlH 4

ether
 CH 3 CH 2 OH
C 
22. In alkaline hydrolysis of a tertiary halide by aqueous

solution of alkali if concentration of alkali is doubled,
then the reaction (AIIMS 2012)
(a) will be doubled
(b) will be halved
(c) will remain constant
(d) None of these
Ans. (c)
Sol. In alkaline hydrolysis of a tertiary halide by aqueous
alkali, if concentration of alkali is doubled, then the
reaction will remain constant because t-alkyl halides
with aqueous alkali give SN1 reaction and rate of SN1
25.
reaction is not based upon concentration of nucleophile,
(i.e. alkali).
23. When alkyl halide is heated with dry Ag2O, it

produces (Manipal 2012)
(a) ester
(b) ether
I and II are (NEET
(c) ketone 2013)
(d) alcohol
Ans. (b) (a) identical
Sol. Alkyl halide on reaction with dry silver oxide (Ag2O) (b) a pair of conformers
gives ether (c) a pair of geometrical isomers
2 RX  Ag 2 O  R  O  R  2 AgX (d) a pair of optical isomers
Alkyl halide Ether
Ans. (b)
Sol. I and II are staggered and eclipsed conformers.
24. An alkyl halide with molecular formula C6H13Br on
dehydrohalogenation gave two isomeric alkenes X and 26. Which of the following alkyl halide is used as a
Y with molecular formula C6H12. On reductive methylating agent? (KCET 2013)
ozonolysis, X and Y gave four compound CH3COCH3,
CH3CHO, CH3CH2CHO and (CH3)2CHCHO. The alkyl (a) C2 H5 Br
halide is (b) C6 H5 Cl
(Kerala CEE 2012)
(c) CH3Cl
(a) 2-bromohexane
(b) 2,2-dimethyl-1-bromobutane (d) C2 H5Cl
(c) 4-bromo-2-methylpentane Ans. (c)
(d) 2-bromo-2,3-dimethylbutane
Sol. CH3Cl is used as methylating agent. The methylating Sol. This problem includes concept of SN1 and SN2 reaction
agent is one which is used for the introduction of methyl and factors affecting SN1 and SN2 reaction.
groups. During SN2 reaction of alkyl halide, inversion of
configuration takes place instead of rearrangement.
27. Which of the following compounds will undergo While SN1 reaction occurs through the formation of
racemization when solution of KOH hydrolyses? carbocation intermediate which is favoured by the
(AIPMT 2014) presence of Lewis acid and aprotic solvent.
(i) Rearrangement of carbocation is also possible in this
case.
Thus, statement (b) is incorrect and all other statements
are correct.
(ii) CH3CH2CH2Cl 29. What is the name of the following reactions?

CH 3 CH 2 CH 2 Br  NaI
 CH 3 CH 2 CH 2 I
(iii) Dry acetone
(EAMCET 2014)
(a) Sandmeyer reaction
(b) Gattermann reaction
(iv) (c) Finkelstein reaction
(d) Swarts reaction
Ans. (c)
Sol. Alkyl bromide reacts with sodium iodide (in acetone or
methanol) to form alkyl iodides. This is called
Finkelstein reaction.
(a) (i) and (iii)
NaI
(b) (ii) and (iv) CH 3CH 2CH 2 Br 
Dry acetone
 CH 3CH 2CH 2 I  NaBr
(c) (iii) and (iv)
(d) only (iv)
30. Two possible stereo-structures of CH3CHOHCOOH,
Ans. (d) which are optically active, are called (AIPMT
Sol. Due to chirality 2015)
(a) atropisomers
(b) enantiomers
(c) mesomers
(d) diastereomers.
only compound (iv) will undergo racemization.
Ans. (b)
Sol.
28. An incorrect statement with respect to SN1 and SN2

mechanisms for alkyl halides is (KCET 2014)
(a) a strong nucleophile in an aprotic solvent increase the
rate or favours SN2 reaction
(b) competing reaction for an SN2 reaction is
rearrangement 31. In an SN1 reaction on chiral centres, there is
(c) SN1 reaction can be catalyzed by some Lewis acids (AIPMT 2015)
(d) a weak nucleophile and aprotic solvent increase the (a) inversion more than retention leading to partial
rate of SN1 reaction racemisation
Ans. (b) (b) 100% retention
(c) 100% inversion
SOLID STATE 31
(d) 100% racemisation Sol. The reaction,

