ORGANIC Chemistry Etoos PDF

ETOOSINDIA
INDIA’S NO. 1 ONLINE COACHING
IIT-JEE ChEmistry by N.J. sir
ORGANIC chemistry
IR
.S
AROMATIC CHEMISTRY
.J
N
1
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ETOOS Education Pvt. Ltd.
Plot No. 68, Near Union Bank of India, Rajeev Gandhi Nagar, Kota, Rajasthan – 324005
Mob. No. : 9214233360
AROMATIC CHEMISTRY
Directive Influence in substituted Benzene
e– donating groups activating e– with drawing groups deactivating

1) Strong E.D.G. (O/P- directing) 1) Strong EWG. (Meta- directing)
CH3 –NO2, – C N, –SO3H,
O –, N , –NH–CH3
CH3 + +
–NF3, –NH3, CF3
–NH2 , –OH, –OCH3
2) Moderately E.D.G. (O/P- directing) 2) Moderately EWG. (Meta- directing)
O O – C – H , – C – R, – C – OR,
– O – C – CH3, – NH – C – CH3 , O O O
– O – CH = CH2, –NH – CH – CH2 – C – NH 2, – C – O – C – R,

O O O
IR
3) Weakly E.D.G. (O/P- directing) 3) Weakly EWG. (O/P- directing)
O
– R, –C , –Ph
O–
Fill in the blanks :

.S
Substitute on Ph ring o/p Meta Activating deactivating
1.
2.
.J
3.  C  CH3
||
O
4.  O  C  CH3
||
N
O
5. –SO3H
6. –CH3

7. N  O
8. –
O
9. –CH = CH–NO2
10. –NH – CH3
2
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Mob. No. : 9214233360
1. Identify the position where electrophilic 3. Compare rate of electrophilic substitution :
substitution is favourable : O O
O
CH2–NH–CH3
NH–C–CH 3 (1)
(1) CH3 (2) (a)
NH–CH2–CH3
CH3 O O
C–OCH 3
CH3
(3) (4) (b) (c)
C–O OH
O
O
NH–C–CH 3
(2)
CH3
(5) (6) (a) (b)
IR
NO2 O
C–NH–CH 3
O
O–CH=CH2
CH2–N(me)3
(c) (d)
Cl NO2 OCH3
(7) (8)
.S C–CH3
N(me)3 (3)
O
2. Identify the ring on which electrophilic (a) (b) (c) (d)

substitution is more favorable : O
O NH2 NH–C–CH3
(1) C NH
.J
O O (4)
(2) C C
(a) (b) (c)
(3) CH2 OCH3 CH3 SO 3H
N
(4) OH
O
(d) (e)
(5) O C CH3 CD3 CT3
O
C NH O
(5)
(6) (7) (a) (b) (c)
(6)
3
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Mob. No. : 9214233360
4. Diazotisation of amines R R R R
N N
NaNO2
(1) HCl diazonium chloride
Ph–N NCl–
(3) (X)
NH 2
1°
N
NaNO2 N
(2) HCl (Nitroso amine) Ph
N N OH
H CH3 CH3 N= 0 (4) Ph–N NCl –

N=N OH
2°
NO OH –
Ph–N NCl
NaNO2 A
mild acidic
(3) HCl (5)
IR
Ph–N NCl–
N N B
NH2 mild basic
CH 3 CH3
3° 6. Typical oxidation/reduction reactions :
H3PO 2 NO2
A
Sn/HCl NH2
H2O HBr/ CuBr
L (1) S nC
Mg
Br
.S HCl/CuCl
B
C Sandmeyer
l2 /HC
l
Ph Fe/HCl NH2
K KCN/CuCN
oH D
Et
CH
HBr/Cu
KS
J HBF4 E NH2
Gattermam
HCl/Cu
F
H (2) Selective reduction :
NO2 NH2
G
.J
NH4HS
Schiemann Reaction
Na2S
NO2 NO2
5. Cupling Reactions of diazonium salts :
NH2 (3) Etard Oxidation :
O
N
(X) CrO2Cl2
(1) NH–N=N–Ph CH3 C–H
N – N Coupling (CrO2Cl 2  etard reagent)
H R (4) Rosenmund Reduction :

N O O
H2
(X) C – Cl C–H
Ph–N NCl– Pd-BaSO4
(2) N – N = N–Ph
CH3
4
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Mob. No. : 9214233360
IIT-JEE ChEmistry by N.J. sir ORGANIC chemistry
DPP-01 Time: 20 Minutes
Q.1 Write only the major product in each case: CH
Cl
AlCl3 AlCl3
(a) + HC
3
 A (b) + H C
3
C
 B
CH
3
Cl
Cl
Cl
(c) (d) AlCl3
AlCl3 +  D
+  C
Cl
(e) + AlCl3
 E (f) AlCl3
+ CH2Cl 2  F
AlCl
+ CH 2Cl 2 
3
H
(g) AlCl3
+ PhCH2Cl  G (h)
IR
(excess)
Cl
AlCl
(i) AlCl3
 I (j) + Me C Cl 
3
J
O
Me Me
AlCl AlCl
(k) + Me C C Cl 
3
K (l) + Me C C Cl 
3
L
.S H O Me O
O
AlCl
(m) Cl (n) + Me C O C Me 
3
N
AlCl3
 M O O
O O
CH
AlCl3
(o) + O  O (p) + O AlCl3
 P
.J
CH
O O
(q) H
+ HNO 2  Q

Q.2. Give structure and names of the priccipal organic products expected from mononitration of
N
(a) o-nitrotoluene (b) m-dibromobenzene

(c) m-dinitrobenzene (d) o-cresol
(e) p-cresol (f) m-nitrotoluene
(g) p-xylene (p-C6H4(CH3)2)
(h) terephthalic acid (p-C6H4(COOH)2)
(i) anilinium hydrogen sulfate (C6H5NH3+HSO4–)
(j) m-cresol (m-CH3C6H4OH)
(k) p-nitroacetanilide (p-O2NC6H4NHCOCH3)
Q.3 Final product of the given reaction:

CH3
CH 2 CH 2
Br2 Mg / ether O

Fe
 (A)   (B) 
(ii) H O 
 (C)
3
(C) is:
5
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Mob. No. : 9214233360
CH3 CH3
(A) (B)
CH2OH CHOH CH2OH

CH3
CH3
(C) (D)
CH2 CH3
CH2 CH2OH
Q.4 For chlorination of benzene which of the following reagent should be used?
(A) BrCl (B) ICl (C) HOCl + H+ (D) All
Q.5 Which of the following statement is not correct regarding desulfonation?

