DPP - Daily Practice Problems

Chapter-wise Sheets

Date : L..�-----l Start Time : End Time :

C H E M I STRY (Cc2�
SYLLABUS : Haloalkanes and Haloarenes

Max. Marks : 180 Marking Scheme : + 4 for correct & (-1 ) for incorrect Time : 60 min.

INSTRUCTIONS : This Daily Practice Problem Sheet contains 45 MCQ's. For each question only one option is correct.
Darken the correct drcle/ bubble in the Response Grid provided on each page.

1. o-Methoxybromobenzene is treated with sodamide and then (a) freon (b) DDT
with ammonia. The product formed is (c) gammexene (d) hexachloroethane
(a) o-Methoxyaniline (b) Aniline 5. Which among MeX, RCH2X, �CHX and �ex is most
(c) Methoxybenzene (d) m-Methoxyaniline reactive towards SN2 reaction?
Gem-dibromide is (a) MeX (b) RC�X
(c) �CHX (d) �ex
2.
(a) CH3CH(Br)CHz(Br) (b) CH3CBrzCH3
6. In the preparation ofchlorobenzene from aniline, the most
(c) CHz(Br)CHzCHz (d) CHzBrCHzBr suitable reagent is
3. Arrange the following compounds in order of increasing (a) Chlorine in the presence ofultraviolet light
dipole moment : (b) Chlorine in the presence ofAICI3
Toluene (I) (c) Nitrous acid followed by heating with Cu2Cl2
m-dicblorobenzene (II) (d) HCI and Cu2Cl2
o-dichlorobenzene (Ill)
p-dichlorobenzene (IV)
7. On sulpbonation ofC6H5Cl
(a) I < IV<ll<ID (b) IV<I<ll<ID (a) m-Chlorobenzenesulphonic acid is formed
(c) IV<I<IIl<Il (d) IV<fi<I<ID (b) Benzenesulphonic acid is formed
4. The compound formed on beating chlorobenzene with (c) o-Chlorobenzenesulphonic acid is formed
chIoral in the presence of concentrated sulphuric acid, is (d) o- andp-Chlorobenzenesulphonicacid is formed

RESPO'iSE 1 . ®®®@ 2. ®®®@ 3. ®®®@ 4. ®®®@ 5. ®®®@

GRID 6. ®®®@ 7. ®®®@
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lc-� �---- DPP/ CC24
Compound (A), C8�Br, gives a white precipitate when
I I
8. (b) CH3-CH -CH3 +OH-------+ CH3 - CH -CH3
warmed with alcoholic AgN03. Oxidation of (A) gives an
acid (B), C8H604. (B) easily forms anhydride on heating. Br OH
(c) CH3CH20H -H20 CH2 CH2
Identify the compound (A).
CH2Br o: C2H 5
=

(d) (CH3)3C - Br+ OH- ----(-+ CH3)JCOH + Br-

Y
15. What would be the product formed when
(a) (b) I 0 l-bromo-3-chlorocyclobutane reacts with two equivalents
Br ofmetallic sodium in ether?

QB
CH3
r
(a)
Bp (b)
D'
D I2J
(c)
(c) (d)
CH3 16. Chlorination of toluene in the presence of light and heat
9. The reaction of C6H5N�Cl- with CuCl gives followed by treatment with aqueous NaOH gives
(a) o-Cresol (b) p-Cresol
(a) C6H5Cl (b) C6H6 (c) 2,4-Dihydroxytoluene (d) Benzoic acid
(d) C6H4Cl 2 17. The starting substance for the preparation of iodoform is
(c) C6H5 -C6H5
any one ofthe following, except
10. Conant Finkelstein reaction for the preparation ofalkyl iodide
is based upon the fact that (a) CH3CH(OH)CH3 (b) CH3CH 20H
(a) Sodium iodide is soluble in methanol, while sodium (c) HCH20H (d) CH3COCH3
chloride is insoluble in methanol 18. The following reaction proceeds through the intermediate
(b) Sodium iodide is soluble in methanol, while NaCl and
NaBr are insoluble in methanol RCOOAg + Br2 ------+
RBr + C0 2 + AgBr
(c) Sodium iodide is insoluble in methanol, whileNaCl and (a) Rcoo· (b) R (c) Br· (d) AU
NaBr are soluble
•