Ans. (a) CH 3CH 2CH 2 Br  NaCN  CH 3CH 2CH 2CN  NaBr
Sol. In case of optically active alkyl halides, SN1 reaction is follows SN2 mechanism which is favoured by polar
accompanied by racemization. The carbocation formed aprotic solvent i.e., N, N’-dimethylformamide (DMF),
in the slow step being sp2 hybridised is planar and attack
of nucleophile may take place from either side resulting
in a mixture of products, one having the same
configuration and other having inverted configuration.
The isomer corresponding to inversion is present in
slight excess because SN1 also depends upon the degree 34. For the following reactions,
of shielding of the front side of the reacting carbon. (i)
CH3CH2 CH2 Br  KOH  CH3CH  CH2  KBr  H2 O
32. The reaction of C6H5CH=CHCH3 with HBr produces
(ii)
(AIPMT 2015)
(a) C6H5CH2CH2CH2Br
(b)
(iii)
(c)
Which of the following statements is correct?

(NEET 2016)
(d) (a) (i) is elimination reaction, (ii) is substitution and (iii)
is addition reaction.
(b) (i) is elimination, (ii) and (iii) are substitution
reactions
Ans. (c) (c) (i) is substitution, (ii) and (iii) are addition reactions
Sol. (d) (i) and (ii) are elimination reactions and (iii) is
addition reaction.
Ans. (a)
Sol.
(i)
CH 3CH 2CH 2 Br  KOH  CH 3CH  CH 2  KBr  H 2O
Elimination reaction
(ii)
33. Consider the reaction,

CH 3CH 2CH 2 Br  NaCN  CH 3CH 2CH 2CN  NaBr
This reaction will be the fastest in (NEET 2016)
(a) ethanol (iii)
(b) methanol
(c) N,N’-dimethylformamide (DMF)
(d) water
Ans. (c)
36. Neopentyl chloride reacts with benzene in presence of a

Lewis acid (AlCl3) to form (JIPMER 2018)
(a)
35. Identify A and predict the type of reaction.

(NEET 2017)
(b)
(a)
(c)
and elimination addition reaction
(b)
(d)
and cine substitution reaction.

(c)
Ans. (b)
and cine substitution.

(d)
and substitution reaction.

Ans. (d)
Sol. m-Bromoanisole gives only the respective meta Sol.
substituted aniline. This is a substitution reaction which
goes by an elimination-addition pathway.
37. Identify the major product that is obtained on treatment
of CH 3 CH 2 CH  F  CH 3 with CH 3 O  / CH 3 OH
is (JIPMER 2018)
(a) CH 3 CH 2 CH  OCH 3  CH 2
(b) CH 3 CH  CHCH 3
(c) CH 3 CH 2 CH  CH 2
(d) CH 3 CH 2 CH 2 CH 2 OCH 3
SOLID STATE 33
Ans. (c) (b) CH 2  CH 2

Sol. F is poor leaving so according to Hoffmann rule, (c) CH  CH
dehydrohalogenation occurs in such a way that the major
product is less substituted. (d) CH 4
CH O  Ans. (d)
CH 3CH 2 CH  F  CH 3 
3
CH OH

3 Sol. The given reaction takes place as follows:
CH 3CH  CHCH 3  CH 3CH 2CH  CH 2 Br / hv Na/dry ether
 Minor   Major  CH 4 
2
Step 1
CH 3 Br 
Wurtz reaction
 CH 3  CH 3
 A Step 2 
 Step 1: Alkyl halide is formed by free radical

