EXERCISE-01 CHECK YOUR GRASP

SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER)

1. The correct order of reactivity towards the electrophilic substitution of the compounds aniline (I), benzene (II)
and nitrobenzene (III) is :-
(A) III > II > I (B) II > III > I (C) I < II > III (D) I > II > III
2. Which of the following order is correct for the decreasing reactivity to ring monobromination of the following
compounds :-

CH3 COOH NO2

I II III IV
(A) I > II > III > IV (B) II > III > IV > I (C) I > III > II > IV (D) III > I > II > IV

3. Electrophile N O 2 attacks the following :

CCl3 NO2 CHO O
(A) (II) (III) (IV)


in which cases N O will attack at meta position
2

(A) II and IV (B) I, II and III (C) II and IV (D) I only

4. The strongest deactivating effect on aromatic ring is
(A) –CH 2 Cl (B) –OCH 3 (C) –CH 3 (D) –CCl 3
5. Which of the following is maximum reactive for nitration is :-

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

6. The order of decreasing rectivity towards electrophilic reagent for the following :
(a) Benzene (b) Toluene
(c) Chloro benzene (d) Anisole
(A) b > d > a > c (B) d > c > b > a (C) d > b > a > c (D) a > b > c > d
7. Increasing order of the following for electrophilic substitution reaction as –

–CH 3 –COOH

(I) (II) ( I II )
(A) I < II < III (B) III < II < I (C) II < III < I (D) I < III < II
8. Among the compounds :

CH3 OCH3 CF3

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

the order of decreasing reactivity towards electrophilic substition is :
(A) II > I > III > IV (B) III > I > II > IV (C) IV > I > II > III (D) I > II > III > IV
9. Choose the most reactive among the following compound :

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

10. The number of possible dichloronitrobenzene isomers is :

(A) 3 (B) 4 (C) 6 (D) 8
11. The major product formed on monobromination of phenylbenzoate is :

Br
(A) (B)
O O Br
O O

Br

(C) O (D)
O
O
O
Br
12. The major product formed in the reaction is :

+
—OCH3 + E
(electrophile)

(A) —OCH3 (B) E— —OCH3

—OCH3 —OCH3
(C) (D)
E E

13. The electrophilic aromatic substitution of a compound C6H5Y produces mainly a meta-disubstituted product.
Among the following which one could be the substituent Y ?
(A) —NH 2 (B) —COOH (C) —CH 3 (D) —OCH 3
14. Which of the following is an o-, p-directing but deactivating substituent in an electrophilic aromatic
substitution :
(A) —CCl 3 (B) —Cl (C) —NHCOCH 3 (D) —OCH 3
15. The major product formed in the reaction is :

OMe
AlCl 3
+ (CH3)2 CHCH2Br  

 OMe OMe

(A) (B)
CH2 CH(CH3)2 (CH3)2CHCH2

OMe OMe
(C) (D)
C(CH3)3 (CH3)3C

16. The dipole moment of chlorobenzene is 1.6 D. The expected dipole moment of meta-dichlorobenzene is:
(A) 1.6 D (B) 3.2 D (C) 1.6 2 D (D) 0.0 D
17. In the nitration of benzene with a mixture of concentrated HNO3 and concentrated H2SO4, the active species
involved is :

(A) NO 3– (B) NO 2 (C) NO 2– (D) NO 2

18. Which of the following substituted benzene derivatives would produce three isomeric products when one
more substituent is introduced ?

Cl Cl Cl Cl Cl

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

(A) I, II and III (B) I and III (C) II and IV (D) I and IV
19. In the sulphonation of benzene, the active electrophilic speices is :
(A) SO 2 (B) SO 3 (C) SO 24  (D) HSO 4
20. The Friedel-Crafts reaction of benzene with n-butyl chloride at 0°C produces :

CH3
(A) C 6 H 5 —CH 2 CH 2 CH 2 CH 3 (B) C6H5CH—CH2CH3

(C) C6H5—CH2—CH—CH3 (D) all of these

CH3

21. Sulfonation differs from most of electrophilic aromatic substitution reactions with the fact that the reaction-
(A) is reversible (B) requires Lewis acid as catalyst
(C) is explosive (D) takes place at high temperature
22. Cumene on treatment with KMnO 4 gives -

H3C COOH COOH CHO COOH

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

23. Benzene reacts with CH 3COCl in the presece of anhyd. AlCl 3 to give :
(A) C6H5CH3 (B) C6H5Cl (C) C6H5O2Cl (D) C6H5COCH3

CH3

Br2
24. 
FeBr2
 A (Major product),

then the major product A is -

CH3 CH3 CH3 CH3 CH3

Br
Br
(A) (B) (C) (D) +

Br
Br Br CH3
50% 50%

25. Arrange the following in correct activating order towards EAS -

O
+
—NHCOCH3 —O—C—CH3 —NR3 —NH2
I II III IV

(A) III < I < II < IV (B) IV < I < II < III
(C) III < II < I < IV (D) II < III < I < IV

CHE CK Y OU R G R ASP ANSWER KEY E XE R CISE -1

Qu e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans . D C B D B C B B B C D C B B D
Qu e. 16 17 18 19 20 21 22 23 24 25
Ans . A D B B A A B D A C
EXERCISE–02 BRAIN TEASERS
SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT ANSWERS)
1. Which of the following groups are m-directing :
(A) —CHO (B) —OH (C) —OCOCH 3 (D) —COOH
2. Amongst the ions the aromatic species are :

