ORGANIC COMPOUND CONTAINING HALOGENS

MULTIPLE CHOICE QUESTIONS

1. The best method to prepare neopentyl chloride is

(a) CH  C  CH  OH 
3 3 2
PCl5 / 

(b)  CH3 3 C  CH2  OH 

HCl / 


(c)  CH3 3 C  CH2  OH 

SOCl2 / Pyridine


(d)  CH3 3 CCH3 

Cl2 / h



Sol. (d)
CH3 CH3 CH3
PCl5 / 
H3C C CH2OH   H3C C CH2  H C C CH2 CH3
HCl, 3
or,
SOCl2 / Pyridine
CH3 CH3

CH3


Cl
 H3C C CH2 CH3

Cl

On the other hand, free radicals do not undergo

rearrangement. Hence, the best method of preparation is
through free radical chlorination.
CH3 CH3

Cl2 / h
H3C C CH3 
 H3C C CH2 Cl

CH3 CH3

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2. Identify (A) in the following reaction
CH3ONa
CH3 + CH3OH (A)
O
CH3
(a) CH3O CH3 (b)
O O OCH3
CH3
(c) CH3O CH3 (d)
HO OH OCH3

Sol. (c)
 CH3OH
CH3O CH3 CH3O  CH3 CH3O CH3
O O CH3O HO

H+
2. ? Identify the product
OH

(a) (b)
O CH3

(c) C2H5 (d) None of these

O
Sol. (b)
+
H+

OH .. +
OH O O
H

2
 O
3. CH 2  CH  CH 2  Cl aq
. KOH

 A. Which of the following is the
correct structure of the compound ‘A’?
O O
(a) CH 2  CH  CH 2  OH (b) HO  CH 2  CH  CH 2
CH 2  CH  CH 2  OH
O O
(c) CH 2  C  CH 2 (d) CH2CCH3
OH

Sol. (b)
O
CH 2  CH  CH 2  Cl

OH

4. Arrange the following compounds in the decreasing order

of reactivity with NBS
(N–bromosuccinimide).
(I)C6H5 – CH3
(II) C6H5 – CH2 – CH2 – CH3
(III)C6H5 – CH2 – CH = CH2 (IV) C6H5  CH  CH  CH 2
|
CH3

Select the correct answer from the codes given below

(a) (IV) > (III) > (I) > (II) (b) (IV) > (III) > (II) > (I)
(c) (I) > (II) > (III) > (IV) (d) (I) > (III) > (II) > (IV)
Sol. (b)
The correct order is decided by the stability of the free
radical formed as intermediate.
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5. Oxidizing agent required for these conversions are
Me COOH
Me Me
X ; Y ;
Me COOH
NO2 NO2

Me COOH
Z then X, Y, Z are.
Br Br

(a) X = KMnO4; Y = H2Cr2O7; Z = H2O2

(b) X = CrO3, Y = MnO2, Z = HNO3
(c) X = Dil HNO3 Y = Na2Cr2O7 / H2SO4; Z = alkaline
KMnO4 / H+
(d) X, Y, Z = Conc. KMnO4
Sol. (c)
Dilute HNO3 is a weak oxidising agent as compared to
KMnO4 and Na2Cr2O7. Therefore, it oxidises one methyl
group among two.

6. Which of the following combination is correctly matched?

H
|
(a) H 3 C  CH 2  C  Cl, SN2, walden inversions
|
D
H
|
(b) H 3 C  CH 2  C  Cl, SN1, only inversion
|
D
H
|
(c) C 6 H 5  C  Cl, SN1, only retension
|
CH3

4
 H
|
(d) C 6 H 5  C  Cl, SN1, only inversion
|
CH3

Sol. (a)

7. An alkyl halide with molecular formula, C6H13Br on

treatment with alcoholic KOH gave two isomeric alkenes,
A and B. Reductive ozonolysis of the mixture gave the
following compounds:
CH3COCH3, CH3CHO, CH3CH2CHO and
(CH3)2CHCHO
The alkyl halide is
(a) 2-Bromohexane
(b) 3-Bromo-2-methylpentane
(c) 2, 2-Dimethyl-1-bromobutane
(d) 2-Bromo-2, 3-dimethylbutane
Sol. (b)
Br
CH3CH2CHCHCH3 + alc. KOH  CH3–CH2–CH=C–CH3 + CH3–CH=CH–CH–CH3
CH3 CH3 CH3
Reductive ozonolysis Reductive ozonolysis
O CH3CHO + CH3–CH–CHO
CH3CH2CHO + CH3–C–CH3 CH3