38. CH3  Br 
Mg / ether
 
(i) CO2
(ii) H2 O
 
CH3 OH / H

P halogenation of alkane in the presence of UV-light.
Which is the product ‘P’ in the above reaction? Step 2: The formed alkyl halide reacts with sodium in
the presence of dry ether to form alkane containing
(JIPMER 2018)
double number of carbon atoms present in alkyl halide.
(a) Methyl ethanoate
This reaction reaction is known as Wurtz reaction.
(b) Ethanoic acid
From the above reaction, it is concluded that option (d)
(c) Propanal is correct as in all other cases the hydrocarbon formed in
(d) Methyl propanoate step 2 will have four carbon atoms.
Ans. (a)
Sol. The reaction is as follows: 41. A bromoalkane ‘X’ reacts with magnesium in dry ether
to form compound ‘Y’. The reaction of ‘Y’ with
methanol followed by hydrolysis yield an alcohol having
molecular formula, C4H10O. The compound ‘X’
is (AIIMS 2018)
(a) bromomethane
(b) bromethane
(c) 1-bromopropane
Hence, the product ‘P’ is methyl ethanoate. (d) 2-bromopropane
Ans. (c)
39. Among the following, the suitable reagent for Wurtz Dry ether
Sol. CH 3 CH 2 CH 2 Br  Mg   CH 3 CH 2 CH 2 MgBr
reaction is (JIPMER 2018) 1 bromopropane Y 
(a) Na/alcohol X 
HCHO
(b) Na/ether   CH 3 CH 2 CH 2 CH 2  O  MgBr
(c) Zn/ether H O

2
 CH3CH 2CH 2CH 2OH 
(d) Zn/alcohol 1 butanol
Ans. (b)
Sol. The suitable for Wurtz reaction is Na/ether. An ethereal
solution of an alkyl halide is treated with sodium to 42. Assertion (A): The boiling points of alkyl halides
produce higher alkanes. This reaction involves the decreases in the order RI > RBr > RCl > RF
formation of new C-C bond. E.g.
Reason (R): The boiling points of alkyl chlorides,
Ether
2CH 3 CH 2 Br  2 Na   CH 3 CH 2 CH 2 CH 3 bromides and iodides are considerably higher than that
Ethyl bromide Butane of the hydrocarbon of comparable molecular mass.
(AIIMS 2018)
40. Hydrocarbon (A) reacts with bromine by substitution to (A) If both assertion and reason are correct and the
form an alkyl bromide which by Wurtz reaction is reason is the correct explanation of assertion.
converted to gaseous hydrocarbon containing less than (B) If both assertion and reason are true but the reason is
four carbon atoms. A is (NEET 2018) not the correct explanation of assertion.
(a) CH 3  CH 3 (C) If the assertion is true but the reason is false.
(D) If the reason is true but the assertion is false.

Ans. (b)
Sol. Assertion and reason both are correct statements but
reason is not the correct explanation of assertion. For the
same hydrocarbon part, boiling point depends upon the Neopentane contains all equivalent
atomic mass of halogen atom. Higher the mass of the hydrogen atoms. So, it will give only one monochloro
halogen atom, higher will be the boiling point. So, derivative on halogenation.
boiling point decreases with decrease in atomic mass of
halogen atom. Thus, the decreasing order of boiling point
is, 45. If react with Cl2 in presence of light and then react
RI > RBr > RCl > RF with Na metal in dry ether, final product is
43. Correct order for reaction with alcoholic KOH. (JIPMER 2019)
(AIIMS 2019) (a)
(b)
(a) A > B > C > D
(b) A > C > B > D
(c) D > B > C > A
(d) A > D > B > C (c)
Ans. (b)
Sol. When alcoholic KOH reacts with haloalkanes, the
reaction (rate) depends on the following factors:
(i) Size of halogen (d)
(ii) Degree of C-atom, to which the halogen atom is
bonded, i.e., more be the degree of haloalkanes, more is
its reactivity on the above basis.
As bromine atom is larger in size, thus
Ans. (d)
Sol. When cyclobutane reacts with Cl2 in presence of light,
substitution reaction takes place.
Hence, correct order is A > C > B > D.

Thus, option (b) is correct. The reaction of product with Na metal in dry ether takes
place as,
44. The alkane that gives only one mono-chloro product on
chlorination with Cl2 in presence of diffused sunlight is
(NEET (Odisha) 2019)
(a) 2, 2-dimethylbutane
(b) neopentane
(c) n-pentane
46. Which of the following in not correct?
(d) isopentane
(JIPMER 2019)
Ans. (b)
(a) PhCH 2 Br  PhCHBrCH 3  PhCBr  CH 3 2  S N 1
Sol. Alkane which contain all equivalent hydrogen atoms
forms only monochoro derivative on halogenation. (b) R  I  R  Br  R  Cl  S N 2 
SOLID STATE 35
(c) CH2  CH  Cl  CH2  CH  CH2  Cl Alc. KOH