H H
H H
(A)  (B) (C) (D)


3. The following three isomeric tribromobenzenes are subjected to mononitriation, which is/are given two
isomers :
Br Br Br
Br

Br Br Br Br
Br
(I) (II) (III)
Which of these would produce three possible mononitrotribromobenzenes :
(A) II and III (B) I and II (C) II (D) III
4. In the reaction the major product formed is :
O

Br2 (1mole )
N—  Fe


O
O
Br N—
(A) N— (B)

Br
O
O

N—
(C) (D) N— Br

Br
5. The major product formed in the reaction is :

conc.H 2 SO 4
+ HNO3  

NO2
NO2

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

NO2
NO2
6. Nitrobenzene reacts with Br2 in the presence of FeBr3 to give m-bromonitrobenzene as the major product.
Which of the following provides the best reason for the formation of m-bromonitrobenzene as the major
product :
(A) The electron density at the meta position is greater than those at the ortho and para positions
(B) Aromaticity is lost in the -complexes formed by the attack of Br + at the ortho and para positioins
but not at the meta position.
(C) The -complex formed by the attack of Br+ at the meta position is the least destabilized and the most
stable among the three -complexes
(D) In the final step of regeneration of benzene ring by the loss of H + from the -complexes, the meta-
oriented -complex loses H + most readily
7. Isopropylbenzene can be prepared by :

H 2 SO 4 H 2 SO 4
(A) Benzene + CH 3 CH = CH 2   (B) Benzene + CH3—CH—CH3  
Cl

AlCl 3 AlCl 3
(C) Benzene + CH3CH—CH3   (D) Benzene + CH 3 CH 2 CH 2 Cl 


Cl
8. Which of the following characteristic does an aromatic compound exhibit :
(A) It should have (4n +2) -electrons in the ring (B) It should be planar and conjugated
(C) It should have 4n -electrons in the ring (D) It should possess high resonance energy
9. Which of the following groups are meta-directing :
(A) —NH 2 (B) —OH (C) —NO 2 (D) —CN
10. Which of the following groups are ortho-and para-directing :
(A) —OH (B) —CHO (C) —CN (D) —NHCOCH 3
11. Which of the following statements are correct :
(A) An activating group is an electron-releasing group
(B) An activating group activates all positions of the benzene ring
(C) The effect of any group–whether activating or deactivating–is the strongest at the ortho-and para-positions
in the benzene ring
(D) An activating group activates only the ortho-and para-positions in the benzene ring
12. The major products formed in the reaction of toluene with chlorine in the presence of ferric chloride are:
(A) o-chlorotoluene (B) m-chlorotoluene (C) p-chlorotoluene (D) benzyl chloride
13. Benzene can undergo :
(A) substitution (B) addition
(C) elimination (D) oxidation
14. Which of the following statements about the nitration of aromatic compounds are correct :
(A) The rate of nitration of toluene is greater than that of benzene
(B) The rate of nitration of benzene is almost the same as that of hexadeutrobenzene
(C) The rate of nitration of benzene is greater than that of hexadeutrobenzene
(D) Nitration is an electrophilic substitution reaction
15. Halogenation of benzene in presence of AlCl 3 (anhy.) is :
(A) nucleophilic substitution (B) nucleophilic addition
(C) electrophilic substitution (D) free radical substitution
16. Which of the following structures correspond to the product expected, when excess of C 6H 6 reacts with
CH 2 Cl 2 in presence of anhydrous AlCl 3 ?

C1
(A) —CH— (B) —CHCl2

Cl

(C) —C— (D) —CH2—

Cl

17. Select the incorrect statement among the following :

(A) benzene undergoes predominantly electrophilic substition reactions
(B) toluene is more easily sulphonated than benzene
(C) benzene reacts with CCl 4 in the presence of anhydrous AlCl 3 to give triphenyl methyl chloride
(D) benzene reacts with chlorine (Cl 2) in presence of light to give benzyl chloride
18. Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds:

C2H5 Cl NO2
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
19. The structure of Wheland intermediate obtained after the attack of Br + on anilinium ion is :

H Br + +
NH3 NH3
H
(A) + (B) + Br

H Br + +
NH3 NH3
H
(C) + (D) + Br
 O O
20. Conjugation of electron withdrawing groups, e.g., —CHO, —C—R, —C—OR,—CN, —NO 2 activates

nucleophilic attack in halobenzene. The order of reactivity of these groups is :

O O O
(A) —NO 2 >—C  N > —C—H > —C—R> —C—OR

O O O
(B) —C—H> —C—R> —C—OR > —C  N >—NO 2

O O O
(C) —C  N >—NO 2 > —C—H> —C—R> —C—OR

O O O
(D) —C—H>—NO 2 >—C  N > —C—OR> —C—R

BRAIN TEASER S ANSWER KEY E XE R CISE -2

Qu e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
An s . A B,C D D B C A ,C ,D A ,B,D C ,D A ,D A ,B,C A A ,B,D A ,B,D C
Qu e. 16 17 18 19 20
An s . D C ,D C B A
EXERCISE–03 MISCELLANEOUS TYPE QUESTIONS

TRUE OR FAL SE :
1. Substitution of benzene occurs through nucleophilic attack.
2. AlCl 3 (aq.) is used as catalyst in Friedel-Crafts reaction.
3. Diphenyl methane is obtained when excess benzene is treated with dichloro methane in presence of anhy-
drous AlCl 3.