8. Bottles containing C6H5I and C6H5CH2I lost their original

labels. They were labelled
A and B for testing. A and B were separately taken in test
tubes and boiled with NaOH solution. The end solution in

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 each tube was made acidic with dilute HNO3 and then some
AgNO3 solution was added. Substance B give a yellow
precipitate. Which one of the following statements is true
for this experiment?
(a) A was C6H5I
(b) A was C6H5CH2I
(c) B was C6H5I
(d) Addition of HNO3 was unnecessary
Sol. (a)

9. The major product obtained on treatment of

CH3CH2CH(F)CH3 with CH3O / CH3OH is
(a) CH3CH2CH(OCH3)CH3 (b) CH3CH=CHCH3
(c) CH3CH2CH=CH2 (d) CH3CH2CH2CH2OCH3
Sol. (c)
Hofmann product.

10. The halide, which undergoes nucleophilic substitution (by

SNAr mechanism) most readily is
(a) pMeC6H4Cl (b) pMeOC6H4Cl
(c) pClC6H4Cl (d) pO2NC6H4Cl
Sol. (d)
The reaction proceeds by carbanion formation, which can
be stabilized by electronwithdrawing groups present at

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 ortho and/or para positions. The most electron
withdrawing group amongst all is NO2.

11. Identify the set of reagents/ reaction conditions ‘X’ and ‘Y’
in the following set of transformations.
(X) (Y)
CH3CH2CH2Br  Product  CH3CHCH3
Br

(a) (X) = dilute aqueous NaOH, 20°C ; (Y) = HBr /acetic

acid, 20°C.
(b) (X) = concentrated alcoholic NaOH, 80°C ; (Y) = HBr
/acetic acid, 20°C.
(c) (X) = dilute aqueous NaOH, 20°C ; (Y) = Br2/CHCl3,
0°C.
(d) (X) = concentrated alcoholic NaOH, 80°C ; (Y) = Br2 /
CHCl3, 0°C.
Sol. (b)
The product obtained in the first reaction can be either
CH3CH2CH2OH or CH3CH=CH2, which is a result of
substitution or elimination respectively. If reaction occurs
at 20°C, substitution would dominate elimination, as
elimination is favoured only at high temperature. At 80°C,
the elimination product is predominant and the subsequent
reaction of addition of HBr to alkene at low temperature
would be greatly favoured.

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12. An unknown alkyl halide (A) reacts with alcoholic KOH to
produce a hydrocarbon (C4H8). Ozonolysis of the
hydrocarbon affords one mole of propionaldehyde and one
mole of formaldehyde. Suggest which organic structure
among the following is the correct structure of the above
alkyl halide (A)?
(a) CH3(CH2)3Br (b) CH3CH(Br)CH(Br)CH3
(c) CH3CH2CH(Br)CH3 (d) Br(CH2)4Br
Sol. (a)
C4H8 is CH3CH2CH = CH2 as it gives propionaldehyde&
formaldehyde on ozonolysis. So, CH3CH2CH = CH2 is
produced by dehydro halogenation of
CH3CH2CH2CH2Br(A)

13. Which one of the following will form benzyne as

intermediate when treated with KNH2 in liquid NH3?
(a) Cl CHO (b) Cl OCH3

(c) Cl NO2 (d) Cl COCH3

Sol. (b)
Aryl halides containing electron releasing groups like 
OCH3 form benzyne as intermediate when treated with
KNH2 in liquid NH3.

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14. H H + KI Acetone
P

CH3 Cl

‘P’ is:
(a) CH3 I (b) H H

H H CH3 I

(c) H I (d) CH3 H

CH3 H H I
Sol. (c)
SN2 reaction proceeds with complete inversion of
configuration.

15. Which of the following compound is most rapidly

hydrolyzed by SN 1 mechanism?
(a) C H Cl
6 5 (b) Cl CH  CH  CH 2 2

(c) C H  CCl
6 5 3 (d) C H CH Cl 6 5 2

Sol. (c)
(C6H5)3CCl is hydrolysed most rapidly by SN1 because
(C6H5)3C+ is most stable.

Me Me Me
OH– OH–
16. OH H II
H Cl I H OH ( Racemic mixture)
Et Et Et
B A
Steps I and II are:
(a) both SN1 (b) both SN2
(c) I SN1, II SN2 (d) I SN2, II SN1

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Sol. (c)
SN1 reaction is accompanied by racemisation while SN2
reaction is accompanied by inversion of configuration.