CH 3CH 2CH 2 Br   CH 3CH  CH 2
Propene
 PhCH 2  Cl  S N 1
In this reaction, hydrogen is eliminated for β-carbon and
(d) R  Cl  R  Br  R  I  S N 1 the halogen is lost form α-carbon atom of 1-
Ans. (a) bormoproapne. As a result, an alkene is formed as a
product. Due to the involvement of elimination of β-
Sol. In SN1 reaction, carbocation are the intermediates.
hydrogen is often called β-elimination.
Greater the stability of carbocation, more easily it is
formed and, hence faster will be the rate of reaction.
The stability of carbocation decreases in the order.
49. Identify compound X in the following sequences of
3o Carbocation  2o carbocation  1o carbocation reactions: (NEET 2020)
  
 Ph Co  CH 3 2  Ph Co HCH 3  Ph Co H 2
3 2 1
Thus, option (a) is incorrect, while trends in other

options are correct.
(a)
47. Which cannot behave as a nucleophile for SN2
reaction? (JIPMER 2019)
(a) H2 O
(b) CN
(c) NH 2 (b)

(d) I
Ans. (a)
Sol. In SN2 reaction, nucleophile transfer electron pair to
carbon of substrate, leading to the formation of transition
state.
(c)
H2O is a neutral nucleophile, while CN  , NH 2 , and I 

are negatively charged nucleophiles.
Thus, H2O cannot behave as a nucleophile for SN2 (d)
reactions.
48. CH 3  CH 2  CH 2  Br 
Alc.KOH
 Final product is
(JIPMER 2019)
(a) Propene Ans. (a)
(b) propanol Sol.
(c) cyclopropane
(d) propane-1,2-diol
Ans. (a)
Sol. When haloalkanes containing β-hydrogen atom is heated
with alc. KOH solution, then alkene is formed.
50. The correct sequence of bond enthalpy of C-X bond is

(NEET 2021)
(a) CH3  F  CH3  Cl  CH3  Br  CH3  I
(b) CH3  Cl  CH3  F  CH3  Br  CH3  I
(c) CH3  F  CH3  Cl  CH3  Br  CH3  I
(d) CH3  F  CH3  Cl  CH3  Br  CH3  I
Ans. (d)
Sol. Due to high bond length C-I has bond strength and has
less bond dissociation enthalpy. Because of short bond C
– F has high bond dissociation enthalpy so that
increasing order of bond dissociation enthalpies.
SOLID STATE 37
Exercise – 3: Achievers Section

Single Choice Questions (c) Formic acid (d) Heptane
Ans. (a)
1. Consider the following Sol. Solvolysis means SN 1
∴ the polar protic solvent is better, so, from the given
options the water is polar protic solvent. The reaction is
given below:
(I) (II) CH3 CH3
-
- Cl
CH3 C Cl CH3 C + Cl
(III) (IV) CH3 CH3

3
when attached to sp -hybridized carbon, their leaving
group ability in nucleophilic substitution reactions
CH3 CH3
decreases in the order:
(a) I > II > III > IV (b) I > II > IV > III CH3 C + OH  H2O
CH3 C OH
(c) IV> I > II > III (d) IV > III > II > I
CH3 CH3
Ans. (b)
Sol. (I) Leaving group ability depends upon stability of
anions more equivalent resonating structure more will be 4. The compound most reactive towards SN1 reaction is
the stability of conjugate ion.
(a) Me3C––CH2Cl (b) MeOCH2Cl
(II) Electron withdrawing group stabilized negative
charge.
2. Which of the following statements is correct about (c) PhCH2CH2Cl (d)

Retention / inversion of configuration during the course Ans. (b)
of a reaction? 
Sol. Me- O.. -CH -Cl  Me- O.. - C H2  ClΘ
(a)Configuration is retained if reagent attacks from the 2
same side of leaving group.
(b)Configuration is inverted if reagent attacks from the 
backside of leaving group. Me- O =CH 2

(c) No change in configuration is possible if any-bond of A carbocation is stabilized by the resonance due to the
the asymmetric centre is not cleaved during the course of presence of lone pair of electrons on the atom which is
reaction. directly attached to the cationic part of the molecule.
(d) all of these
Ans. (d) 5. Which of the following is an example of SN2 reaction?
Sol. The configuration is retained because of the attack from
the same side of the leaving group and if the leaving (a) CH 3 Br  OH   CH3 OH  Br 
group attack from the back-side then the configuration is (b)
inverted. And if there is no cleavage of bond in the
asymmetric center then there will be no change in the
configuration. Hence, the correct answer is an option (d)
3. Which is the best solvent to use for the solvolysis

reaction of t-butyl chloride?
(a) Water (b)Carbon tetrachloride
7. An SN2 reaction at an asymmetric carbon of a

