CPP FIITJEE EAS

HOME ASSIGNMENT – 1

PART – A (OBJECTIVE )
Only one option is correct :

1. Among the following, the compound that can be most readily sulphonated is
(a) benzene (b) nitrobenzene
(c) toluene (d) chlorobenzene

2. The presence of which one of the following groups on benzene nucleus activates it towards
electrophilic substitution?
(a) CN (b) CHO
(c) COOR (d) OCOR

3. Which species will undergo electrophilic substitution reaction most easily?

(a) Ph–OH (b) PhSH
(c) Ph – O– (d) Ph – S–

4. The relative reactivities of benzene, aniline, nitrobenzene and toluene are

(a) benzene > toluene > aniline > nitrobenzene
(b) nitrobenzene > aniline > toluene > benzene
(c) toluene > aniline > nitrobenzene > benzene
(d) aniline > toluene > benzene > nitrobenzene

5. Which of the following is electrophilic substitution reactions:

OH OH
Br Br
CuCl Br2
(1) C6H5N2Cl  C6H5Cl (2)
HCl HOH

Br
Cl NO2

Cl2 HNO3
(3) (4)
Fe H2SO4

Select the correct answer from the codes given below:

(a) only (1) (b) (2), (3) and (4)
(c) (1) and (3) (d) (1), (2), (3) and (4)

6. Which of the following species is expected to have maximum enthalpy in an electrophilic

aromatic substitution reaction?
H E+ H E +
H E E
+ +
+ E+ + H+

(I) (II) (III) (IV) (V)

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 (a) species (II) (b) species (III)
(c) species (IV) (d) species (V)

7. Electrophile NO 2 attacks the following aromatic species.


CCl3 NO2 NR3 O

(I) (II) (III) (IV)


In which cases NO 2 will be at meta position?
(a) (II) and (IV) (b) (I), (II) and (III)
(c) (II) and (III) only (d) (I) only

8. Which of the following aromatic compound will undergo nitration most easily?
CH3 CMe3

(a) (b)
CH2OH CN

(c) (d)

9. Which of the following is meta directing group?

(a) COOH (b) OH
(c) NH2 (d) Cl

10. Identify the correct order of reactivity in electrophilic substitution reaction of the following
compounds
NO2 Cl OH

1 2 3 4
(a) 1 > 2 > 3 > 4 (b) 4 > 1 > 2 > 3 (c) 4 > 3 > 2 > 1 (d) 4 > 1 > 3 > 2

11. When cinnamic acid ( 3- phenylpropenoic acid ) is nitrated, the incoming electrophile ( NO 2 )
goes at
(a) ortho position only (b) para position only
(c) meta position only (d) both ortho and para positions

12. Which of the following substituted benzenes would furnish three isomeric compounds when
one more substituent is introduced?
Cl Cl
Cl
(1) (2)

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 Cl Cl

(3) (4)
Cl

Cl
Select the correct answer using the codes given below:
(a) (1), (2) and (3) (b) only (1) (c) (2) and (4) (d) (1) and (3)
13. Which one of the following will undergo meta substitution on mono chlorination?
(a) chloro benzene (b) phenol
(c) ethyl benzoate (d) ethoxybenzene

14. The following groups when attached to benzene increase the electron density of the benzene.
In which case the increase in electron density is maximum?
(a) OH (b) NH2
(c) CH3 (d) X (Halogen)

15. Which of the following triad of group activates the benzene ring and directs the electrophile
to o and pposition for substitution
(a) NO2, CHO, COOH (b) OH, O, CH3
(c) OH, SO2OH, NO2 (d) NH2, CHO, SO2OH

16. A particular form of tribromobenzene (A) melts at 44°C. On nitration it forms one possible
mononitro tribromo benzene. The structure of compound (A) is
Br Br
Br
(a) (b)
Br Br
Br
Br
Br
(c) (d) Both (a) and (b)
Br

17. The order of reactivity of following compounds

CH3 CH2CH3 CH(CH3)2 C(CH3)3
(I) (II) (III) (IV)
towards electrophilic substitution will be-[where φ = C6H5]
(a) (I) > (II) > (III) > (IV) (b) (IV) > (III) > (II) > (I)
(c) (II) > (I) > (III) > (IV) (d) (III) > (II) > (I) > (IV)

18. Halogen shows overall deactivation effect for electrophilic aromatic substitution because
(a) it is meta directing.
(b) it has higher (I) inductive effect than (+R) resonance effect.
(c) it has higher (+R) resonance effect than (I) inductive effect.
(d) it is orthopara directing.