19. The major product ofthe following reaction is :

(d) The three halogens differ considerably in their
CH3
I
electronegativity
11. Tertiary alkyl halides are practically inert to substitution by C6H5CH2 - C -CH2 -CH3 C2HsON a
0
C2H5 H
SN2 mechanism because of 1
(a) steric hindrance (b) inductive effect Br
(c) instability (d) insolubility C H3
12. Which one is most reactive towards SN l reaction ?
I
(a) C6H5CH2 - C -CH2 -CH3
(a) C6H5CH(C6H5)Br (b) C6H5CH(CH3)Br I
OC2H5
(c) C6H5C(CH3)(C6H5)Br (d) C6H5CH2 Br
13. The major product ofthe following reaction is :
(b) C6H5CH = C -CH2 -CH3.
KOH,CH30H I
CH3 CHCH2 C HCH2CH3 heat CH3
1 1
Br Br (c) C6H5CH2-C = CHCH3
(a) C�= CHC�CH=CHCH3 I
(b) C�= CHCH=CHC�CH3 CH3
(c) CH3CH=C= CHC�CH3 (d) C6H5CH2- C =CH2
(d) CH3CH=CH-CH= CHCH3 I
14. Which ofthe following is an example ofSN2 reaction? CH 2CH3
(a) CH3Br + OH- ----.+ CH30H + Br-

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DPP/ CC24 --------t c-95 1
20. The reaction : 27. Which reagent cannot be used to prepare an alkyl halide
from an alcohol ?
C2H50H +SOCI2
Pyridine
(a) HCI + ZnCI2 (b) NaCI (c) PCI5 (d) SOCI2
is known as 28. A is an optically inactive alkyl chloride which on reaction
(a) Kharasch effect (b) Williamson's synthesis with aqueous KOH gives B. B on beating with Cu at 300°C
(c) Darzen's procedure (d) Htmsdiecker reaction gives on alkene C, what areA and C
21. T fchloroform is left open in air in the presence ofsunlight, it (a) CH3CH2Cl, CH2 = CH2
gives
(a) carbon tetrachloride (b) carbonyl chloride (b) Me3 CCI, MeCH = CH.Me
(c) mustard gas (d) lewisite (c) Me3 CCI, Me2 C=CH2
22. In the following reaction sequence : (d) Me2 CH. CH2 Cl, Me2 C=CH2
KOH(aq) (i) CH3MgBr ) ill
29. CH3Br + Nu - ----+CH3 - Nu + Br- The decreasing
(ii) H20/H+
fl
order of the rate ofthe above reaction with nucleophiles
given (Nu- ) A to D is
Anhy.ZnCI2+ Conc.HCI
turbidity [Nu- =(A) Pho-, (B)Aco-, (c) Ho-, (D) CH30-J
immediately (a) A > B > C > D (b) B>D>C>A
The compound I is : (c) D > C> A > B (d) D > C> B > A
30. Which ofthe following will have a mesoisomer also?
(a) CH2 -CH-CH3
(a) 2, 3- Dichloropentane (b) 2, 3-Dichlorobutane
I I
Cl Cl (c) 2-Cblorobutane (d) 2-Hydroxypropanoic acid
Cl 31. The major product formed when 1, 1 , 1-tricbloro-propane is
I treated with aqueous potassium hydroxide is:
(c) CH - CH - CH2 - CH3 (d) CH3 - - CH3 cr (a) Propyne (b) !-Propanol
I (c) 2-Propanol (d) Propionic acid
Cl Cl
23. Mg reacts with RBr best in 32. The major product obtained in the following reaction is :