 H2 O
(c) CH3CH2 OH 
 CH2  CH2 compound always gives
(d)  CH3 3 C  Br  OH   CH3 3 COH  Br (a) an enantiomer of the substrate
 
(b) a product with opposite optical rotation

Ans. (a)
(c) a mixture of diastereomers
Sol. SN 2 reaction means nucleophilic substitution bi
(d) a single stereoisomer
molecular reaction. This reaction takes place when the
Ans. (d)
leaving group is attached to the primary carbon
atom. Sol. SN 2 reaction is the nucleophilic substitution bi-
Let us look at each option: molecular reaction in which the leaving group is
substituted by a nucleophile.
Option A: CH 3 Br+OH -  CH 3 OH+Br -
This is a bi-molecular reaction which means that in
Here in this reaction, the Br is replaced by the OH  this reaction, the slowest step involves two
group which means it is a substitution reaction and molecules. Let us see the mechanism of SN 2
the attacking agent is the OH - group which is a reaction.
nucleophile. This means that this is a nucleophilic
Now, the leaving group i.e. Br is attached to a primary
carbon which means that this reaction will be
nucleophilic substitution bi-molecular reaction i.e.
SN 2 reaction.
Since this is a single choice question, we don’t have As we can see that a transition state is formed where
to look into other options. both the leaving group and the nucleophile is
Hence, option (a) is the correct one. involved. Now, in this transition state, we can see that
the nucleophile is attached from the opposite
direction to the leaving group. This means that there
6. The organic chloro compound, which shows complete will be an inversion of configuration which we can
stereochemical inversion during an SN2reaction is see in the end product.
(a) (C2H5)2CHCl (b) (CH3)3CCl Hence a single stereoisomer is produced and the
correct answer is the option (d).
(c) (CH3)2CHCl (d) CH3Cl
Ans. (d)
Sol. SN 2 reaction means nucleophilic substitution bi-
8. CH3CD2CHBrCH2CD3 on reaction with alc. KOH
molecular reaction. This reaction takes place when
the leaving group is attached to a primary carbon gives
(a) CH3CD2CH CHCD3
atom. The order for
Option A:  C 2 H 5 2 CHCl . Here, the chloride is CHCD
(b) CH3CD C
attached to a secondary carbon.
Option B:  CH 3 3 CCl . Here, the chloride is attached (c) CD3CD2 CH CHCH3
to a tertiary carbon. (d) CH 3CD CHCH2CD3

Option C:  CH 3 2 CHCl . Here, the chloride is Ans. (a)
attached to a secondary carbon. Sol.
Option D: CH3Cl . Here, the chloride is attached to a CH 3CD2CHBrCH 2CD3  alc . KOH
 CH 3CD2CH  CHCD3
primary carbon. C – D is bond is stronger than C – H bond. So, there will
So, as we can see that option (D) is the one which will be the release of HBr not DBr in the reaction.
undergo SN 2 reaction most easily and hence, it
will show complete stereochemical inversion. 9.
SOLID STATE 39
CH3
(a) (b)
Br
(c) (d)
Ans. (b)
Sol.
CH2
(a)
CH3
(b) H
Thus, (b) is the correct option.
(c) CH2 CH3

11. Debromination of meso dibromobutane will give the
(d) None of these product as:
Ans. (b) (a) n-butane (b) 2-butyne
Sol. E1 elimination reaction proceeds via carbocation (c) cis-2-butene (d) Trans-2-butene
intermediate. It is a two-step mechanism. The Ans. (d)
carbocation is formed by the removal of the existing
halide atom. In the next step, base abstracts a proton. The Sol. E 2 elimination follows an antiperiplanar structure
proton abstraction results in a double bond. It is similar
to the SN1 reaction. But it is an elimination reaction. In
the first step, bromine takes its pair of electrons and
generates a carbocation at the carbon. In the next step,
the hydrogen is abstracted from the beta-position. There
is two beta position. Thus, the abstraction of the proton
would result in two products.
The carbocation can be stabilized by the rearrangement.
The secondary positive charge is a shift to the adjacent
carbon atom to generate a most stable tertiary
carbocation. 12. 1-hexene is formed when methoxide reacts with
(a) 2-iodohexane
10. Find the major product of the following reaction: (b) 2-iodohexane
(c) 2-fluorohexane
(d) 3-fluorohexane
Ans. (c)
Sol. 2-fluorohexane on reaction with methoxide forms 1-

hexene as major product. When Fluoride is leaving
group then less substituted alkene is the major product.
13. CH3  CH 2  CH 2  CH 2  Br Thus, (c) is the correct option.