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19. How many  electron are there in the following species :

(A) 2 (B) 4 (C) 6 (D) 8

20. Number of  electrons present in naphthalene is:

(A) 2 (B) 4 (C) 10 (D) 14

21. Which order is correct for the decreasing reactivity to ring monobromination of the following
compounds:
(I) C6H5CH3 (II) C6H5COOH (III) C6H6 (IV) C6H5NO2
(A) I > II > III > IV (B) I > III > II > IV (C) II > III > IV > I (D) III > I > II > IV

22. Number of benzene derivatives of C7H7Cl is:

(A) 2 (B) 4 (C) 5 (D) 6

23. The number of benzene derivatives of the formula C7H8O is:

(A) 2 (B) 3 (C) 4 (D) 5

24. Reaction of SO3 is easier in:

(A) Benzene (B) Toluene (C) Nitrobenzene (D) chlorobenzene

25. Which of the following is the strongest o,p-directing group?

(A) OH (B) Cl (C) Br (D) C6H5

26. The highest yield of m-product is possible by the electrophilic substitution of the following:
(A) C6H5CH3 (B) C6H5CH2COOC2H5
(C) C6H5CH(COOC2H5)2 (D) C6H5C(COOC2H5)3

27. Which of the following is not an aromatic compound:

(A) (B) (C) (D)

28. Which of the following undergoes chlorination at fastest rate?

(A) (B) (C) (D)

29. Which of the following is most reactive towards sulphonation?

(A) m-Xylene (B) o-Xylene (C) Toluene (D) p-Xylene

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30. Which of the following carbocations is expected to be most stable?

(A) (B) (C) (D)

Fe
31. C 6 H 4 Cl 2  Cl 2  C 6 H 3Cl
(x) (y)
Only one isomer of ‘y’ is formed. Hence ‘x’ is
(a) o-isomer (b) m-isomer
(c) p-isomer (d) either o or pisomer

SUBJECTIVE

32. Using resonance contributors, answer the following. Which is a more stable carbocation
intermediate?
OH CH3

or
+ +
H NO2 H NO2

33. Which is a more stable carbanion intermediate?

NO2 NO2

or Cl

HO Cl OH

34. A phenyl group has an electronwithdrawing inductive effect. However, each ring of the
biphenyl is more reactive than benzene towards electrophilic substitution and the chief
products are ortho and paraisomers. Show how reactivity and orientation can be accounted
for on the basis of resonance.

35. Compare the rate of nitration under similar conditions of PhOMe and PhSMe. Explain.

36. Explain the following percentages of meta product when these compounds undergo
electrophilic substitutions:
(a) ArCH3, ArCH2Cl, ArCHCl2, ArCCl3
4.4% 15.5% 33.8% 64.6%
(b) ArN Me3, ArCH2N+Me3, ArCH2CH2N+Me3
+

100% 88% 19%

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 HOME ASSIGNMENT – 2

1. p-Nitrotoluene on further nitration gives

CH3
CH3
NO2
(a) (b)

NO2 NO 2 NO 2
CH3 CH3
NO2
(c) (d)
NO2 O2N
NO2

2. Naphthalene undergoes electrophilic substitution reaction at C1 forming naphthalinium ion as

intermediate. Some of the structures of naphthalinium ion are given below. Choose the most
stable structure.
H E H E H E H E
 

(a) (b) (c) (d)

8 9 1
7 2
3. AlCl3
6
+ CH3Cl major product
3
5 10 4

In this reaction the electrophile will attack at the position.

(a) 6 or 7 (b) 1 or 2 (c) 9 or 10 (d) 5 or 8

4. In the following reaction, the major product will be

HNO3
H2SO4
(major product)
N
NO2
NO2
(a) (b) (c) (d)
N N N NO2 N
NO2

+
5. O2N + NO2
Product of this reaction by single electrophilic substitution is
NO2
(a) O2N (b) O2N NO2
NO2 O 2N
(c) O2N (d) O2N

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6. The major product expected from the monobromination of phenyl benzoate is
Br Br

(a) —COO—C6H5 (b) C6H5COO—

(c) Br— —COO—C6H5 (d) C6H5COO— —Br

7. During electophilic substitution the major product in the following reaction will be
FeCl3
+ Cl2 ?
N
H
Cl

Cl
N N
(a) (b)
H H

(c) (d) both (a) & (b)