(A) All steps are reversible
IR
(B) it exhibits kinetic isotope effect.
(C) Phenol when reacts with SO3 at low temperature o-product is formed and at high
temperature p-product is formed as mojor product.
(D) none
Q.6 Point out the wrong formulation.
(A)
.S AlCl3
C6H5─Br + (CH3─CO)2 O   Br CO CH3
CH3 CH3
CO CH3
AlCl3
(B) + CH3─COCl 
CH CH
H3C H3C
CH3 CH3
.J
CH3 CH3
AlCl3
(C) + CH3─COCl  
CO CH3
CH CH
H3C H3C
CH3 CH3
N
AlCl3
(D) C6H5─NO2 + EtCl  no reaction
6
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Mob. No. : 9214233360
DPP NO-02 Time: 15 minutes
AlCl3
AlCl3 Q.11 + CH2 = CH – Cl  
Q.1 +  
Cl
AlCl3
FeCl3 Q.12 + — Cl  
+  
Cl ZnCl2
CH2 Q.13 Strong e— with drawing groups like.

O
— NO2, — C  N, —C–OH, — SO3H give
Explain poor yield in friedel craft alkylation. Explain.
Strong e— releasing group — NH2 donot not
IR
Q.14
H or give friedel craft alkylation. Explain
Q.2 + 
BF3
OH CH3
CH3Cl/ AlCl3
H or Q.15 +   +
Q.3 + 
AlCl3
Cl
.S
AlCl3 +
Q.4 +  
AlCl3
Q.5 + CH3 – CH2 – CH2 – Cl   Write the major product for these reactions.
O
AlCl3
.J
AlCl3
Q.6 +   Q.16 + R—C–Cl  
Cl
H or O O
Q.7 +  AlCl3
AlCl3 Q.17 + CH3—C C—CH3  
O O
AlCl3
N
Q.8 +  O
 
AlCl3
Q.18 + O  
AlCl3
Q.9 + CH2 = CH – CH2 – Cl  
O
Cl
AlCl3
Q.19  
AlCl3
Q.10 + CHCl3  
OH
Q.20 1.SOCl2 / AlCl3
AlCl3 AlCl3 O 
2.Conc.H2SO4 / 

A B C
7
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Mob. No. : 9214233360
DPP NO -03 Time: 15 minutes
Q.1 Compare the rate of nitration NH—C—CH3
OCH3 Cl CH3 O HNO3
Q.7 
H2SO4
Cl CH3
(a) (b) (c) (d) HNO3 HNO3
Q.8  Q.9 
H2SO4 H2SO4
C6D6 C6T6
(e) (f)
Q.2 Q.10 Compare the rate of sulphonation:–
O Cl CH3
HNO3/H2SO4 HNO3/HClO4
A O—C E
C6H6 C6D6 C6T6
IR
N2O5
Conc.HNO3
NO2F/BF3 HNO3/A2O
F (a) (b) (c) (d) (e)
B C D OH OH
Q.3 Q.11 Convert Cl

Explain
NH2
.S NH2 (hint:– protection of para position)
HNO3 /H2SO4 OH

Q.12 Fe+2/H2O2
NO2 Zn/dust
51% CH3
NH2 NH2
.J
NO2 Br2/Fe
Q.13 A
+ +
NO2 Br2/h
B
47% 2% OH
OH Br2/CS2/5°C
NH2 O O
N
Q.14
Br
CH3—C C—CH3 OH
O Br2/H2O Br Br
Q.4
Br
HNO3 /H2SO4 H3O
(A)  (B)   (D)+(C
I2
O Q.15   (A)
HNO3
Q.5 C—NH Q.16 Compare rate of iodination of
C6H6 C6D6 C6T6
HNO3 /H2SO4 (a) (b) (c)

ICl/ AlCl3
CF3 Q.17  
HNO3 /H2SO4 Q.18 Br Cl 


Q.6  AlCl3
8
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Mob. No. : 9214233360
DPP NO-04 Time: 15 minutes
Q.1 Write mechanism of following reactins:–
(a) Gatterrnann aldehyde synthesis:– Q. Write mechanism
O
O OH O
1.HCN/HCl/ AlCl3 C—H O
 
2.H2O 1. 2 + O  
(b) Stephen Reduction O OH
SnCl2 CH = NH
  HO
HCl
O Phenolphthalein
C—H O
H2O
 2. H 
Cl 
CCl3 — C — H + 2
Cl
IR
AlCl3 CHO
(c) + CO + HCl   Cl — C — C — H
Cl
OEt Cl
AlCl3
(d) PhMgBr + H — C — OEt   (A) Cl
OEt
.S
O Claisen Rearrangement
O — CH2—CH=CH2
H3O
 Ph — C 200C
H 