17. An alkyl halide (X) having molecular formula C6H13Cl

 
O
reacts with (CH3)3 CO K to form two isomeric alkenes (Y)
and (Z) of molecular formula (C6H12). Both the alkenes
give
2,3Dimethyl butane on hydrogenation. The halide (X) is
CH3 CH3
(a) CH3 CH CH CH2 Cl (b) CH3 CH2 CH2 CH CH2 CH3
Cl
CH3 CH3 CH3
(c) CH3 C CH CH3 (d) CH3 C CH2 CH2 CH3
Cl Cl

Sol. (c)
CH3 CH3
CH3 CH3
CH2 C CH CH3
CH3 C CH CH3 (major) CH3 CH3
H2/Ni
CH3 CH3 CH3CHCHCH3
Cl
2, 3 Dimethyl Butane
CH3 C CH CH3
(minor)

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18. In the following reaction,
Cl
H Ph NaI
EtO H acetone

Ph
the structure of product is
I Cl
(a) H Ph (b) H Ph
EtO H I H
Ph Ph
I Cl
(c) Ph H (d) H Ph
EtO H H I
Ph Ph
Sol. (a)
Due to neighbouring group participation of OEt group.

19. Which chloroderivative of benzene among the following

would undergo hydrolysis most readily with aqueous
NaOH to give the corresponding hydroxy derivative?
(a) C6H5Cl (b) (CH3)2N Cl

NO2 NO2 NO2

(c) O2N Cl (d) O2N Cl

NO2 O2 N

Sol. (c)
Aryl halides containing maximum number of electron
withdrawing groups at the ortho and para positions undergo
hydrolysis most readily.

11
20. Which one of the following form benzyne as intermediate
when treated with KNH2 in liquid NH3:
(a) Cl CHO (b) Cl OCH3

(c) Cl NO2 (d) Cl COCH3

Sol. (b)
Aryl halides containing electron releasing groups like 
OCH3 form benzyne as intermediate when treated with
KNH2 in liquid NH3.

CH3 Cl
21. H OH
SOCl2
H D
D CH3
Which of the following statements about the above reaction
is true?
(a) It is unimolecularnucleophilic substitution
(b) It is bimolecular nucleophilic substitution
(c) It is internal nucleophilic substitution
(d) It is unimolecular electrophilic substitution
Sol. (c)

22. End product of the following sequence of reaction is:

NBS Mg/ether CH3CN
(A) (B) H3O+
(C)

COCH3
COCH3
(a) (b)

12
 CN COOH

(c) (d)

Sol. (b)
CH3
+
Br MgBr C=NMgBr CH3C=O
Mg/ether CH3CN
H3O+

(A)

23. The product formed in the given reaction is

CH3
CH3OH
CH3 C CH2 CH3ONa
Product
O
CH3

(a) (CH3)2CCH2OCH3 (b) CH3 C CH2OH

OH OCH3

(c) (CH3)2C=CHOCH3 (d) None of these

Sol. (a)
O O OH
H3C H3C H3C
C CH2 CCH2OCH3 H–OCH3
– CCH2OCH3
H3C H3C –OCH3
H3C
OCH3

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24. The correct order of boiling point is
(a) CH I  CH Br  CH Cl  CH F
3 3 (b) CH Br  CH I  CH Cl  CH F
3 3 3 3 3 3

(c) CH F  CH Cl  CH Br  CH I
3 3 (d) CH Cl  CH F  CH I  CH Br
3 3 3 3 3 3

Sol. (a)
Larger the size of the halogen atom, higher is the B.P.

INTEGER TYPE QUESTIONS

25. Consider the following reaction,
CH3
CH3–C–CH2–Br + NaOH
CH3

Total number of possible products in this reaction is:

Sol. (4)
Two substitution and two elimination products.


( CH 3 )3 C O K  Cold alk .
26. (CH3)3CBr     (A) 

NBS
(B)  (C).
 
KMnO4

The total number of stereoisomers possible for the

compound (C) is
Sol. (2)

CH2Br CH2Br
(CH3)3COK+ NBS cold alk. *
(CH3)3CBr (CH3)2C=CH2 CH3C=CH2 CH3 C CH2
KMnO4
(A) (B) OH OH
(C)

Compound (C) has one chiral Catom. Therefore, it has

two stereoisomers.

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27. For the reaction, R – X + OH– R – OH + X–, the rate
of reaction is given as, rate
= 4.7  10–5 [R – X] [OH–] + 0.24  10–5 [RX]. What
percentage of R – X react by SN2 mechanism when [OH–] =
0.001 molar?
Sol. 1.9

28. The total number of stereoisomeric forms of C6 H 6 Cl6 known

is
Sol. 8
C H Cl has 8 stereoisomer.
6 6 6

29. Number of   bonds present in B.H.C. (Benzene hexachloride)

are
Sol 0

30. 2, 6 - Dimethylheptane on monochlorination produces…….

derivatives
Sol. 4

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