N
Cl
8. Ring nitration of dimethyl benzene results in the formation of only one nitro dimethyl
benzene. The dimethyl benzene is:

(A) (B) (C) (D) None of these

9. If p-methoxy toluene is nitrated, the major product is:

(A) (B) (C) (D) No reaction

10. If meta-nitroaniline is chlorinated, the major product is:

(A) (B) (C) (D)

11. An aromatic compound of molecular formula C6H4Br2 was nitrated when three isomers of
formula C6H3Br2NO2 were obtained. The original compound is:
(A) o-dibromobenzene (B) m-dibromobenzene
(C) p-dibromobenzene (D) None of these

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12. Which of the following is the effective electrophile in the sulphonation of benzene?
  
(a) H S O 4 (b) H S O 3 (c) S O 3 (d) SO3

13. Among the following statements on the nitration of aromatic compounds, the false one is
(a) The rate of nitration of benzene is almost the same as that of hexadeuterobenzene.
(b) The rate of nitration of toluene is greater than that of benzene.
(c) The rate of nitration of benzene is greater than that of hexadeuterobenzene.
(d) Nitration is an electrophilic substitution reaction.

14. Which of the following will have fastest rate of reaction with Br2/FeBr3.
NO2 CH3 OCH3
(a) (b) (c) (d)

15. The conversion

CH2CH2CH3 CH2CH2CH3

Br
can be effected using
(a) Br2/CCl4 (b) Br2/OH-
(c) Br2/Fe (d) Br2/benzoyl peroxide

16. In the halogenation of aromatic nucleus, the halogen carrier, is used to generate the species
(a) Cl  (b) Cl+ (c) Cl (d) Cl

17. In the presence of iron catalyst, benzene reacts with chlorine to form
(a) chlorobenzene (b) benzene hexachloride
(c) hexachloro benzene (d) none of these

18. Phenol reacts with bromine in carbon disulphide at low temperature to give
(a) mbromophenol (b) o and pbromophenol
(c) pbromophenol (d) 2,4,6tribromophenol

19. The direct iodination of benzene is not recommended because

(a) I2 is an oxidising agent. (b) resulting C6H5I is reduced to C6H6 by HI
(c) HI is unstable (d) the ring gets deactivated

CCl3

Cl2, Fe
20. X. What is X as a main product?

CCl3 CCl3 CCl3 CCl3

Cl Cl Cl
(a) (b) (c) (d)
Cl
Cl Cl
21. The species responsible for nitration and sulphonation by concentrated nitric acid +
concentrated H2SO4 and fuming H2SO4 respectively, are
(a) NO2 and SO3 (b) NO2+ and SO3 (c) NO+ and SO2 (d) NO2 and SO2
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 CH 3COOH
22.  HOCl   A. A is

OH Cl OCOCH3 OCl

(a) (b) (c) (d)

23. The major product obtained in the reaction

O
Br2
—C—CH2— FeBr

3

is expected to be
O O
(a) Br— —C—CH2— (b) —C—CH2— —Br

O O

(c) —C—CH — (d) —C—CH2— —Br

Br
Br
24. Which of the following sequence regarding the rate of reaction is true for the electrophilic
substitution involving sulphonation?
(a) k C6 H 6  k C6 D 6  k C6T6 (b) k C 6H 6  k C 6D 6  k C6T6
(c) k C6 H 6  k C6 D 6  k C6T6 (d) k C6 H 6  k C6T6  k C 6D 6

25. Which of the following reagents and conditions convert benzene to chloro-benzene:
(A) Cl2, sunlight, heat (B) HCl, heat (C) HCl, sunlight, heat (D) Cl2, AlCl3

SUBJECTIVE

26. For each of the following compounds, indicate the ring carbon that would be mononitrated if
the compound were treated with HNO3/H2SO4.
NO2 O OCH3
NHCCH3
(a) (b) (c)
COOH
Cl
O
OH O
CCH3 OCCH3
(d) (e) (f)
Br CH3OC
COOH O

CH3 Cl OCOCH3

(g) (h) (i)

Cl CH3
NO2

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 CH3 NO2 SO3H
OH
(j) (k) (l)

27. Give the product(s) obtained from the reaction of each of the following compounds with
Br2/FeCl3.
O
(a) OC (b) CH2O

O O NO2

(c) H3C C COCH3 (d)