OH NH2 OH
Br2 /H2O Q.3 Br2 /H2O

— CH2—CH=CH2
Q.2    
.J
SO3H SO3H Mechanism:–

NH2 (1)
CH2
SO3H Br2 /H2O O CH
O — CH2 O
Q.4   CH2
CH — CH2—CH=CH2
CH2
N
OH
SO3H Tautomer
Br2 /H2O
Q.5   OH
— CH2—CH=CH2
Q. Explain Characteristics
Cl 1. first order reaction
2. migration is intramolecular.
Cl Cl O — CH2 — CH = CH2
Cl2
 
h
Cl Cl Q.1 

Cl
Lindane /666/ C6H6Cl6 /Gammaxene /BHC
9
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O — CH2 — CH = CH2 Mechanism:–
1.
Q.2  O O
 O — C — CH3
+
CH3–C—O—AlCl3
AlCl3
O — CH2 — CH = CH = CH2   
Q.3 
O—AlCl2
 O
—
CH3—C + + Cl +
O — CH2 — CH = CH2
D D E.A.S.
Q.4 

OH OAlCl2
D
H2O
CH3
IR
O — CH2 — CH = CH2 C C
O CH3 O CH3
Q.5 O
O—C—CH3
Fries Rearrangement 1. AlCl3 / 
Q.1  
O 2. H2O
O — C — CH 3 OH O
.S
1. AlCl3 O—C—CH3
 
2. 
3.H2O 1. AlCl3 / 
C—CH3 Q.2  
2. H2O
O
.J
N
10
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Mob. No. : 9214233360
EXERCISE – I Q.9 In the reaction of p-chlorotoluene with KNH2 in
liquid NH3, the major product is :
Q.1 How many  electron are there in the following NH2
species : CH3
(o-Toluidine)
(A) 2 (B) 4 (C) 6 (D) 8 (A ) o-Toluidine (B) m-Toluidine

(C) p-Toluidine (D) p-Chloroaniline
OCH3
Q.2 Benzene is a resonance hybrid mainly of two NaNH2
Kekule structures. Hence Q.10   A, major product A and
(A) Half of the molecules correspond to one Br
structure, and half of the second structure reaction R are :
(B) At low temperatures benzene can be OCH3
separated into two structures OCH3
(C) Two structures make equal contribution to (A) (B)
resonance hybrid NH2
NH2
(D) An individual benzene molecule changes
back and forth between two structures OCH3
IR
OCH3
Q.3 Which one of the following is the most basic (C) Br (D)
compound :
(A) C6H5 – NH2 (B) C6H5 – NHCH3 NH2
(C) C6H5 – N(CH3)2 (D) C6H5N(C2H5)2
AlCl3
Q.4 Which of the following groups is divalent : Q.11 CH2CH2CH2Cl hydrocarbon (X)
(A) Benzoyl (B) Benzyl CH3
(C) Benzal
.S (D) p-Tolyl
major product X is :
Q.5 The number of benzylic hydrogen atoms in (A) CH2CH –CH3
ethylbenzene is :
(A) 3 (B) 5 (C) 2 (D) 7 CH3
CH3
Q.6 Which of the following is not an aromatic (B) C – CH3
compound :
CH3
(A) (B) (C) (D)
.J
(C) CH2CH2CH2CH3
S + O
(D) None of these
Q.7 Product obtained when benzoyl acetic acid is
heated with soda-lime is : AlCl3
O O Q.12 C6H6 + A   C6H5CONH2
C—CH2—C—OH (Benzoyl acetic acid) A in the above reaction is :
(A) NH2CONH2 (B) ClCONH2
N
(C) CH3CONH2 (D) CH2(Cl)CONH2

(A) COCH3 (B) COOH
Q.13 In the sulphonation, acetylation and formylation of
benzene the group of effective electrophiles would
(C) CH3 (D) be :
 
(A) SO 3 , CH3  O,H C O
Q.8 Benzyne intermediate is not observed in :  
OCH3 Cl (B) SO 3 , CH3  C  O,H C O
F H3C CH3 (C) SO3, CH3CHO, CO + HCl
(A) (B) (D) HSO3, CH3CO, HCO
Cl Q.14 p-Nitrotoluene on further nitration gives :
N2 CH3 CH3
(C) (D) NO2
–
COO (A) (B)
NO2
NO2 NO2
11
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Mob. No. : 9214233360
CH2OH Q.22 In a reaction of C6H5Y, the major product (>60%)
CH3 is m-isomer, so the group Y is :
NO2 NO2 (A) – COOH (B) – Cl
(C) (D)
(C) –OH (D) – NH2
NO2 O2N
Q.23 Which of the following will undergo sulphonation
Q.15 Which of the following species is expected to of fastest rate ?
have maximum enthalpy in an electrophilic
aromatic substitution reaction ?
E (A) (B) (C) (D)
H E+ H E H+ E
+ + +
+E  
+ Q.24 Aniline under acidic medium, when chlorinated,
(I) (II) (III) (IV) (V) produces :
(A) Species (II) (B) Species (III) (A) o-chloro aniline (B) m-chloro aniline
(C) Species (IV) (D) Species (V) (C) p-chloro aniline
(D) Mixture of ortho and para-chloro aniline
Q.16 For the electrophilic substitution reaction
involving nitration, which of the following Q.25 Which of the following is most reactive towards
sequence regarding the rate of reaction is true ? sulphonation ?
IR
(A) k C6H6  k C6D6  k C6T6 (A) m-Xylene (B) o-Xylene
(C) Toluene (D) p-Xylene
(B) k C 6H6  k C6D 6  k C 6 T6
(C) k C6H6  k C6D6  k C6T6 Q.26 When sulphonilic acid (p-H2NC6H4SO3H) is
treated with excess of bromine, the product is
(D) k C6H6  k C6D6  k C6T6 (A) tribromo product (B) dibromo product
(C) monobromo product (D) tetrabromo product
Q.17 For the electrophilic substitution reaction
.S
involving sulphonation, which of the following Q.27 Ring nitration of dimethyl benzene results in the
sequence regarding the rate of reaction is true ? formation of only one nitro dimethyl benzene.
(A) k C6H6  k C6D6  k C6T6 The dimethyl benzene is :
CH3
(B) k C6H6  k C6D6  k C6 T6
CH3
(C) k C6H6  k C6D6  k C6T6 (A) (B)
CH3 CH3
(D) k C 6H6  k C6D 6  k C 6 T6 CH3
.J
Q.18 Which of the following carbocations is expected (C) (D) None of these
to be most stable ?
CH3 CH3 CH3 CH3 CH3
+ H
(A) (B) (C) + Q.28 If p-methoxy toluene is nitrated, the major
+ H (D) + Y
Y product is :
H Y H Y CH3 CH3
N
Q.19 Which of the following carbocations is expected NO2