 CH 3  CH 2  O 
DMF

15. Which of the following bases would give the best yield
This reaction would follow which of the following for the substitution product when reacted with
pathway predominantly? 2-chloropropane?
(a) SN1 (b) SN2 – –
(a) CH3COO (b) OH
(c) E1 (d) E2
– –
Ans. (b) (c) NH2 (d) CH3CH2O
o
EtO- is strong nucleophile and the halide is 1. Thus, the Ans. (a)
Sol.
- - -
Sol. O H, N H 2 and CH 3 CH 2 O can act as a strong base.
conditions are excellent for S N 2 . [E2 is not possible
because no heat] Therefore E 2 product is also expected.
–
So, CH3COO will give the best yield for the substitution
14. Which of the following is the best synthesis of
compound shown? product.
O Assertion and Reason Type Questions

(A) If both assertion and reason are correct and the reason is the
correct explanation of assertion.
Br (B) If both assertion and reason are true but the reason is not the
+ correct explanation of assertion.
(a) ONa (C) If the assertion is true but the reason is false.
(D) If the reason is true but the assertion is false.
(b) 16. Assertion: Consider the following synthesis

ONa CH3ONa + PhBr
Path  I Path  II
+ CH3CH2Br   CH3OPh  CH3 Br  PhONa
(c)
ONa Path–II yields better yield of product than Path-I.
Reason: CH3ONa is stronger base than PhONa.
+ CH3CH2 OH
(d) (a) A (b) B
Ans. (c) (c) C (d) D
Sol. Williamson’s synthesis is the best method for preparing Ans. (b)
symmetrical and unsymmetrical ethers. In this method, Sol. Both the reactions that are given in the assertion are
alkyl halide is treated with suitable sodium alkoxide substitution reactions in which nucleophiles change.
prepared by the action of sodium on suitable alcohol. Bromine is a better leaving group and Hence, the
The reaction involves nucleophilic substitution SN 2 reaction gives a better yield. Path II yields better yield of
attack of an alkoxide ion on primary alkyl halide. The the product than path I. CH 3 ONa is a stronger base than
general reaction is represented as follows, PhONa , the basicity increase with the increase in the
2R'  O  Na + X  R  R'  O  R + NaX electron density of the molecule and possess a greater
negative charge due to the positive inductive effect.
SOLID STATE 41
Hence, the correct answer is an option (b) 20. Assertion: Rate of reaction is dependent only on the
concentration of nucleophile in SN1 reactions.
17. Assertion: Benzyl bromide when kept in acetone – Reason: Polar solvent favors SN1 reaction.
water, produces benzyl alcohol.
(a) A (b) B
Reason: The reaction follows SN2 mechanism.
(c) C (d) D
(a) A (b) B Ans. (d)
(c) C (d)D Sol. Rate of S N 1 reaction is dependent only on the
Ans. (a) concentration of the substrate and independent of the
Sol. The assertion that on keeping benzyl bromide in acetone concentration of the nucleophile.
water it produces benzyl alcohol is correct.
Because C6H5CH2Br hydrolyzed to produce 21. Assertion: Consider the following SN2 reactions.
C6H5CH2OH. This conversion is by SN2 mechanism. –
CH3S
Cl SCH3
(I)
and
–
(CH 3)2CHS
Cl SCH(CH 3)2
(II)
18. Assertion: In SN1 mechanism, the product with Reaction (II) occurs at a faster rate than (I)
inversion of configuration is obtained in a higher amount Reason: Anion of reaction (II) is a stronger base than
compared to the product with the retention of the anion of reaction (I).
configuration. (a) A (b) B
Reason: Front side attack of nucleophile is hindered due (c) C (d) D
to the presence of leaving group in the vicinity.
Ans. (d)
(a) A (b) B
Sol. Reaction I occur at a faster rate than reaction II because
(c) C (d) D. the anion in reaction II is a stronger base than the anion
Ans. (a) in the reaction I and the rate of the SN 2 reaction the
Sol. Initially, all the attack is from the backside in S N 1 as strong nucleophile (The species which can donate
leaving group is very close to carbocation and repels the electrons are known as nucleophiles) is used. The reason
is true but the assertion is false.
nucleophile on the front side. So, in SN1 reaction there
Hence, the correct answer is option (d)
is the formation of two products, and the major product
is the in which the new nucleophile is in the opposite
direction of the leaving group which is formed by 22. Assertion: Allyl halide (CH2=CH–CH2X) is more
inversion of configuration. reactive than CH3CH2CH2X in a SN2 reaction.
+ 2+ Reason: Allyl halide forms a resonance stabilized

