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SHEET – 1 – EAS
ELECTROPHILIC AROMATIC SUBSTITUTION
SECTION - 1
1. Oxidation of benzene with air at 723 K in the presence of V2O5 gives
(a) Malic acid (b) Maleic acid
(c) Malonic acid (d) Maleic anhydride

2. nButyl benzene on oxidation will give

(a) Benzoic acid (b) Butanoic acid
(c) 4Phenyl butanoic acid (d) Benzaldehyde

3. Which reaction sequence would be best to prepare 3chloroaniline from benzene?

(a) Chlorination, nitration, reduction.
(b) Nitration, chlorination, reduction.
(c) Nitration, reduction, chlorination.
(d) Nitration, reduction, acylation, chlorination, hydrolysis.

4. All the following groups are activating and ortho, para directors when attached to a benzene ring
except
O
(a) OCH3 (b) NHCCH3
(c) Cl (d) N(CH3)2

5. Rank the following compounds in terms of increasing reactivity towards nitration with conc. HNO3/
conc. H2SO4.
Cl NH–CH3

(1) (2) (3)

(a) (1) < (2) < (3) (b) (2) < (1) < (3)
(c) (3) < (1) < (2) (d) (3) < (2) < (1)

6. For the reaction,

Br
?
NO2
the best reactants are
(a) C6H5Br + HNO3, H2SO4 (b) C6H5Br + H2SO4, 
(c) C6H5NO2 + Br2, FeBr3 (d) C6H5NO2 + HBr

7. Consider the following statements concerning the effect of a trifluoroemethyl group, CF3, on an
electrophilic aromatic substitution.
1. The CF3 group will activate the ring.
2. The CF3 group will deactivate the ring.
3. The CF3 group will be a meta director.
4. The CF3 group will be an ortho, para director.
Which of these statements are correct?
(a) 1,3 (b) 1,4
(c) 2,3 (d) 2,4

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

9. 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.

10. Which of the following reactions is not an example of electrophilic substitution

AlCl 3
(a) C 6H 6  CH 2 CH CH 3   C6H5CH(CH3)2
AlCl3
(b) C 6H 6  CH 2 Cl 2   C 6 H5  CH2 Cl
UV light
(c) C 6H 6  3 Cl 2   C 6 H 6 Cl 6
OH

AlCl
(d) C 6H 5 OH  CO  HCl 3 

CHO
11. Toluene when treated with Br2/Fe gives pbromotoluene as the major product because the CH3
group
(a) has  I effect. (b) is meta directing.
(c) activates the ring by hyperconjugation. (d) deactivates the ring.

12. In the nitration of benzene with a mixture of conc. HNO3 and conc. H2SO4, the active species
involved is
(a) NO 3 (b) NO2
(c) NO 2 (d) NO 2

13. In the sulphonation of benzene, the active species involved is

(a) HSO 4 (b) SO3
(c) SO2 (d) SO 24

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

15. 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
16. Identify the correct order of reactivity in electrophilic substitution reactions of the following
compounds:
CH3 Cl NO2

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

(a) (I) > (II) > (III) > (IV) (b) (IV) > (III) > (II) > (I)
(c) (II) > (I) > (III) > (IV) (d) (II) > (III) > (I) > (IV)

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17. Sulphonation of benzene differs from most of the electrophilic aromatic substitution reactions. Which
one of the following statement is correct?
(a) is reversible.
(b) requires the presence of Lewis acid as catalyst.
(c) takes place with explosive violence.
(d) requires elevated temperature.
18. 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

19. Which one of the following will undergo meta substitution on mono chlorination?
(a) chloro benzene (b) phenol
(c) ethyl benzoate (d) ethoxy benzene

20. NH2, Cl, OH and CH3 groups when attached to benzene ring activate/deactivate it for
electrophilic substitution reaction. Their decreasing order of reactivity is
(a) NH2 > OH > Cl > CH3 (b) NH2 > Cl > OH > CH3
(c) NH2 > OH > CH3 > Cl (d) OH > NH2 > Cl > CH3

21. The function of anhydrous aluminium chloride in the Friedel-Craft’s reaction is

(a) to absorb water. (b) to absorb hydrochloric acid.
(c) to produce an electrophile. (d) to produce nucleophile.
22. Isopropylbenezene can be obtained by
H+ AlCl3
(a) + CH3–CH=CH2 (b) + CH3 CH2CH2Cl

CH3 AlCl3
(c) + CHCl (d) all of these
CH3
23. 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

24. To prevent the formation of carbocation in Friedal craft alkylation the best possible condition
(a) AlCl3 + high temperature (b) SnCl 4 + high temperature
(c) AlCl3 + low temperature (d) SnCl 4 + low temperature
NO2

25. To prepare from , which of the following is the correct sequence of steps?
Et
(a) Nitration followed by Friedel Crafts ethylation.
(b) Friedel Crafts ethylation followed by nitration.
(c) Friedel Crafts acylation (CH3COCl), nitration followed by Clemenson’s reduction.
(d) Friedel Crafts acylation (CH3COCl), Clemenson’s reduction followed by nitration.
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SECTION - 2
1. Using resonance contributors, answer the following. Which is a more stable carbocation
intermediate?