CH3O

HOME ASSIGNMENT – 3

1. Which of the following statement made on FriedelCrafts reaction is false?

(a) Friedel Crafts alkylation and acylation leads to new carboncarbon bond formation.
(b) Alcohol/acid combination can be used as reagent for FriedelCrafts alkylation.
(c) When benzene and nitrobenzene, both liquids, are mixed and treated with
CH3COCl/AlCl3 under proper reaction conditions, the products obtained are macetyl
nitrobenzene and acetophenone.
(d) npropylbenzene can be made in good yield from benzene using npropyl chloride and
anhydrous AlCl3 combination as reagent at low temperature.

2. The halide that will not react with benzene in the presence of anhydrous AlCl3 is
(a) CH3CHClCH3 (b) C6H5CH2Cl (c) C6H5Cl (d) CH3CH2CH2Cl

3. Which one of the following aromatic compounds fails to undergo FriedelCrafts reactions?
(a) C6H5CH3 (b) C6D6 (c) C6H5NO2 (d) C6H5Cl

4. In the Friedel-Crafts acylation, the electrophile is

(a) C 6 H 5 (b) AlCl 3 (c) CH3CO+ (d) C 6 H 5 CH 2

5. The major product obtained by the Friedel-Craft’s reaction of n-butylbromide with benzene
in the presence of anhydrous AlCl3 is
CH2CH2CH2CH3 CH3–CH2–CH–CH3

(a) (b)

CH3
CH3–C–CH3
(c) (d) none of these

6. Benzene reacts with acetyl chloride in presence of anhydrous aluminium chloride to form
(a) acetophenone (b) phenyl acetate
(c) chlorobenzene (d) benzoic acid

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7. The function of anhydrous aluminium chloride in the FriedelCrafts reaction is
(a) to absorb water. (b) to absorb hydrochloric acid.
(c) to produce an electrophile. (d) to produce nucleophile.

8. Benzene reacts with npropyl chloride in the presence of anhydrous AlCl3 to give
predominantly
(a) npropyl benzene (b) isopropyl benzene
(c) 3propyl1chloro benzene (d) no reaction

9. Which of the following is wrong?

CH3
Anhydrous
AlCl3
(a) + CH3Cl (b)

CH2CH2CH3
Anhydrous
AlCl3
+ CH3CH2CH2Cl
Room
Temperature
O
CH(CH3)2 CH3C
Anhydrous Anhydrous
AlCl3 AlCl3
(c) + CH3CH2CH2Cl Room
(d) + CH3COCl
Room
Temperature Temperature

O Anhydrous
AlCl3
10. + CH3CH2CCl X. Identify X.

O
O
C OH
(a) (b) (c) (d)
O

11. For preparing monoalkyl benzene, acylation process is preferred than direct alkylation
because
(a) In alkylation, a poisonous gas is evolved
(b) In alkylation, large amount of heat is evolved
(c) In alkylation, polyalkylated product is formed
(d) Alkylation is very costly

12. In which of the following reaction tbutylbenzene is formed?

(a) Benzene + t-butyl chloride, AlCl3 (b) Benzene + (CH3)2C=CH2 BF
3 .
HF

H SO
(c) Benzene + t-butyl alcohol 2 
4
 (d) All of these

13. Isopropylbenezene can be obtained by

AlCl3 AlCl 3
(a) + CH3–CH=CH2 (b) + CH3 CH2CH2Cl
Δ

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 CH3 AlCl3
(c) + CHCl (d) all of these
CH3

14. Product (X) of the following reaction is

SnCl4
(X).

OH

(a) (b) (c) (d)

15. An aromatic compound 'A' C7H6Cl2, gives AgCl on boiling with alcoholic AgNO3 solution,
and yields C7H7OCl on treatment with sodium hydroxide. 'A' on oxidation gives a mono
chlorobenzoic acid which affords only one mononitro derivative. The compound A is:

(A) (B) (C) (D)

16. m-Bromotoluene is prepared by:

(A) Bromination of toluene
(B) Friedel Craft's reaction of bromobenzene with CH3Cl
(C) Bromination of nitrobenzene and subsequent reduction of –NO2 group.
(D) Bromination of aceto-p-toluidine followed by hydrolysis and deamination.