(A) (B)
to be most stable ? NO2
NO2 NO2 NO2 NO2
H OCH3 OCH3
+ +
(A) (B) + (C) Y (D) H CH2NO2
+ Y
H Y H Y
(C) (D) No reaction
Q.20 Reaction of SO3 is easier in :
(A) Benzene (B) Toluene OCH3
(C) Nitrobenzene (D) Chlorobenzene Q.29 If meta-nitroaniline is chlorinated, the major
product is :
Q.21 Which order is correct for the decreasing NH2 NH2
reactivity to ring monobromination of the
following compounds : Cl
(A) (B)
(I) C6H5CH3 (II) C6H5COOH NO2 NO2
(III) C6H6 (IV) C6H5NO2
(A) I > II > III > IV (B) I > III > II > IV Cl
(C) II > III > IV > I (D) III > I > II > IV
12
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Mob. No. : 9214233360
NH2 NH2 Q.36 m-Aminophenol on treatment with NaOH and
Cl CO2 gives which of the following as major
(C) (D) product ?
Cl NO2 NO2 COOH
H2 H2O OH
Q.30 An aromatic compound of molecular formula (A) (B)
C6H4Br2 was nitrated then three isomers of
formula C6H3Br2NO2 were obtained. The original OH COOH
compound is : H2N OH OH
(A)o-dibromobenzene (B) m-dibromobenzene
(C) (D)
(C) p-dibromobenzene (D) Both A & C
COOH COOH
Q.31 Which of the following substituted benzene NH2
derivatives would furnish only three isomers in
significant amount when one more substituent is Q.37 3
OCOCH3  ?
AlCl
Major
introduced :
Cl Br Product is :
Br Br (A) OH
(A) (B) (C) (D)
IR
Cl COCH3
Cl Cl (B) H3COC OH
CH=CH2 OCH3
(C)
Br2 KMnO4
Q.32 A 
   B CHO
(D) OH
Compound A and B respectively are :
.S
(A) o-Bromostyrene, benzoic acid COCH3
(B) p-Bromostyrene, benzaldehyde
(C) m-Bromostyrene, benzaldehyde 
O – CH2CH = CH2
(D) Styrene dibromide, benzoic acid
Q.38 R R 
 ? Product is :
Q.33 m-Bromotoluene is prepared by :
(A) Bromination of toluene OH
(B) Friedel Craft’s reaction of bromobenzene with
R R
.J
CH3Cl
(C) Bromination of nitrobenzene and subsequent (A)
replacement of –NO2 group with methyl 
group CH2CH = CH2
(D) Bromination of aceto-p-toluidine followed by OH
hydrolysis and deamination R R
(B)
N
Q.34 Which chloroderivative of benzene among the 

following would undergo-hydrolysis most readily CH2 – CH = CH2
with aq. NaOH to furnish the corresponding OH
hydroxy derivative. R R
NO2 (C)

(A) O2N Cl (B) O2N Cl CH2 – CH = CH2
NO2 (D) no reaction
(C) Me2N Cl (D) Cl EXERCISE – II

Conc. H2SO 4
Q.35 Chloral + Cl     product. The
 Q.1 Benzene reacts with n-propyl chloride in the
presence of anhydrous AlCl3 to give
product is :
predominantly :
(A) Lindane (B) DDT
(A) n-Propylbenzene (B) Isopropylbenzene
(C) Tefflon (D) Ethaneperchlorate
(C) 3-Propyl-1-chlorobenzene
(D) Cumene
13
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Mob. No. : 9214233360
Q.2 In which of the following reaction t-butylbenzene Q.9 Which of the following will undergo nitration
is formed : faster than benzene ?
(A) Benzene + iso-butyl chloride, AlCl3 NH2
BF .HF
(B) Benzene + (CH3)2C = CH2  3
H2SO4 (A) (B)
(C) Benzene + t-butyl alcohol  
AlCl3
(D) Benzene + (CH3)2C = CH2   Cl NHCOCH3
Q.3 The replacement of a hydrogen atom in benzene (C) (D)

by alkyl group can be brought about with the
following reagents :
O
(A) Alkyl chloride and AlCl 3
(B) Alkene and AlCl3 Q.10 Of the species PhSH, PhSR , PhSR and
(C) Alkanol and alkali O O
(D) Alkanol and acid O
Ph – S – ORthe meta-substituted product is
Q.4 Which of the following can be used in Friedel O
Crafts reaction ? obtained from
Cl (A) PhSR (B) PhSR
IR
O
(A) (B) CH2 = CH – Cl O O
(C) PhSR (D) Ph – S – OR
(C) CH3CH2Cl (D) CH2 = CH – CH2 – Cl
O O
Q.5 The good method for converting benzene into
Q.11 Which of the following is not an ortho-para
propyl benzene is :
directing group ?
(A) C6H6 + CH3CH2CH2Cl + Anhyd. AlCl 3 (A) CF3 (B) CCl 3
.S
(B) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and 
(C) – CH = CH – COOH (D) – N  C
then treatment with Zn/Hg/HCl
(C) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and Q.12 Which of the following statement is incorrect for
then treatment with H2Ni electrophilic substitution
(D) C6H6 + Anhyd. AlCl3 + cyclopropane (A) Ortho-and para-directing groups increase
electron density at ortho-and para-position
Q.6 The structure of the compound that gives a (B) Meta-directing group increase electron
tribromo derivative on treatment with bromine density at meta-position
water is : (C) Meta-directing groups decrease electron
.J
density at meta-position
CH3 CH3 SO3H COOH (D) Ortho-and para-directing groups decrease
OH electron density at meta-position
(A) (B) (C) (D)
Q.13 Which of the following statement is/are not true ?
OH (A) All ortho-para directing group activates the
OH OH
ring
N
Q.7 Electrophilic attack of NO 