OH CH3

or
+ +
H NO2 H NO2

2. Give the products of the following reactions.

O CH3
OCCH3 1. Mg/Et2O
(a) + HNO3
H2SO4
? (b) 2. D2O ?
Br

OCH3 O N

AlCl3 Fe
(c) + O ? (d) + Br2 ?


O
CH3 CF3
1. NBS/
2. Mg/Et2O FeCl3
(e) 3. ethylene oxide
? (f) + Cl2 ?
4. H+

3. 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
4. What products would be obtained from the reaction of the following compounds with hot and
acidified KMnO4?

CH2CH3 CH3 CH2CH2CH2CH3

(a) (b) (c)

CH3 CHCH3
C(CH3)3
CH3
5. Propose a mechanism for each of the following reactions.

CH2CH2CHCH=CH2
CH3 +
H
(a)

H3C CH2CH3

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CH=CH2
CH3
+
(b) H

6. Show how the following compounds could be prepared from benzene.

O
CH3 OCH3
CH3C SO3H Br
(a) (b) (c)
CH2CH(CH3)2
CH3C=CH2 NO2

7. Determine the major product for each of the following reactions.

OH
CO2H
Br2 in
(a) H 2O
?

Anhydrous
(b) + AlCl3
O ?

CH3
O Cl2/Fe
(c) ?
N
H
OEt
(d)
Conc. HNO3 CH2O
? ?
HCl
ZnCl2

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

9. PhNH2 reacts with Br2 in H2O to give more than 90% yield of 2,4,6tribromoaniline, while PhNMe2 is
mononitrated at the meta position with the more powerfully electrophilic reagent HNO3/H2SO4.
Explain.

10. Explain the following percentages of meta 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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ANSWER KEY
SHEET – 1 – EAS
ELECTROPHILIC AROMATIC SUBSTITUTION

SECTION-1
1. (d) 2. (a) 3. (b) 4. (c) 5. (d)

6. (a) 7. (c) 8. (c) 9. (c) 10. (c)

11. (c) 12. (d) 13. (b) 14. (a) 15. (b)

16. (c) 17. (a) 18. (b) 19. (c) 20. (c)

21. (c) 22. (d) 23. (a) 24. (d) 25. (c)

SECTION-2
OH

1.  is the most stable Intermediate.

H NO2


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.

OCOCH3 OCOCH3 CH3 CH3

NO2 (1) Mg/Et 2O
2. (a) + (b) (2) D2O
Br D
NO2
(Major) (Minor)

OCH3 OCH3
CO(CH2)2COOH N N
(c) + (d) Br
+
C=O (Minor)
CH2CH2COOH (Minor) Br
(Major)
(Major)

CH2CH2CH2OH CF3
(e) (f)
Cl

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Page 7 of 8
O
3. (a) Br O C (b) CH2 O Br

O O NO2
(c) CH3 C COCH3 (d) Br
Br OCH3

COOH COOH COOH

4. (a) (b) (c)

COOH COOH
C(CH3)3

CH3 CH3 CH3


(CH2)2CHCH=CH2 (CH2)2CHCH CH3 (CH2)2CCH2CH3
H 1, 2 hydride shift
5. (a)


H H


CH=CH2 CHCH3
H
(b)


CH=CH2 CHCH3


CH3
CH3 CH3


H
H

CH3 CH3 CH3

CH3Cl, CH3CH=CH2 1 eqv. Br2 + h alc KOH,
6. (a) AlCl3, Heat
H
Heat H3C H3C
CH CBr
H3C H3C
(4)

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Page 8 of 8
COCH3 COCH3
(CH3)2CHCH2Cl + AlCl3 CH3COCl, Conc. H2SO4
(b) Cold AlCl3 + 
(No rearrangement) SO3H
CH2CHMe2 CH2CH(CH3)2 CH2CH(CH3)2

NO2 NH2 NH2 NO2

Conc. HNO3 Sn/HCl Cl2/Fe CF3CO3H
(c)
+ conc.H2SO4

Cl Cl
 NaOCH3,

NO2 NO2
Br2/Fe

Br
OCH3 OCH3

OH
OH CH3
Br Br Cl
7. (a) (b) (c) O
N
Br H

OEt OEt

OH
(d)

NO2 NO2

8. 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.

9. The tribromoderivative forms because NH2 is a strongly activating o,porienting substituent (as is
NMe2). Recall that amines are also proton acceptors, so in strong acid they are completely
protonated. Consequently, the only species present in HNO3/H2SO4, is the conjugate acid
PhNMe2H+ and it is the species undergoing nitration. The NR2H+ group, with a full + charge, is a
deactivator that orients meta.

10. (a) Successive replacement of H’s in electronreleasing CH3 by electronegative Cl’s makes G
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.

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