4. —NH2 gives ortho-methyl aniline when treated with CH Cl in presence of AlCl (anhydrous).
3 3

5. —CCl 3 and —Cl are the meta director.

FILL IN THE BLANKS :

1. Give the structure of the electrophile formed as per the major product :

(i) FeBr 3 + Br 2  .................. (ii) HNO 3  H 2 SO 4  ..................

conc. conc.

(iii) SO 3  H 2 SO 4  .............. (iv) CH 3 Cl + AlCl 3  ..................

fu min gsulphuricacid

(v) CH3—CHCH2Cl + AlCl3 

 ..................
CH3

2. Write the structure of -complex (carbocation) in the following S E reactions :

(i) + SO3  .................. (ii) + NO2  ..................

neutral

3. Write hybridisation of carbon atoms as indicated :

d (a) ..................
(b) ..................
CH3
(c) ..................
c (d) ..................
a b

MATCH THE COLUMN

1. Match the column I with column II.
Column-I Column-II
(A) Cyclic conjugated polyenes with (p) Arenes and alkyl halides in
(4n + 2) -electrons presence of anhydrous AlCl 3
(B) Dichlorobenzene (q) Aromatic compounds
(C) Friedel crafts reaction (r) Delocalization of -electrons
(D) Meta directing group (s) Deactivates the ring towards
electrophilic substition
2. Match the column I with column II.
Column-I Column-II
(Compounds) (orientat ion of at tacki ng electroph i le)
Me

(A) (p) Meta position with respect to –NO 2

Me

NO2

(B) (q) ortho with respect to methyl group

NO2

NO2

(C) (r) only one mono substituted product

Me

NO2

(D) (s) meta with respect to –CH 3

ASSERTION & RE ASON QUESTION :

These questions contains, Statement-I (assertion) and Statement-II (reason).
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
1. Statement-I : In nitration H 2 SO 4 is used as sulphonating agent.
Because
Statement-II : Benzene has multicentre  -bonding.
2. Statement-I : C 2 H 5 is a meta-directing group.
Because
Statement-II : The groups which direct the incoming group to meta position are called meta-directing
groups.
3. Statement-I : Tropylium cation is aromatic in anture.

Because
Statement-II : The only property that determines its aromatic behavior is its planar structure.
4. Statement-I : Benzene on heating with conc. H 2 SO 4 gives benzene sulphonic acid which when heated
with superheated steam under pressure gives benzene.
Because
Statement-II : Sulphonation is a reversible process.
5. Statement-I : Chlorination of ethyl benzene with Cl 2 in prescence of heat and light nearly yield 1-chloro-
1-phenyl ethane as major product.
Because
•
Statement-II : The reaction occurs through intermediate formation of the radical C 6 H 5 C H — CH 3 .
6. Statement-I : Nitration of toluene is easier than benzene.
Because
Statement-II : The methyl group in touene is electron-releasing.
7. Statement-I : Benzene reacts with n-propyl chloride in presence of AlCl 3/ to give isopropyl benzene.
Because
Statement-II : Benzene undergoes electrophilic substitution readily.
8. Statement-I : Most o-, p -directing substitution are deactivating.
Because
Statement-II : o-, p-directors have at least one lone pair of non-bonding electrons.
9. Statement-I : Nitrobenzene does not undergo Friedel-Craft's reaction.
Because
Statement-II : Nitrogroup is a deactivating group.
10. Statement-I : The rate of nitration of benzene is less than hexa deutero benzene.
Because
Statement-II : Deuterium is an isotope of hydrogen.

COMPREHENSION BASED QUESTIONS :

Comprehension # 1
The typical reaction of benzene and other aromatic compounds are electrophilic substitution. Presence of
electron donating group activates the ring towards electrophilic substitution, while presence of electron
withdrawing group deactivates the ring towards electrophilic substitution but at the same time activates the
ring towards nucleophilic substitution. Some groups are predominantly meta-directing and all of these are
deactivating. Except halogen, most of the o-and p-directing groups are activating groups.

C 2 H 5 Cl,AlCl 3
1.  
 (A) major..

A is trisubstituted benzene. The structure of A is :

C2H5
C2H5 C2H5

(A) (B) C2H5

C2H5 H5C2

C2H5 CH2CH2CH2CH3

(C) (D)
H5C2 C2H5
 O

AlCl 3 H 2 SO 4 (i) Zn – Hg / HCl

2. + O   (A)   (B) + (C) 
(ii ) Se, 
D + E

D and E are :

(A) and

(B) and

(C) and

(D) and

3. Which of the following compound is not formed.

CH2CH3

(i ) NBS,CCl 4 , hv

(ii ) Br / FeBr
 (X)
2 3

X represents mixture of organic compounds. The mixture does not contain.