2 at meta position is (B) All ortho-para directing groups excepting
observed in : halogens activate the ring

 (C) All meta-directing groups have -bond on the
CCl 3 NO2 NMe3 O atom directly attached to the ring
(D) All meta directing groups are deactivating
(A) (B) (C) (D)
Q.14 Amongst the following, the moderately activating
group is
Q.8 Which of the following does not gives Friedel- (A) – NHR (B) – NHCOCH3
Crafts reaction ?
 R
NH2 NO2 NMe3 (C) – O – C – R (D) – CH3
(A) (B) (C) (D)
14
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Mob. No. : 9214233360
Q.15 False statement is/are : EXERCISE – III
(A) Although benzene contains three double
bonds, normally it does not undergo addition Q.1 Write the most stable resonating structure for the
reaction cyclohexadienyl anion formed by reaction of
(B) m-chlorobromobenzene is an isomer of m- methoxide ion with o-fluoronitrobenzene.
bromochlorobenzene
(C) In benzene, carbon uses all the three p Q.2 Write the principal organic product in each of the
orbitals for hybridization following reactions :
(D) An electron donating substitutent in benzene
orients the incoming electrophilic group to the Cl
meta position NO2
(i) + C6H5CH2SK  A
Q.16 Benzoic acid may be prepared by the oxidation
of : CH3
CH2CH3 CH2OH
Cl
(A) (B) NO2
H NNH
(ii) 2 
2
B
triethylene
glycol
COCH3 OH NO2
IR
CH2CH3 CH3
(C) (D) CF2
( i ) HNO , H SO
(iii) 3
   2
 
4
C
Q.17 Which of the following reactions of benzene ( ii ) NaOCH3 ,CH3 OH
proves the presence of three carbon-carbon
Cl
double bonds in it :
(A) Formation of a triozonide Cl
.S
(B) Hydrogenation of benzene to cyclohexane NO2
(C) Formation of C6H6Cl6 by addition of chorine
(D) Formation of nitrobenzene on heating (iv) + CH3CH2ONa  D
benzene with a mixture of concentrated nitric
acid and sulphuric acid NO2
Cl
Q.18 Which of the following are classified as
aromatic? NO2
(A) 1,2, 3-Triphenylcyclopropenium cation (v) + C6H5CH2SNa  E
(B) Cyclooctatetraenyl dianion
.J
(C) Azulene NO2

(D) Annulene
Q.19 Match the column : Cl NH2

Column I Column II
NO2 ( i ) NaNO ,HBr
Q.3 (i)   2  E
( ii ) CuBr
N
(A) (P)Group attached with phenyl ring is +M

Br OCH3 ( i) NBS, Benzoylperoxide CCl , heat
(ii)         4  F
( ii) NaSCH3
CH3
N
(B) (Q) Rate of electrophilic aromatic Q.4 Reaction of 1, 2, 3-tribromo-5-nitrobenzene with
sodium ethoxide in ethanol gave a single
product C8H7Br2NO3, in quantitative yield.
substitution is less than benzene ring Suggest a reasonable structure for this
CH3 compound.
(C) (R) Group attached with phenyl ring will Q.5 2-Bromo-1,3-dimethylbenzene is inert to
nucleophilic aromatic substitution on treatment
show (+H) (Hyperconjugation) with sodium amide in liquid ammonia. It is
(S) Group attached with phenyl ring will recovered unchanged even after extended
show (–H) effect (Hyperconjugation) contact with the reagent. Suggest an explanation
for this lack of reactivity.
15
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Mob. No. : 9214233360
Q.6 In each of the following reactions, an amine or a
lithium amide derivative reacts with an aryl Q.6 Choose the correct statement from the ones
halide. Give the structure of the expected given below for two aniline in : [JEE 1993]
product and specify the mechanism by which it +
NH3 NH3
is formed.
Br +
(a) + LiN
(I) (II)
Br (A) II is not an acceptable canonical structure
NO2 because carbonium ions are less stable than
(b) + ammonium ions
N
NO2 H (B) II is not an aceptable canonical structure
because it is non aromatic
Q.7 1,2,3,4,5-Pentalfluoro-6-nitrobenzene reacts (C) II is not an acceptable canonical structure
readily with sodium methoxide in methanol at because the nitrogen has 10 valence
room temperature to yield two major products, electrons
each having the molecular formula C7H3F4NO3. (D) II is an acceptable canonical structure
IR
Suggest reasonable structures for these two
compounds.
Q.7 Most stable cabonium ion is : [JEE 1995]
+
EXERCISE – IV(A) (A) p – NO2 – C6H4 – CH2
Q.1 The chlorination of toluene in presence of ferric +
(B) C6H5 CH2
chloride gives predominatly : [JEE 1986]
(C) p– Cl – C6H4 – +CH2
(A) Benzyl chloride (B) m-chlorotoluene +
(C) Benzal chloride (D) p– CH3O – C6H4 – CH2
.S
(D) o-and p-chlorotoluene
Q.2 Aryl halides are less reactive towards Q.8 Arrange in order of decreasing trend towards SE
nucleophilic substitution reaction as compared to reactions : [JEE 1995]
alkyl halide due to [JEE 1990] (I) Chlorobenzene (II) Benzene
(A) The formation of less stable carbonium ion (III) Anilinium chloride (IV) Toluene
(B) Resonance stabilization
(C) Longer carbon-halogen bond (A) II > I > III > IV (B) III > I > II > IV
(D) The inductive effect (C) IV > II > I > III (D) I > II > III > IV
Q.3 The most basic compound among the following
.J
is : [JEE 1990] Q.9 Among the following statements on the nitration