)J
Br
(a) C2H50C2H5 (b) C6H50CH3
(c) C6H5N(CH3)2 (d) Equally in all the three
24. Which chloride is leastreaclivewith the hydrolysis point ofview? c,H, t-B OK :
(a) CH3Cl (b) CHF�Cl
C6Hs
(c) (�)3CCI (d) CH2 =CH-CI
(a) (±)C6lfsCH(O'Bu)C�C6Hs
25. CH3 -CH2 - C H - CH3 obtained by chlorination of
I (b) C6H5CH = CHC6lfs
Cl (c) (+)C6H5CH(01Bu)C�C6H5
n-butane, will be (d) (-)C6H5CH(O'Bu)C�C6H5
(a) /-fonn (b) d-fonn 33. A major component ofBorsch reagent is obtained by reacting

tCr
(c) Meso form (d) Racemicmixture hydrazine hydrate with which ofthe following ?
The reaction oftoluene with CI2 in presence of FeCI3 gives Cl Cl

No, o,N No,

26.
'X' and reaction in presence of light gives 'Y'. Thus, 'X'
(a)
O (b)

¢' *
and 'Y' are:
(a) X = Benzal chloride, Y = o - Chlorotoluene Cl Cl
(b) X = m - Cblorotoluene, Y =p -Chlorotoluene
(c) X = o -and p - Chlorotoluene, NO, O,N NO,
(c) (d)
Y = Trichloromethylbenzene
(d) X= Benzyl chloride, Y = m - Chlorotoluene
N02 N02

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-------
RI-. SPO:\Sl-.
GRID
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Spacefor Rough Work
lc-oo �------ DPP/ CC24
34. Bottles containing C6H5I and C6H5C�I lost their original 40. Silver benzoate reacts with bromine to form
labels. Theywere labelled A and B for testing. A and B were COOBr

0 6
separately taken in test tubes and boiled with NaOH solution.
The end solution in each tube was made acidic with dilute (a) �)
HN03 and then someAgN03 solution was added. Substance
B gave a yellow precipitate. Which one of the following COOAg

6-s,
statements is true for this experiment ?
(a) A and C6H5CHzi (c)
(b) B and C6Hsl
(c) Addition ofHN03 was unnecessary 41. Benzene reacts with n-propyl chloride in the presence of
(d) A was C6H5I anhydrous AICI3 to give
35. Aryl fluoride may be prepared from arene diazonium chloride (a) 3 - Propyl - 1 - chlorobenzene
using : (b) n-Propylbenzene
(a) HBFi6 (b) HBF/NaN02,Cu,6 (c) No reaction
(c) Cu.F/HF (d) Cu/HF (d) Isopropylbenzene
36. The reagent(s) for the following conversion, 42. Match the columns
Br, /""...
'v"'" '- Br
� H - H Colwnn - 1 Column-11
Cl2 /UV light
is/are A. C2H6 I. Finkelstein reaction
(a) alcoholic KOH C2HsCl
(b) alcoholic KOH followed byNaNH2 B. C6H5� ll. Freemdicalsub>titution
(c) aqueous KOH followed by Na� NaN02+HCI!Cu2CI2
(d) Zn/C�OH 273 -278K
37. An organic compound A (C4H9Cl) on reaction with C6H5Cl
Na/diethyl ether gives a hydrocarbon which on C CH3Cl + Nal � ill. Swarts reaction
monochlorination gives onlyonechloro derivative, then A is CH3I+ NaCI
(a) tert-butyl chloride (b) sec-butyl chloride D. CH3 - Br + AgF � IV Sandmeyer's reaction
(c) isobutyl chloride (d) n-butyl chloride CH3F+ AgBr
Read the following statements and choose the correct (a) A- II; B - IY; C -I; D -I l l
(b) A - II; B -III; C - 1; D - IY
38.
answer
(c) A-III;B-1; C - IV; D - 11
(i) The boiling points of isomeric haloalkanes decrease
(d) A - N; B -IIl ; C - l; D - 11
with increase in branching.
43. Which of the following statements is correct?
(ii) Among isomeric dihalobenzenes the para-isomers
(a) SN 2 reactions of optically active halides are
have higher melting point than their ortho and meta­ accompanied by inversion of configuration.
isomers. (b) SN l reactions of optically active halides are
(iii) The isomeric dihalobenzene have large difference in accompanied by racemisation.
their boiIing and melting points 2
(c) Carbocation formed in SN I reaction is sp hybridized.
(iv) The isomeric dihalobenzene have nearly same boiling (d) All of the above.
point. 44. The reaction is described as
(a) (i), (ii) and (iii) are correct CH3(C�)5
'-... oH- _.,.. (CH-7)5CH3
.. C - Br � HO - C ..
(b) (i) and (iii) are correct
(c) (ii) and (iv) are correct
H ·
··�
·