19. Assertion: Heavy metal ions Ag or Pb decrease
carbocation
SN1 reactivity.
(a) A (b) B
Reason : They aid ionisation of RX. (c) C (d) D
(a) A (b) B Ans. (b)
(c) C (d) D Sol. Allylic halides exhibit faster SN2 reactivity than alkyl
Ans. (d) halide because the bimolecular transition state is
Sol. Ag + ,Pb 2+ on reaction with X - gives ppt and shift the stabilized by hyperconjugation between the orbital of
nucleophile and conjugate  bond of the allylic group.
reaction in the forward direction. Due to this ionization
of R – X takes place easily and hence the rate of S N 1  Hence, the correct answer is an option (b)
23. Assertion: SN2 reaction of CH3––Br is faster in

DMSO than in H2O. Thus, (b) is the correct option.

Reason: DMSO has greater capability to solvate
nucleophile.
(a) A (b) B
(c) C (d) D
Ans. (c)
Sol. DMSO is a polar aprotic solvent. It solvates nucleophile
very less and therefore favors SN 2
24. Assertion: Chlorination of allylic hydrogen is 26. Assertion: Ph–CO–CH2CH2OCH3 has greater
difficult than vinylic hydrogen. reactivity for E1CB than for E2 reaction.
Reason: Allyl radical is stabilised by resonance.
Reason: A poor leaving group and acidic —H
(a) A (b) B favour E1CB mechanism.
(c) C (d) D (d) (a) A (b) B
D
(c) C (d) D
Ans. (d)
Ans. (a)
Sol. Chlorination of allylic hydrogen is easy as it form allyl
Sol. The substituents are bulkier group therefore they are
radical (more – stable).
poor leaving group and due to the presence of an
electronegative oxygen atom the β-H is acidic. Greater
25. Assertion: Treatment of either enantiomer of the stability of carbanion intermediate faster will be
2-chlorobutane with ethanolic KOH results in trans-2- reaction in case of E1CB mechanism.
butene as major elimination product.
Reason: Elimination with ethanolic KOH is a 27. Assertion: The reaction of bulky base such as
bimolecular reaction. potassium tertiary butoxide [(CH3)3CO–K+] with
(a) A (b) B secondary alkyl halides gives predominantly E2
(c) C (d) D elimination product rather than SN2 substitution
Ans. (b) product.
Sol. The elimination reaction of either of the enantiomers of Reason: The transition state for the SN2 reaction is
2-chlorobutane with ethanolic KOH is an E2 elimination. more sterically hindered than for E2 elimination
The halide and the hydrogen should be anti to each other. reaction.
The mixture of enantiomers gives trans as the major
(a) A (b) B
product. Let's consider an E2 elimination of 2-
chlorbutane. The elimination of halide and hydrogen are (c) C (d) D
possible in their enantiomers. The elimination results in Ans. (a)
two products which are trans-2-butene and cis-2- Sol. In elimination reaction, bulky bases such a ter-
butene.In the two sawhorse conformations, the first butoxide or LDA (lithium Di-isopropyl Amide) will
conformation is more stable which in turn results in trans give the higher yield of less substituted alkenes. E2
product. Therefore, trans butane is a major product. The elimination reaction takes place in presence of tert-
cis -2-butene is a minor product. This is because the butoxide.
steric clash between the methyl groups reduces its
However, the SN2 reaction cannot proceed in presence
stability.
of bulky bases. SN2 proceeds via the transition state.
Reason and assertion are correct but the reason is not a The stability of the transition state is well reflected in
proper explanation of assertion. the product. The transition state of the SN2 reaction
involves the nucleophile. If the nucleophile is bulky it
will create a steric hindrance in the transition state.
This destabilizes the transition state and will form an
unstable product.
SOLID STATE 43
Therefore, bulkier bases are well suited for the Sol. When chlorobenzene is heated with chloral in the
elimination reaction but not for substitution reaction. presence of conc. H2SO4, DDT is formed by
Both assertion and reason are correct and the reason is elimination of water molecule.
a proper explanation of assertion.
Thus, (a) is the correct option.
28. Assertion: p-nitrochlorobenzene is more reactive than