Br Br
C2H5 CH—CH3
CH—CH3
(A) (B) Br (C) (D) all of them
Br
Br
Br

Comprehension # 2
It is not always easy to predict the position of attack on multiply substituted benzene. If the benzene ring
bears different ortho/para directing group at the 1 and 4 positions, the position of further substitution
is not immediately clear. Sometimes steric effects determine the outcome. In other cases, electronic factors
determine the outcome, and further reaction will be at the position activated by the more strongly activating
group.
Some substituens are so strongly activating that no catalyst is needed, and it is often difficult to stop substitution
after mono substitution. Mild conditions are needed to restrict the reaction to mono-substitution.
 It is possible to reduce the activity such groups (by side chain reaction) so that the reaction can be stopped
after mono substitution then and again by a side chain reaction the original group is restored. Effective
use can sometimes be made of removable blocking groups on the ring.

1. Which of the following synthesis could be done in the ring step ?

OH OH OH OH
Br Br

(A) (B)
CH3 Br CH3 Br

NH2 NH2
OH OH
Br
(C) (D)
CH3 Br
2. Which of the following is the correct major product ?

CH3 CH3 O
OCH3 OCH3CH3 O
CH3–C–Cl CH3
(CH3)2CHBr CH3 AlCl3,CS2 5°C
(A) AlCl3,15–25°C (B)
H3C CH3 H3C CH3
CH3 CH3

NH2 NH2
OH OH
Br Br Br
Br2–.H2O Br
40–50°C Br2
(C) OH O (D) CS2,0°C

O Br OH Br

3. Which of the following side chain reaction/s can be used to reduce the activity of strongly activating groups
like —OH ?
(A) benzoylation (B) acetylation (C) both of the above (D) none of the above

Comprehension # 3
A third group is least likely to enter between two groups in the meta relationship. This is the result of
steric hindrance and increases in importance with the size of the groups on the ring and with the size of
the attacking species.
When a Meat-directing group is meta to an ortho-para directing group, the incoming group primarily goes
ortho th the meta directing group rather than para.

1. Chlorination of m-chloro nitro benzene gives :

NO2 NO2 NO2 NO2

Cl
(A) (B) (C) (D)
Cl Cl Cl Cl Cl
Cl
 CH3
OH 
2. E
 ......... ?

CH3
CH3 CH3
OH
OH OH
(A) (B) (C) (D) all of them
E E
E
O

HN CH3
CH 2 / CH 3 COOH
3.   ?


O O O O

HN CH3 HN CH3 HN CH3 HN

Cl Cl Cl
(A) (B) (C) (D)
Cl
CH3 CH3 Cl CH3
CH3
HNO 3
4. 
H 2 SO 4
 , unlikely to form is -
NO2
CH3
CH3 CH3 CH3
NO2 NO2
(A) (B) NO2 (C) (D)
NO2 NO2 O2N NO2 NO2

M ISCEL L AN E OU S TYP E Q U ESTION ANSWER KEY E XE R CISE -3

 Tr u e / Fals e
1. F 2. F 3. T 4. F 5. F
 F i ll i n t h e B lanks
  – 
1. (i) Br+ ; (ii) N O 2 ; (iii) SO3 ; (iv) [CH 3 — Cl — AlCl 3 ] ; (v) CH3—C—CH3
CH3

H H
+ SO3 + NO2
2. (i) (ii) 3. (a) sp2 ; (b) sp3 ; (c) sp3 ; (d) sp2

 Matc h th e C o lu mn
1. (A) q,r ; B q,r,s ; (C)  p ; (D) s 2. (A) q, r ; (B) p, r ; (C)  q, p ; (D) p
 A s s er ti o n - R eas o n Qu es ti o ns
1. D 2. D 3. C 4. A 5. A
6. A 7. B 8. D 9. A 10. D
 C o mp rehe ns i o n B as ed Qu e st i o ns
C o mp re he ns i o n # 1 : 1. (A) 2. (B) 3. (A)
C o mp re he ns i o n # 2 : 1. (C) 2. (D) 3. (C)
C o mp re he ns i o n # 3 : 1. (A) 2. (D) 3. (B) 4. (C)
EXERCISE–04 [A] CONCEPTUAL SUBJECTIVE EXERCISE

H
 Br
Br H
1. + FeBr4– + FeBr3
H Br

Why does the given step does not occur ................

2. Write resonance structures of arenium ions with :

(i) NO 2 , (ii) C H
3

3. C6H 4(NO 2)CH 3 can form different isomers. Write three isomers.
(I) ........................... (II) ............................ (IIII) .............................
4. Write the structure of the products formed in the following S E reactions :
CO2H CH3

(i) HNO 3 / H 2 SO 4 CH 3 COCl / AlCl 3

  ............. (ii)   ..............
CO2H CH3

OH Cl

(iii) Br2 / H 2 O HNO 3 / H 2 SO 4

  ................. (iv)   ..................

CH3

(v) Br2  Fe
  .................