(A) Benzylamine (B) Aniline of aromatic compounds, the false one is :
(C) Acetaniline (D) p-nitro aniline [JEE 1997]
Q.4 Chlorination of toluene in the presence of light (A) The rate of benzene is almost the same as
and heat followed by treatment with aqueous that of hexadeuterobenzene
NaOH gives : [JEE 1990]
(B) The rate of nitration of toluene is greater than
(A) o-cresol (B) p-cresol
N
that of benzene
(C) 2,4-dihydroxytoluene (D) Bezoic acid
(C) The rate of nitration of benzene is greater
Q.5 When nitrobenzene is treated with Br2 in than that of hexadeuterobenzene
presence of FeBr3 the major product formed is (D) Nitration is an electrophilic substitution
m-bromonitrobenzene. Statements which are reaction
related obtain the m-isomer are : [JEE 1992]
(A) The electron density on meta carbon is
Q.10 Nirtobenzene can be prepared from benzene by
more than on ortho and para position
using a mixture of conc. HNO3 and conc. H2SO4.
(B) The intermediate carbonium ion formed
+ In the nitrating mixture HNO3 acts as a :
after initial attack of Br attack the meta
[JEE 1997]
position is least destabilized
+
(C) Loss of aromaticity when Br attacks at the (A) Base (B) Acid
ortho and para positions and not at meta (C) Reducing agent (D) Catalyst
position Q.11 Benzyl chloride (C6H5CH2Cl) can be prepared
(D) Easier loss of H+ to region aromaticity form from toluene by chlorination with : [JEE 1998]
the meta position than from ortho and para
position (A) SO2Cl2h (B) SOCl 2
(C) Cl2h (D) NaOCl
16
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Mob. No. : 9214233360
Q.12 The most unlikely representation of resonance O
NH
structure of p-nitrophenoxide ion is :[JEE 1998] Q.19 Me Me 
2 Br
 [JEE 2004]
O
–
O O– + O
–
Fe
+
N N
Major product of above reaction is :
(A) (B) O
O NH
NH Me Me
–
O O Me Me
–
O O O + O (A) (B)
+
N N Br Br
O
(C) (D) O NH
–
NH Me Me
– Me Me
O O
(C) (D)
Br Br
Q.13 Benzenediazonium chloride on reaction with
phenol in weakly basic medium gives :
Q.20 Which of the following is obtained when 4-
[JEE 1998]
Methylbenzenesulphonic acid is hydrolysed with
(A) Diphenyl ether
excess of sodium acetate? [JEE 2005]
(B) p-hydroxyazobenzene
(C) Chlorobenzene –+ + SO3
COONa (B) CH3
IR
(A) CH3
(D) Benzene

(C) CH3 SO 3 N a  CH3COOH
Q.14 A solution of (+) –1-chloro-1-phenylethane in
toluene racemises slowly in the presence of (D) CH3 SO3O.COCH3 + NaOH
small amount of SbCl 5, due to the formation of :
[JEE 1999]
(A) Carbanion (B) Carbene AlCl
(C) Free-radical (D) Carbocation Q.21 + Cl – CH2CH2 – CH3 3
 P
.S (i) O / 
Q.15 Toluene, when treated with Br2/Fe, gives p-
2
  

 Q + Phenol [JEE 2006]
( ii ) H3 O
bromotoluene as the major product, because the
CH3 group : [JEE 1999] The major products P and Q are
(A) is para directing (B) is meta directing
(C) activates the ring by hyperconjugation
(D) deactivates the ring (A) and CH3CH2CHO
Q.16 Amongst the following the strongest base is :

.J
[JEE 2000]
(B) and CH3COCH3
(A) C6H5NH2 (B) p-O2NC6H4NH2
(C) m-O2NC6H4NH2 (D) C6H5CH2NH2
Q.17 Identify the correct order of reactivity in (C) and CH3COCH3

electrophilic substitution reactions of the
following compounds [JEE 2002]
N
CH3 Cl NO2
(D) and CH3CH2CHO
(I) (II) (III) (IV)
Q.22 In the following reaction, [JEE 2007]
(A) I > II > III > IV (B) IV > III > II > I
(C) II > I > III > IV (D) II > III > I > IV O
.. conc .HNO
N
3
   X
conc .H2SO 4
( CH ) NH H
Q.18 F NO2   
3 2
 A
DMF the structure of the major product ‘X’ is
(i) NaNO 2 HCl 05C O2N
      B [JEE 2003] O O
(ii) H2 Catalytic Reduction (A) N NO2 (B) N
H3C H H
(A) O2N NH2 (B) N NH2
H3C O O
H3 C H3C (C) N (D) O N N
2
(C) N NO2 (D) N NO2 H
NO2 H
H2 C H3C
NH2
17
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Mob. No. : 9214233360
O
Q.23 Statement – 1: Bromobenzene upon reaction COOH OCH3
with Br2/Fe gives 1,4-dibromobenzene as the C
O NO 2
major product. [JEE 2008] H 3C
(D) HO NO2 NO2
and
Statement - 2 : In bromobenzene, the inductive
OH
effect of the bromo group is more dominant than
the mesomeric effect in directing the incoming NaOH ( aq .) / Br2
electrophile. Q.26 In the reaction   the
(A) SATEMENT -1 is True, SATEMENT-2 is True;
STATEMENT-2 is a correct explanation for intermediate(s) is(are) [JEE 2010]
STATEMENT-1 O O O O
(B) SATEMENT -1 is True, SATEMENT-2 is True; Br
STATEMENT-2 is NOT a correct explanation for
(A) (B) (C) (D)
STATEMENT-1
(C) SATEMENT -1 is True, SATEMENT-2 is Br
Br Br
False. Br Br
(D) SATEMENT -1 is False, SATEMENT-2 is
True. Q.27 Amongst the compounds given, the one that
would form a brilliant colored dye on treatment
Q.24 Statement – 1 : Aniline on reaction with
with NaNO2 is dil. HCl followed by addition to an
IR
NaNO2/HCl at 0°C followed by coupling with -
alkaline solution of -naphthol is [JEE 2011]
naphthol gives a dark blue coloured precipitate. N(CH3)2 NHCH 3
[JEE 2008] (A) (B)
and
Statement – 2 : The colour of the compound NH 2
formed in the reaction of aniline with NaNO2/HCl CH 2NH 2
at 0° followed by coupling with -naphthol is due (C) (D)
to the extended conjugation. H3C
(A) SATEMENT -1 is True, SATEMENT-2 is True;
.S
STATEMENT-2 is a correct explanation for EXERCISE – IV(B)
STATEMENT-1
AlCl3
(B) SATEMENT -1 is True, SATEMENT-2 is True; Q.1 + (CH3)2CH.CH2Cl   (A)
STATEMENT-2 is NOT a correct explanation for
STATEMENT-1 [JEE 1992]
(C) SATEMENT -1 is True, SATEMENT-2 is
( i ) Br ,Heat , light
False. Q.2 C6H5C2H5  
2
   [JEE 1994]
( ii ) NaCN
(D) SATEMENT -1 is False, SATEMENT-2 is
True.
.J
Q.3 An organic compound (A), C8H6 on treatment