x.···· H
(d) (i), (ii) and (iv) are correct CH3 CH3

39. Chloroform cannot be prepared from which ofthe following? (a) Sr;2 (b) SN 1 (c) SN2 (d) SNO
(a) CH30H (b) C2H50H 45. Which ofthe following is not used in Friedel-Crafts reaction?
(c) CHFHO (d) (CH3)2CO (a) N-Phenyl acetanilide (b) Bromobenzene
(c) Benzene (d) Chlorobenzene
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RI-.SPO:\SI-.
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 DAILY PRACTICE C H E M I STRY
PROBLEMS SOLUTIONS

1.
(d) .J:
u
B< N•NH,

(- HBr) �
6
� 0C l31
l N
H2
5.

6.
(a)

(c)
l 0 Alkyl halides (having least steric hindrance at the a­
carbon atom) are most reactive towards SN2 reaction.
+
Cl

J:M!, ;::� � �NS�•�m•�:":�;" '"' 6

Benzyne intemlediate

)::
'

NH, ":c�'
(Oiawti�ation)

Ue + UNH2 c-NH2 l U 7. (d) -Cl is p-directing.

o,

2. (b)
More stable
Gem-dihalides are those in which two halogen atoms
NH2
m-Methoxyaniline
8. (d)
o: CH,Br
7
Alc holic

1
, AgBrJ.
are attached on the same carbon atom. A
h CH3 AgN03
3. (b) In p-dicblorobenzene, the two equal dipoles are in

I():
opposite direction, hence the molecule has zero dipole Oxidation
moment. In and dichlorobenzenes, the two dipoles
o- m-

are at 60° and 120° apart respectively, and thus COOH --� �cob
according to parallelogram law of forces, the dipole
moment ofo-dichlorobenzene is much higher than that COOH �co/
ofm-isomer. Lastly, toluene with a +I group possesses Acid (B) Phthalic Anhydride
Iittle dipole moment. Thus the overall order is

¢< 0
9. (a)
acet one
10. (b) R - X + Nai
Soluble in
(CH30H, Me2CO)
Cl

6
IV R-1 + NaX ..!-
Insoluble in
Cl (CH30H, Me2CO)
Cl (where X= Cl or Br)
< I 11. (a) Due to steric hindrance tertiary alkyl halide do not react
by SN2 mechanism they react by SN l mechanism. SN2
II III mechanism is followed in case ofprimary and secondary
4. (b) DDT is prepared by heating chlorbenzene and chloral alkyl halides of

O
with concentrated sulphuric acid C�-X > C�-C�X > (�)2-CH.X > (�)3-C-X
12. (c) SN l reactions involve the formation of carbocations,
cclpJo + 2 • c• order of stability of carbocation is 3° > 2° > 1° hence

N CI
higher the stability of carbocation, more will be the

CC
reactivity ofthe parent alkyl halide. Moreover the tertiary
carbocation formed from (c) is stabilized by two phenyl
groups.