m-nitrochlorobenzene towards aromatic nucleophilic
Reason: Nitro group from para and meta positions has
opposite effect in aromatic nucleophilic substitution
reaction.
(a) A (b) B
(c) C (d) D
Ans. (c)
Sol.
p-nitrochlorobenzene is more reactive than m-nitro

chlorobenzene toward aromatic nucleophillic
substitution reaction. Due to –R group at para reduce
the effect of –ve charge on ring.
29. Assertion: A dichlorobenzene is slightly more
reactive than chlorobenzene towards an aromatic
nucleophilic substitution reaction.
Reason: Chlorine has electron withdrawing effect on
aromatic ring.
(a) A (b) B
(c) C (d) D
Ans. (b)
Sol. In case of chlorine attached to benzene ring the -I
effect dominates over +R effect. So disubstituted
benzene derivative is more reactive than
chlorobenzene towards nucleophilic substitution
reaction.
30. Assertion: Chloral reacts with phenyl chloride to form

DDT.
Reason: It is an electrophilic substitution reaction
(a) A (b) B
(c) C (d) D
Ans. (c)

Alkyl and Aryl Halides Exercise 1

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Alkyl and Aryl Halides Exercise 1

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1 ALKYL AND ARYL HALIDES

Exercise – 1: Basic Objective Questions

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

(a) C H 3  N H 2  O H> F Mechanisms of substitution reactions

18. Which of the following two reactions would be

Ans. (a) (b) CH 3 -Cl+ OH  CH 3 -OH+ Cl

20. Which one of the following is most reactive towards

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

22. SN1 reaction of alkyl halides leads to

(a) SE2 (b) SN1

Sol. For S N 2 reaction,

29. Following reaction

30. The increasing order of reactivity of the following

28. Formation of free radical takes place with absorption of

31. Arrange the following halides in decreasing order of

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

less stable compared to option (A) and (B).

Option B: 35. Which of the following compounds will undergo SN1

Here, after the bromine leaves, the carbocation (a) (b)

rate of SN2 reaction.

39. Arrange the following in the deceasing order of their

37. Which of the following reactions follows SN2

(c) RCl > RBr > RF > RI

43. The order of reactivities of the following alkyl halides

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

CH3 CHClCH 2 CH3 

(c) (d) Both (a) and (b)

(a)Only substitution product is formed.

(c) (d) none of these

57. Find the major product of the following reaction

62. Find the major product of the reaction:

(b) (a) (b)

(c) (d) Both (a) and (b)

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

65. The major product obtained when this alkyl halide is

(c) (d) none of these

(c) (d) all of these

CH3 C CH2 NaNH2

73. Choose the correct major product of the reaction:

The products obtained when this substrate is

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

opposite or anti position.

77. Choose the major product of the reaction.

CH3 ONa CH3 H

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

81. What is the major product of the reaction sequence?

83. SN1 competes with E1 and SN2 competes with E2.

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

(b) 90. What will be the product in the following reaction

(c) No reaction (d) n-Propyl chloride

(d) 93. Which of the following reactions will yield 2,

95. In CH3CH2Br, % of Br is Ans. (a)

Bromo, iodo and polychloro derivatives of hydrocarbons

98. Which of the following has the highest normal boiling

Sol. Here, according to the question ethylene dichloride and (a)

1 CH 2 (Cl)  CH 2 (Cl) 

Now, for option (a)

Since, the order of electronegativity: Cl  Br  I

R 2 CuLi  R 'X  R  R ' RCu  LiX

(c) both (a) and (b)

107. Silver acetate + Br2 The main product of this reaction is

Sol. Moreover, the hydrogen atoms on nitrogen are easily

112. CH3 – CH2 – CH2 – I 