Q.25 The compounds P, Q and S with dilute sulphuric acid containing mercuric
COOH
O sulphate gives a compound (B), which can also
OCH3 be obtained from a reaction of benzene with an
C
O acid chloride in the presence of anhydrous
HO H 3C aluminium chloride. The compound (B), when
P Q S treated with iodine in aqueous KOH, yields (C)
were separately subjected to nitration using
N
and a yellow compound (D). Identify (A), (B), (C)

HNO3/H2SO4 mixture. The major product formed and (D) with justification. Show how (B) is
in each case respectively, is [JEE 2010] formed from (A) ? [JEE 1994]
COOH O
OCH3
C Q.4 Toluene reacts with bromine in the presence of
O
HO H3C light to give benzyl bromine while in presence of
(A) NO2 NO2 NO2 FeBr3 it gives p-bromotoluene. Give explanation
O for the above observations. [JEE 1996]
OCH3
COOH C
O Q.5 Show the steps the carry out the following
H3C transformations: [JEE 1998]
(B) HO NO2 NO2 NO2 (a) Ethylbenzene  benzene
COOH O NO2 (b) Ethylbenzene  2-phenylpropionic acid
OCH3
C
O
HO alcoholic KOH, heat
H3C NO2
Q.6 C6H5CH2CHClC6H5     (A)+ (B)
(C) NO2
[JEE 1998]
18
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Mob. No. : 9214233360
Q.7 Normally, benzene gives electrophilic .. O O
.. O ..
substitution reaction rather than thus N N N
electrophilic addition reaction although it has Conc .HNO NO2
(c) (i)  
3

double bonds. [JEE 2000] Conc .H2SO4 +
Q.8 How would you synthesis 4 methoxyphenol from NO2

bromobenzene in NOT more than five steps ? NO2 NO2
State clearly the reagents used in each step and
show the structures of the intermediate Conc.HNO
3
(ii)    
 
compounds in your synthetic scheme. Conc.H2SO 4 NO2
[JEE 2001]
Q.9 Carry out following conversions in 3 or less

steps. [JEE 2003]
Pd / C
(d) 
 is
COOH COOH 3 moles of H2
IR
Q.10 A compound C9H7O2Cl exists in keto form A and
enolic form B. Enolic form B predominates at
equilibrium. On oxidation with KMnO4 it gives m- formed but not
chlorobenzoic acid. Give structures of A and B.
[JEE 2003]
Q.11 7-bromo-1,3,5-cycloheptatriene is ionic

compound, whereas 5-bromo-1,3-  Brown fumes and  NaBr MnO 2
Q.13   B     A
pungent smell
.S
cyclopentadiene can’t ionise even in the
presence of Ag, Explain why? [JEE 2004]
 
CH3
Conc .HNO 3
     C(intermediate) D
Q.12 Give reasons : [JEE 2005] (Explosive product)
H3C Br Find A, B, C and D. Also write equations A to B
C 2H5OH(aq.)
(a) (i) CH     acidic solution and A to C. [JEE 2005]
3
CH3 C 2H5OH(aq.)
(ii) Br     neutral
CH3
.J
F
NaOH( aq.)
(b) (i) O N    F (liberated)
2
CH3
F
N
NaOH( aq.)
(ii)    F is not liberated
H3C
CH2NO2
19
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Mob. No. : 9214233360
ANSWER KEY
EXERCISE - I
Ques. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. C C D C C B A B B A D B B A A C A B D B
Ques. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38
Ans. B A B B A A C B B B C D D A B C A A
EXERCISE – II
Ques. 1 2 3 4 5 6 7 8
Ans. B,D A,B,C,D A,B,D C,D B,D B,C,D A,B,C B,C,D
Ques. 9 10 11 12 13 14 15 16
Ans. A,B,D C,D A,B,D B,C,D A,C B,C B,C,D A,B
Ques. 17 18
Ans. A,B,C A,B,C
Q.19 (A) Q ; (B) P ; (C) R
EXERCISE – III
–
O O
NO2
IR
N
F OCH3
Q.1 F
SCH2 – C6H5 NH – NH2 CF3 OCH2CH3 SCH2 – C6H5

NO2 NO2 NO2 NO2
Q.2 (i) (ii) (iii) (iv) (v)
.S NO2
CH3 NO2 OCH3 NO2 NO2
Cl Br
Br
Q.3 (i) (ii) OCH3
CH2
CH3S
Br Br
.J
Br OC2H5
Q.4 Q.5
O2N Br O2N Br
NO2
Q.6 (a) Ph – N (b) O2N N
N
NO2 NO2
F OMe F F
Q.7
F F F F
F OMe
EXERCISE – IV(A)
Ques. 1 2 3 4 5 6 7 8
Ans. D B A D A,B C D C
Ques. 9 10 11 12 13 14 15 16
Ans. C A A,C C B D A,C D
Ques. 17 18 19 20 21 22 23 24
Ans. C B D C C B C D
Ques. 25 26 27
Ans. C A,C,D C
20
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ETOOS Academy Pvt. Ltd.
F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
EXERCISE – IV(B)
CHCNCH3
CH2CH3 CHBrCH3
C(CH3)3 Br
2 NaCN
Q.1 Q.2 
   