5. Indicate the position of the electrophile in the following compounds :

Cl

CO2H
(i) H3C (ii) (iii)
HO2C
CH3
6. Indicate the compound which can be nitrated most easily : CH3

CH3 CH3 CH3

NO2
(i) (ii) (iii)

NO2 NO2
7. Indicate wrong electron-migration :

+
:O—CH :O—CH

:
:
3 :O—CH 3 3




H E H E E H
I II III

8. Indicate more stable carbocation and explain :

OCH3

::
OCH3

(i) (ii) 

E H H E
9. In case of meta- attack on aniline (where —NH 2 group is o-, p-directing) and in case of ortho-attack on
nitrobenzene, resonating structures are possible. Which of them are more stable ?

NH2 NO2
H

H E

E
(I) (II)
(meta-attack) (ortho-attack)

10. What are the major products of the following :

CH3 OH
NO2
Br2 / Fe HNO 3 / H 2 SO 4
(i)  A (ii)  B
NO2

OH

Br2 / Fe
(iii)  C
NO2
 CON CEP TUAL SU BJ ECTIVE E X ER CISE ANSWER KEY E XE R CISE -4 (A)

1. The given reaction does not occur because on addition the ring lost its aromaticity and on deprotonation of -
complex it retains the aromaticity hence substitution reaction takes place.
O– + O O– + O O– + O O– + O
N N N N
+ +
2. (i) +

+
CH3 CH3 CH3 CH3
+ +
(ii) +

CH3 CH3 CH3

NO2
3. (i) (ii) (iii)
NO2
NO2
CH3
COOH OH Cl
Br Br

4. (i) (ii) (iii) (iv)

CH3
O2N CO2H NO2
COCH3
Br CH3
Br

(v) + —Br

Cl
E

5. (i) H3C E (ii) CO2H (iii)

CH3 HO2C E
CH3
6. (i) ; because —CH 3 is an activating group hence toluene is most reactive.
7. (III)
8. (I) is more stable, due to the + M effect of —OCH 3.
9. (I)

OH
CH3 OH
Br NO2 Br
10. (i) (ii) (iii)
NO2 NO2
NO2
EXERCISE–04 [B] BRAIN STORMING SUBJECTIVE EXERCISE

1. Unlike most hydrocarbons, azulene (C10H8) is highly coloured (deep blue), although its isomer, naphthalene,
does not have significant zwitter-ionic character, azulene does.
(i) Draw a resonance structure of azulene in which five-membered ring is anionic and the seven-membered
ring cationic.

(ii) Can azulene be considered aromatic ?

2. Explain, which of these compounds is a stronger acid. :

CN CN

or or or
(i) (ii) (iii)
Ph Ph Ph Ph

3. Arrange A, B, C in increasing potential energy :

CH3 CH3 NO2

NO2
H H
+ + E + + E
+E , +E , + E
+ + H
E
A B C

4. C 6 H 5 has electron withdrawing inductive effect yet each ring of biphenyl, C 6 H 5 –C 6H 5 is more reactive
than benzene towards SE reaction and chief products are ortho and para-isomer. Show how reactivity and
orientation can be accounted for on the basis of resonance.
5. What are the major products in the following reactions :

CH3
AlCl 3 AlCl
(a) + CH3—C—CH2Br 

C (b) 3
+ CH 2 Cl 2  D
CH3 (excess)

6. Arrange the following in increasing order of electrophilic strength :

+ +
+

I II III
7. Which is more reactive towards S E and explain ?

I II I II
OH O OH OH
NO2
(i) (ii)
 O

8. What are the major products when NO 2 (nitronium) reacts with —O—C— .

9. Which of the following compounds has the greater dipole moment ?

O
C O
C

10. Explain why pyridine does not undergo Friedel-Craft's reaction ?

 BRAIN STOR MIN G SUBJ ECTIVE E X ER CISE ANSWER KEY E XE R CISE -4 (B)

1. (i) (ii) Azulene is an aromatic specie.

CN

2. (i) (ii) (iii)

Ph Ph

3. A < B < C
+ – +

4. –

CH3
—C—CH3 —CH2—
5. (a) (b)
C2H5

6. I > II > III

7. (i) (II) is more reactive, (ii) (II) is more reactive

8. O2N— —O—C—

9. In the case of the compound on the left, the three membered ring becomes aromatic when the charges are
separated. In the case of the compound on the rignt, the resonance contributor with separated charges does
not have any additional aromaticity. Thus, the resonance contributor with separated charges is more stable
and, therefore, makes a greater contribution to the hybrid for the compound on the left than for the compound
on the rignt. The compound on the left, therefore, has the greater dipole moment.

O O–
C+ O O–
C
C C+

10. The Lewis acids AlCl3 or FeCl3, used as catalyst in Friedel - Craft's reaction coordinate with nitrogen of the
pyridine through lone pair of electrons and form a complex. The +ve charge on N greatly diminishes the
reactivity towards electrophilic substitution.