�C
J, 13. (d) CH3 - CH -CH2 -CH-CH2 -CH3
I I
Br Br

,
l
KOH, CH30H 6.
E2
l, l, l-trichloro-2 2 bis
(p-chlorophenyl) ethane CH3 -CH = CH-CH = CH2 -CH3
or (Saytzeff product)
DDT
ls-66 ...,._---- DPP/CC24
14. (a) Only 1° alkyl halides (i.e. CH3Br) tmdergo SN2 reaction. 21. (b)
15. (d) lt is an example ofintramolecular Wurtz reaction.
Cl OH
I I
P
Cl eel
H3C - C - CH,, KOH)
CH3 - C - CH-,
LJ .. LJ I I
22. (<0
� ? � 17J + NaCI (aq.)
ether
e Cl OH
Br

Br is a better leaving group than chloride. In this (C3H6CI0 Unstable

reaction alkali metal (Na) is electron donor. (I)

CH3 CC13
II
0

6 6
- 112o (I) CH3MgBr
•q N•OH � CH3 - C - CH3
(ll) 1120 I HEll
16. (d)
3�:;• (11)
CH3
ZnCl2 +HCl given turbidity
I
CH3 - C -CH3 immediately
1
OH
23. (a) Although all the three compOtmds can be used for
preparing Grignard reagents, diethyl ether is
17. (c) C�OH does not undergo iodoform reaction, all others considered as the best because it provides electron
do so. pairs to Mg of the reagent fully for coordination, in
18. (d) Mechanism of Hunsdiecker's reaction is caseofC6H50CH3 and C6H5N(CH3)2 electron pair on
Br2
0 and N are partialy delocalised over the benzene and
R- COO
+
Ag -A
-,.-
-=- -? RCOOBr �
•
RCO 0 + Br
•
hence are less available for coordination with Mg.
g Br
-

R O(C2H5)2
"-- /
Mg
/ '
)( 0(C2fls)2
•
R + RCOOBr � R-Br+
• RCOO 24. (d) CH2 • CH • C l
(Vinyl Chloride)

The halogen atom in vinyl chloride is not reactive as in

19. (b)
other alkyl halides. The non-reactivityofchlorine atom
is due to resonance stabilisation. The e.p. on Cl-atom
can participate in delocalisation (Resonance) to give
two canonical structure.
.
C\• CH •{).
.
Cfl2 .GJ: • CH2 • CH • q :
-

25. (<0 Chlorination of n-butane taken place via free radical

l CC2HH550H0Na formation i.e., Cl2 � Cl. + C(
2
CH3
C6H5 - CH =
I
C - C� - CH3 (F\ �
20. (c) Alkyl halides can be prepared by treating alcohol with
I2 s
H - C - Cl

CH
I2 s + CI - C - H

CH
SOC12. d I
CH3CH20H + SOC12 � Racemic mixture
50% d fonn + 500/o
/lonu
CH3CH2Cl + S02 + HCl cr may attack on either side and give a racemic mixture
TI1is reaction is known as Darzen's procedure. of2 chloro butane which contain 50% d form and 50%
Note : SOBr2 and SOI2 are not used in this reaction /-form.
because SOBr2 is less stable and SOI2 does not exist.
DPP/CC24 ------� S-67 1
CH3 CH3 0 Br

6 '6
Cl2 Cl ':?"
+
I
26. FeCI3
(c) � 2 elimination
I,
Cl
CH3 CH2CI CHC12

6 6 6
C12,hv C12 ,hv
� C6Hs
+ t-BuOH + Br
C6H5 '
CCI3 33. (c) The major component of Borsch reagent is 2,4-

6
Cl2,hv dinitrophenyl hydrazine which can be obtained by
reaction of2,4-dinitrochloro benzene and hydrazine
27.
28.
(b)
(c) Me3C.ct KOH
Me 3 COH
tert. alcohol
Cu/300° O,N -Q- Cl + H.NH- NH,
(A)
N02
CH3 - C = CH2 +H20

29.
CH3
I

(c) The acid character follows the order :

O,N -Q- NH- NH,

CH3COOH> C6H50H> �0> CH30H N02

The basic character will follow the order 2,4 -dinitrophenyl hydrazine
-
CH3COO-< C6H50-< OH <CH3o-
The stronger the acid, the weaker the conjugate base
fonned.
30. (b) The compound has two similar assymmetric C6H,QH
AgN03
No yellow ppt.
C-atoms. It has plane ofsymmetry and exist in meso C6RsC�I
NaOH
C6H C�ONa
5
fonn.