17. C6H6 + A   C6H5CONH2

A in the above reaction is:
(A) NH2CONH2 (B) ClCONH2 (C) CH3CONH2 (D) CH2(Cl)CONH2

18. C6H6 CH COCl A Zn

  B
 Hg
3
AlCl3 HCl
The end product in the above sequence is:
(A) Toluene (B) Ethyl benzene (C) Both the above (D) None

19. The mixture of the following four aromatic compounds on oxidation by strong oxidising
agent gives:

, , and

(A) Mixture of C6H5CH2OH + C6H5COOH (B) Mixture of C6H5CHO + C6H5COOH

(C) Only C6H5COOH (D) None of the above

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 Br2 KMnO4
20. A      B
Compound A and B respectively are:
(A) o-Bromostyrene, benzoic acid (B) p-Bromostyrene, benzaldehyde
(C) m-Bromostyrene, benzaldehyde (D) Styrene dibromide, benzoic acid

21. The number of benzylic hydrogen atoms in ethylbenzene is:

(A) 3 (B) 5 (C) 2 (D) 7

22. Benzene on reaction with 'A' forms which on reaction with 'B' forms

'A' and 'B' are:

(A) Zn(Hg) + conc. HCl, (B) , LiAlH4

(C) , NaBH4 (D) , Zn(Hg) + conc. HCl

23. Reaction of toluene with CO and HCl in presence of AlCl3/Cu2Cl2 yields

(a) benzoyl chloride (b) p–tolualdehyde
(c) p–chlorotoluene (d) benzyl chloride

24. Which of the following structure corresponds to the product expected, when excess of C6H6
reacts with CH2Cl2 in presence of anhydrous AlCl3?
(a) Ph2CHCl (b) PhCHCl2
(c) Ph2CCl2 (d) Ph2CH2

ANSWERS

Home Assignment -1 (Objective)

Part – A
1.C 2.D 3.C 4.D 5.B 6.A 7.B

8.A 9.A 10.D 11.D 12.D 13.C 14.B

15.B 16.A 17.A 18.B 19.C 20.C 21.B

22.B 23.D 24.B 25.A 26.D 27.B 28.D

29.A 30.B 31.C

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(Subjective)

OH
32.

H  
N O
O

is the most stable Intermediate.


OH OH OH OH

 etc

H NO2 H NO2 H NO2 H NO2
Here OH stabilises adjacent carbocation by +R effect but in the other one methyl stabilizes the
adjacent carbocation only by +I effect.
NO2

33. 
is more stable carbanion because of several resonating structures.
HO Cl
   
O  O O  O O  O
NO2 N N N
..

 
HO Cl HO Cl HO Cl HO Cl


 E E
34. + E 
H H


E E E

H H H


When the attack occurs at ortho or para position; the positive charge is most delocalized in
the other benzene ring.
35. PhOMe > PhSMe. The bond from O (which uses a 2porbital) to the ring C is shorter and
stronger than the comparable bond from S (which uses a 3porbital) to the ring C.
Therefore, +R effect of –OMe group will be more than that of –SMe group.

36. (a) Successive replacement of H’s in electronreleasing CH3 by electronegative Cl’s makes
the group increasingly electronattracting and morienting.
(b) The + charge on N in +NMe3 makes the substituent electronattracting and mdirecting
by an inductive effect. Its influence wanes with increasing CH2’s between +N and Ar. With
two CH2’s, the electronreleasing effect of the alkyl group is more significant and
o,porientation dominates.
Home Assignment -2
1. A 2. A 3. C 4. B
5. B 6. D 7. A 8. C
9. B 10. B 11. B 12. D
13. C 14. D 15. C 16. B
17. A 18. B 19. B 20. B
21. B 22. B 23. B 24. A
25. D

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 Subjective

NO2 OCH3
NHCOCH3
26. (a) (b) (c)
CO2H
Cl
OH OCOCH3
COCH3
(d) (e) (f) CH3OC
Br O
CO2H
CH3 Cl OCOCH3
(g) (h) (i)
Cl CH3
NO2
SO3H
CH3 NO2
OH
(j) (k) (l)

O
27. (a) Br O C (b) CH2 O Br

O O NO2
(c) CH3 C COCH3 (d) Br
Br OCH3
Home Assignment -3

1. C 2. C 3. C 4. C
5. B 6. A 7. C 8. B
9. C 10. A 11. C 12. D
13. D 14. A 15. A 16. D
17. B 18. B 19. C 20. B
21. C 22. D 23. B 24. D

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