+ AlCl3
N +N
–AlCl
3
complex
EXERCISE - 05 [A] JEE-[MAINS] : PREVIOUS YEAR QUESTIONS
1. Which of these will not react with acetylene - [AIEEE-2002]
(A) NaOH (B) ammonical AgNO3 (C) Na (D) HCl
2. What is the product formed when acetylene reacts with hypochlorous acid - [AIEEE-2002]
(A) CH3COCl (B) ClCH2CHO (C) Cl2CHCHO (D) ClCH2COOH
3. 1–Butene may be converted to butane by reaction with - [AIEEE-2003]
(A) Pd/H2 (B) Zn - HCl (C) Sn - HCl (D) Zn - Hg/HCl
4. On mixing a certain alkane with chlorine and irradiating it with ultraviolet light, it forms only one
monochloroalkane. This alkane could be - [AIEEE-2003]
(A) neopentane (B) propane (C) pentane (D) isopentane
5. Which one of the following is reduced with Zn-Hg/HCl to give the corresponding hydrocarbon
(A) Butan-2-one (B) Acetic acid [AIEEE-2004]
(C) Acetamide (D) Ethyl acetate
6. Which one of the following has the minimum boiling point : [AIEEE-2004]
(A) isobutane (B) 1–butyne (C) 1–butene (D) n–butane
7. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly[AIEEE-2005]
(A) 2–bromo-2–methylbutane (B) 1–bromo-2–methylbutane
(C) 1–bromo-3–methylbutane (D) 2–bromo-3–methylbutane
8. Alkyl halides react with dialkyl copper reagent to give [AIEEE-2005]
(A) alkyl copper halides (B) alkenes
(C) alkenyl halides (D) alkanes
9. Reaction of one molecule of HBr with one molecule of 1,3–butadiene at 40°C gives predominantly
(A) 1–bromo–2–butene under thermodynamically controlled conditions [AIEEE-2005]
(B) 3–bromobutene under kinetically controlled conditions
(C) 1–bromo–2–butene under kinetically controlled conditions
(D) 3–bromobutene under thermodynamically controlled conditions
10. Acid catalyzed hydration of alkenes except ethene leads to the formation of [AIEEE-2005]
(A) secondary or tertiary alcohol
(B) primary alcohol
(C) mixture of secondary and tertiary alcohols
(D) mixture of primary and secondary alcohols
11. Elimination of bromine from 2–bromobutane results in the formation of [AIEEE-2005]
(A) predominantly 2–butene (B) equimolar mixture of 1 and 2–butene
(C) predominantly 2–butyne (D) predominantly 1–butene

Me
12. Me OH

N
Et
n Bu

The alkene formed as a major product in the above elimination reaction is- [AIEEE-2006]
Me Me
(A) Me
(B) CH2=CH2 (C) (D)
13. Reaction of trans-2-phenyl-1-bromocyclo pentane on reaction with alcoholic KOH produces-
(A) 4-phenyl cyclopentene (B) 2-phenyl cyclopentene [AIEEE-2006]
(C) 1-phenyl cyclopentene (D) 3-phenyl cyclopentene
14. Phenyl magnesium bromide reacts with methanol to give- [AIEEE-2006]
(A) A mixture of anisole and Mg(OH)Br (B) A mixture of benzene and Mg(OMe)Br
(C) A mixture of toluene and Mg(OH)Br (D) A mixture of phenol and Mg(Me)Br
15. Which of the following reactions will yield, 2, 2-dibromopropane [AIEEE-2007]
(A) CH3—C CH + 2HBr  (B) CH3CH CHBr + HBr 
(C) CH CH + 2HBr  (D) CH3 — CH CH2 + HBr 
16. In the following sequence of reactions, the alkene affords the compound ‘B’ :- [AIEEE-2008]
H O
CH3CH=CHCH3 
O
 A 
3
Zn
 B. 2

The compound B is
(A) CH3CH2CHO (B) CH3COCH3 (C) CH3CH2COCH3 (D) CH3CHO
17. The hydrocarbon which can react with sodium in liquid ammonia is [AIEEE-2008]
(A) CH3CH2CH2C  CCH2CH2CH3 (B) CH3CH2C  CH
(C) CH3CH=CHCH3 (D) CH3CH2C  CCH2CH3
18. The treatment of CH3MgX with CH3C  C–H produces [AIEEE-2008]

H H
| |
(A) CH3–CH=CH2 (B) CH3C  C–CH3 (C) CH3—C=C—CH3 (D) CH4

19. The main product of the following reaction is [AIEEE-2010]

C6H5CH2CH(OH)CH(CH3)2 Conc. H2SO4 ?

H5C6CH2CH2 H5C6 H
(A) C = CH2 (B) C= C
H3C H CH(CH3)2

C6H5CH2 CH3 C6H5 CH(CH3)2

(C) C= C (D) C= C
H CH3 H H

20. One mole of a symmetrical alkene on ozonolysis gives two moles of an aldehyde having a molecular
mass of 44 u. The alkene is :- [AIEEE-2010]
(A) ethene (B) propene (C) 1-butene (D) 2-butene
21. Ozonolysis of an organic compound gives formaldehyde as one of the products. This confirms the
presence of :- [AIEEE-2011]
(A) an isopropyl group (B) an acetylenic triple bond
(C) two ethylenic double bonds (D) a vinyl group
22. Ozonolysis of an organic compound 'A' produces acetone and propionaldehyde in equimolar mixture.
Identify 'A' from the following compounds :- [AIEEE-2011]
(A) 2 - Methyl - 1- pentene (B) 1 - Pentene
(C) 2 - Pentene (D) 2 - Methyl - 2 - pentene
23. 2–Hexyne gives trans –2–Hexene on treatment with :- [AIEEE-2012]
(A) Li AlH4 (B) Pt/H2 (C) Li/NH3 (D) Pd/BaSO4
24. In the given transformation, which of the following is the most appropriate reagent ? [AIEEE-2012]