,h
2-phenylpropane niitrile
C CH COCH3 COOK

Q.3 (A) (B) (C)
Q.4 In presence of FeBr3, Br2 Produces Br+ (an electrophile) which attacks the benzene ring at o-,
p-position to give p-bromotoluene. In presence of light, side chain is attacked to produce benzyl bromide.
C2H5 COOH
[O ] Soda lim e
Q.5 (b) (i) 
   
CN COOH
CH2CH3 CHXCH3 CHCH3 CHCH3
IR
X2 KCN HOH
(ii) 
  
h
KOH( alc .)
Q.6 C6H5CH2CHClC6H5    C6H5CH = CHC6H5

(Cis and trans forms)
Q.7
.S
Benzene has resonance stabilization due to delocalization of -electrons. Also during electrophilic addition
reactions, it is loses its aromaticity. In electrophilic substitution reaction aromaticity is retained.
Br ONa OMe OMe
NaOH conc.H SO
2 4 NaOH
Q.8  
   
       

 high presence Me2SO 4
SO3H
OMe OMe
.J
H O
3 

ONa OH
Alternative rout
Br Br Br Br
N
conc .H SO
2 4 NaOH NaOH
      
   
  

Me2SO 4  high pressure
SO3H ONa OMe

OMe OMe
H O
3 

ONa OH
COOH COOH
COOH
conc .H SO
2 4 HBF / KHF
Q.9       4  
2

 
SO3H F
21
----------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
O OH
C – CH2 – CHO C – CH – CHO
Q.10
Cl Cl
(A) (B)
Keto Enol
Enol form is more stable due to extended conjugation.
O
C – OH
KMnO
4
(A)   
Cl
Q.11 On ionization 7-bromo-1,3,4-cycloheptatriene gives tropolium ion which is aromatic with 6 electrons.
Br
 + Br
IR
5-bromo-1,3-cyclopentadiene can't ionize as it will in that case give highly unstable antiaromatic cation with
4 electrons.
Br

+ Br
CH3
Q.12
.S
(a) (i) H5C6 – C – OC2H5 + HBr (acid) ; (i) no reaction due to partial double bond character
CH3
OH
–
(b) (i) O2N + F is liberated ; (ii) Bimomecular mechanism is not possible in (ii) case
CH3
(c) (i) due to presence of lone pair of nitrogen atom NO group is electron donating and ortho, para
directing
.J
(ii) NO2 group is electron withdrawing and meta directing

(d) Due to reduction of central ring, three four membered antiaromatic rings become stable while on
reduction of terminal ring only one antiaromatic ring can be stabilized.
CH3
O2N NO2
N
Q.13 (A) H2SO4, (B) Br2, (C) NO 

2 , (D)
NO2
22
----------------------------------------------------------------------------------------------------
Mob. No. : 9214233360

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ETOOSINDIA

INDIA’S NO. 1 ONLINE COACHING

IIT-JEE ChEmistry by N.J. sir

e– donating groups activating e– with drawing groups deactivating

– O – CH = CH2, –NH – CH – CH2 – C – NH 2, – C – O – C – R,

Fill in the blanks :

(1) CH3 (2) (a)

(5) (6) (a) (b)

2. Identify the ring on which electrophilic (a) (b) (c) (d)

(6) (7) (a) (b) (c)

H CH3 CH3 N= 0 (4) Ph–N NCl –

N – N Coupling (CrO2Cl 2  etard reagent)

H R (4) Rosenmund Reduction :

(a) o-nitrotoluene (b) m-dibromobenzene

Q.3 Final product of the given reaction:

CH2OH CHOH CH2OH

Q.5 Which of the following statement is not correct regarding desulfonation?

Q.6 Point out the wrong formulation.

CH2 Q.13 Strong e— with drawing groups like.

Strong e— releasing group — NH2 donot not

Q.3 Q.11 Convert Cl

HNO3 /H2SO4 Q.18 Br Cl 

Br2 /H2O Q.3 Br2 /H2O

SO3H SO3H Mechanism:–

Lindane /666/ C6H6Cl6 /Gammaxene /BHC

(A) 2 (B) 4 (C) 6 (D) 8 (A ) o-Toluidine (B) m-Toluidine

(C) CH3CONH2 (D) CH2(Cl)CONH2

Q.19 Which of the following carbocations is expected NO2

Q.34 Which chloroderivative of benzene among the 

(C) Me2N Cl (D) Cl EXERCISE – II

Q.3 The replacement of a hydrogen atom in benzene (C) (D)

Q.7 Electrophilic attack of NO 

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

(C) Azulene NO2

Q.19 Match the column : Cl NH2

(A) (P)Group attached with phenyl ring is +M

is : [JEE 1990] Q.9 Among the following statements on the nitration

Q.16 Amongst the following the strongest base is :

Q.17 Identify the correct order of reactivity in (C) and CH3COCH3

Q.3 An organic compound (A), C8H6 on treatment

and a yellow compound (D). Identify (A), (B), (C)

Q.8 How would you synthesis 4 methoxyphenol from NO2

Q.9 Carry out following conversions in 3 or less

Q.11 7-bromo-1,3,5-cycloheptatriene is ionic

SCH2 – C6H5 NH – NH2 CF3 OCH2CH3 SCH2 – C6H5

C CH COCH3 COOK

SO3H ONa OMe

(ii) NO2 group is electron withdrawing and meta directing

Q.13 (A) H2SO4, (B) Br2, (C) NO 

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