--:+��-
+
HN03/H
CH
3

PI"' of •ymmwy
yellow ppt.
AgN03
·

Since benzyl iodide gives yellow ppt. hence this is

compmmd B and A was phenyl iodide (C6H5l).
CH3
Meso •
2,3 dicWorobutanc 35. (a)

heat

HBF4

(Da!z.Schicmann's reaction)

BrC�- C�Br --_-HB- CHz = CHBr

Alc.KOH
36. (b) . r�

NaNl"lz
-HBr CH "" CH
)

Elimination ofHBr from CHz = CHBr requires a stronger

32. (b) Elimination reaction is highly favoured if base because here, Br acquires partial double bond
(a) Bulkier base is used character due to resonance.
(b) Higher temperature is used
Hence in given reaction biomolecular elimination
reaction provides major product.
l s -6a ...,._
______________________ DPP/CC24

fH3
H3 CH3COC'H3 + 3C�-----? CC13COCH3 + 3HCl
f
1
CH. - C - Cl + 2Na + Cl- C - CH3
Acetone 'l'richloroacetone
37. (a)
�I I 2CC13CO.CH3 + Ca(OH)2 -----?
CH3 CH3 2CHC13 + (CH3C00)2Ca
t-Butyl chloride
;;o !E Hunsdiecker reaction
� g N

fH3fH3 H3 yH3 C 6H5 Br + C0 2 + AgBr

CH3 - C - C -CH2Cl lMono
<(
CH.- C - C - CH3 CH3
I I I I �
cH3cH3 Chlorination CH3 CH3
41. (d) C6H6 +CH3CH2CH2CI Anhyd. I
C6H5 -CH-CH3
38. (d) The boiling points of isomeric haloalkanes decrease AICl3 Isopropyl benzene
with increase in branching. For example, 2-bromo-2- 42. (a) Alkyl iodides are often prepared by the reaction of
methylpropane has the lowest boiling point among alkyl chlorides/bromides with Nal in dry acetone. This
the three isomers. reaction is known as Finkelstein reaction.
R-X + Nal -----7 R - I + NaX
X=Cl,Br
NaCl orNaBr thus formed is precipitated in dry acetone.
It facilitates the forword reaction according to le
chatelier's principle. The synthesis of alkyl fluorides
Boiling points of isomeric dihalobenzenes are very is best accomplished by heating an alkyl chloride/
nearly the same. However, the para-isomers are high bromide in the presence ofa metallic fluoride such as
melting as compared to their ortho and meta-isomers. AgF, Hg2F2, CoF2 or SbF3 . The reaction is termed as
It is due to symmetry ofpara-isomers that fits in crystal Swarts reaction.
Ianice better as compared to ortho- and meta-isomers.
H3C -Br + AgF -----7 H3C -F + AgBr
�
0
Cl Cl Cl
In case of optically active alkyl hal ides, the product

0
43. (d)
CI formed as a result of�2 mechanism has the inverted
llJ llA c,
configuration as compared to the reactant. This is
Y Cl
because the nucleophile attaches itself on the side
opposite to the one where the halogen atom is present.
In case of optically active alkyl halides, SN l reactions
b.p/K 453 446 448 are accompanied by racemisation. The carbocation
m.p/K 256 249 323 formed in the slow step being sp2 hybridised is planar
oxidation (achiral).
39. (a) CH3CH 20H + Cl2 C F I 3 crr:I· 0 + 2HC1
44. (c) lnversion in configuration occurs in SN2 reactions.
Ethanol Ethanal
45.
CH3CHO + 3Cl2 -----? CC13CHO + 3HCI (a)
Ethanal Chloral
2CC13CHO + Ca(OH)2 -----?
2CHC13 + (HC00)2Ca
Chloroform Cal. formate