CH=CHCOCH 3 CH=CHCH2CH3
Re agent


HO HO

(A) NaBH4 (B) NH2 NH2, OH (C) Zn – Hg / HCl (D) Na, Liq.NH3

JEE-[MAIN] : PREVIOUS YEAR QUESTIONS ANSWER KEY E XE R CISE -5 [A]

Q u e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans 1 3 1 1 1 1 1 4 1 1 1 2 4 2 1
Q u e. 16 17 18 19 20 21 22 23 24
Ans 4 2 4 2 4 4 4 3 2
EXERCISE - 05 [B] JEE-[ADVANCED] : PREVIOUS YEAR QUESTIONS

1. The clorination of toluene in presence of ferric chloride gives predominantly : [IIT -86]
(A) Benzyl chloride (B) m-chlorotoluene
(C) Benzal chloride (D) o–and–p–chlorotoluene
2. Aryl halides are less stable towards nucleophillic substitution reaction as compared to alkyl halides due to-
(A) The formation of less stable carbonium ion (B) Resonance stabilization
(C) Longer carbon-halogen bond (D) The inductive effect [IIT -90]
3. The most basic compound among the following is - [IIT -90]
(A)Benzylamine (B) Aniline (C) Acetanilide (D) p-nitro aniline
4. Excess chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives :
(A) o-cresol (B) p-cresol (C) 2, 4-dihydroxytoluene (D) Benzoic acid [ I I T - 9 0 ]
5. Choose the correct statement from the ones given below for two anilium in - [IIT-93]

NH3 NH3
+

(I) (II)
(A) II is not an acceptable canonical structure because carbonium ions are less stable than ammonium ions
(B) II is not an acceptable canonical structure because it is aromatic
(C) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons
(D) II is an acceptable canonical structure
6. The major product of nitration of benzoic acid is : [IIT-93]
(A) 3–nitrobenzoic acid (B) 4–nitrobenzoic acid
(C) 2–nitrobenzoic acid (D) 2,4–dinitrobenzoic acid
7. Most stable carbonium ion is : [IIT-95]
(A) p–NO 2 –C 6 H 4 – + CH 2 (B) C 6 H 5 + CH 2
(C) p–Cl–C 6 H 4 – + CH 2 (D)p–CH 3 O–C 6 H 4 – + CH 2
8. Arrange in order of decreasing trend towards S E reactions, [IIT-95]
Chlorobenzene, Benzene, Anilinium chloride, Toluene
I II III IV
(A) I > I > III > IV (B) III > I > II > IV (C) IV > II > I > III (D) I > II > III > IV
9. Among the following statements on the nitration of arotmatic compounds, the false one is - [ I I T - 9 7 ]
(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. Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO 3 and conc. H 2SO 4. In the
nitrating mixture HNO 3 acts as a - [IIT-98]
(A) Base (B) Acid (C) Reducing agent (D) Catalyst
11. Benzyl chloride (C 6 H 5 CH 2 Cl) can be prepared from toluene by chlorination with - [IIT-98]
(A) SO 2 Cl 2 /h (B) SOCl 2 (C) PCl 5 (D) NaOCl
12. The most unlikely representation of resonance structure of p-nitrophenoxide ions is - [IIT -98]

O– + O
– – –
O + O O + O O + O
N N N N

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

:
– –
O O O O

13. The reaction of CH 3–CH=CH– –OH with HBr gives - [IIT -98]

(A) CH3–CHBrCH2 OH (B) CH3CH2CHBr OH

(C) CH3CHBrCH2 Br (D) CH3CH2CHBr Br

14. A new C–C bond is formed in - [IIT -98]

(A) Cannizzaro' reaction (B) Friedel Crafts reaction
(C) Both (A) & (B) (D) None of these
15. Amongst the following the strongest base is - [IIT-2000]
(A) C6H5NH 2 (B) p–O 2 NC 6H 4NH 2 (C) m–O 2NC 6H 4NH 2 (D) C6H 5CH 2NH 2
O
NH
Me Me
Br2
16. ? Major product in this reaction is : [IIT-2004]
Fe

O
O NH
NH Me Me
Me Me
(A) (B)

Br Br
O O
NH
NH Me Me
Me Me
(C) (D)

Br Br

NO2
SO3H NO2
NaHCO3 NaHCO3
(I) (II)
17. Gases released in reaction (I) and (II) are : [IIT-06]

OH
,
(A) CO 2 CO 2 (B) SO 2 ,NO 2 (C) SO 2 , CO 2 (D) SO 2 , NO
18. Order of boiling point for the following compounds is - [IIT -06]

OH OH OH OH
OH

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

(A) (I) < (II) < (III) < (IV) (B) (I) < (II) < (IV) < (III)
(C) (IV) < (I) < (II) < (III) (D) (II) < (I) < (III) < (IV)

19. Identify the correct order of reactivity in electrophilic substitution reaction of the following compounds
[IIT-2002]
CH3 Cl NO2

1 2 3 4
(A) 1 > 2 > 3 > 4 (B) 4 > 3 > 2 > 1 (C) 2 > 1 > 3 > 4 (D) 2 > 3 > 1 > 4

AlCl3
20. C6H 6 + (CH3)2CHCH2Cl ? [IIT 1992]


—COO— HNO 3 / H 2 SO 4
21. 
mononitration
 [IIT 1993]

H SO
22. C6H 6 + (CH3)2CH.CH2OH 
2 4
? [IIT 1994]

23. Fill in the blanks with appropriate structure of reaction products in the following transformation :
SOCl2 anlydrous Zn Hg
O—HOOC—C 6 H 4 —CH 2 —C 6 H 5   A 
AlCl 3
 B 
HCl
C [IIT 1995]
24. Predict the structures of the intermediates/products in the following reaction sequence. [IIT 1996]
OMe O
O
MeO
+ O 
(i ) AlCl 3 Zn  Hg / HCl
 A  H 3 PO 4
 B 
 

(ii )H 3 O

25. Predict the product [IIT 1997]

CCl3
Me CH3
Anlydrous Cl2
(i) Br   ? (ii)  
AlCl 3 /  Fe
+ H3C
H

26. Each of the following raction gives two products. Write the structure of the products : [IIT 1998]
Br2 ,Fe
CH3CONHC6H5  
27. Predict the product [IIT 2002]

Br2 / Fe
N— 
(1eq.)
 ?

28. Predict the product [IIT 2002]

Cl 2 ,FeCl 3 Na Hg / HCl HNO 3 / H 2 SO 4

  A   B  C
Cl

CO2H CO2H

29. Convert : [IIT 2003]

F
30. 7-bromo-1, 3, 5-cycloheptatriene exists as a ionic substance whereas 5-bromo-1, 3-cyclopentadiene does
not ionize even in the presence of Ag + ion. Explain ? [IIT 2004]

CH3

NaBr  MnO
2 3 Conc.HNO
31. (B)   (A )   (C) (D).

(brown fumes & Pungent smell) (Explosive Product intermediate)

Identify the missing compounds. Give the equation from A to B and A to C. [IIT 2005]
32. Give reason :

O
O O
:

N
:

N N
Conc.HNO 3 NO2
(a) (i) 
Conc.H SO
 +
2 4

NO2

NO2 NO2

Conc.HNO 3
(ii) 
Conc.H SO

2 4
NO2

Pd / C
(b) 
3mole of H

 is formed but not
2
33. CH3–CH=CH2 + NOCl P [IIT 2006]
Identify the adduct.
CH 3  CH  CH 2 CH 3  CH  CH 2
(A) | | (B) | |
Cl NO NO Cl

NO
| CH 2  CH 2  CH 2
CH 3  CH 2  CH
(C) | (D) | |
NO Cl
Cl
34. The number of stereoisomers obtained by bromination of trans-2-butene is [IIT 2007]
(A) 1 (B) 2 (C) 3 (D) 4

35. The number of structural isomers for C6H14 is [IIT 2007]

(A) 3 (B) 4 (C) 5 (D) 6

36. The reagent(s) for the following conversion, [IIT 2007]

?

 H H
is / are
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn / CH3OH
37. The synthesis of 3-octyne is achieved by adding a bromoalkane into a mixture of sodium amide and an alkyne.
The bromoalkane and alkyne respectively are [IIT-2010]
(A) BrCH2CH2CH2CH2CH3 and CH3CH2CCH
(B) BrCH2CH2CH3 and CH3CH2CH2CCH
(C) BrCH2CH2CH2CH2CH3 and CH3CCH
(D) BrCH2CH2CH2CH3 and CH3CH2CCH
JE E-[A DVAN CE] : PRE VIOUS YE AR QUE STIONS ANSWER KEY E XE R CISE -5 [B]

1. (D) 2. (B) 3. (A) 4.(D) 5. (C) 6. (A) 7.(D) 8. (C)

9. (C) 10. (A) 11. (A) 12. (C) 13. (B) 14. (B) 15. (D) 16. (D)
17. (A) 18. (C) 19. (A)

20. CMe3 21. —COO— —NO2

(Major)

H SO
22. C6H6 + (CH3)2CH.CH2OH 
2 4
 CMe3

—CH2—
23. , ,
COCl
O
OMe OCH3
Me CCl3

24. (A) CO2H (B) CO2H 25. (i) (ii)

Cl
O
CMe3

O
O
26. CH3—C—NH— —Br 27. N— —Br

O
O
Cl Cl
Cl
28. (A) (B) (C)
Cl Cl NO2
Cl

30.  is aromatic whereas is antiaromatic.



CH3 CH3
O2N NO2

NaBr  MnO 2 Conc.HNO 3
31. Br2   H 2 SO 4   ( NO 2 )
NO2

32. (a) (i) —NO is ortho and pera director. (ii) —NO2 is meta director.
(b) due to high resonence energy of the product.
33. A 34. A 35. C 36. B 37. D