Aromatic Compounds

IIT-JEE ChEmistry by N.J.
sir ORGANIC chemistry
IR
.S
AROMATIC CHEMISTRY
.J
N
1
----------------------------------------------------------------------------------------------------
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)
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 , NHCH3
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
C NH 2, C O C R,
IR
O CH = CH2, NH CH CH2
O O O
3) Weakly E.D.G. (O/P- directing) 3) Weakly EWG. (O/P- directing)
O
R, C , Ph
O
.S
Fill in the blanks :
Substitute on Ph ring o/p Meta Activating deactivating
1.
.J
2.
3. C CH3
||
O
N
4. O C CH3
||
O
5. SO3H
6. CH3

7. N O
8.
O
9. CH = CHNO2
10. NH CH3
2
----------------------------------------------------------------------------------------------------
1. Identify the position where electrophilic
substitution is favourable :
O O
CH2NHCH3
NHCCH 3
CH3 (b) (c)

(1) (2)
OH
NHCH2CH3
CH3 O (2)
COCH 3
CH3
(3) (4) (a) (b)
CO
O
O
O
NHCCH 3 CH3
(5) (6) (c) (d)

NO2 Cl NO2 OCH3
IR
CNHCH 3
O (3)
OCH=CH2
CH2N(me)3
(a) (b) (c) (d)
O
(7) (8)
NH2 NHCCH3
CCH3
.S
N(me)3
O
(4)
2. Identify the ring on which electrophilic
substitution is more favorable : (a) (b) (c)
O CH3 SO 3H
(1) C NH
O O
.J
(2) C C
(d) (e)
(3) CH2 OCH3
CH3 CD3 CT3
(4) OH (5)
N
O
(a) (b) (c)
(5) O C
O
C NH O (6)
(6) (7)
4. Diazotisation of amines
3. Compare rate of electrophilic substitution : NaNO2
(1) HCl diazonium chloride
O O
NH 2
(1)
1
(a)
3
----------------------------------------------------------------------------------------------------
R R R R
NaNO2 N N
(2) HCl (Nitroso amine)
PhN NCl
N N (3) (X)
H CH3 CH3 N= 0
2 N
NO N
Ph
NaNO2
(3) HCl OH
N N (4) PhN NCl

N=N OH
CH 3 CH3
3 OH
H3PO 2 PhN NCl

A A
mild acidic
H2O HBr/ CuBr (5)
L B
IR
Br PhN NCl
B
Mg HCl/CuCl
C Sandmeyer NH2 mild basic
Ph
K KCN/CuCN
oH D
Et
CH
HBr/Cu
6. Typical oxidation/reduction reactions :
KS
J HBF4 E NO2
Gattermam
HCl/Cu
F Sn/HCl NH2
H (1) S nC
l2 /HC
.S l
G Fe/HCl NH2
Schiemann Reaction
NH2
5. Cupling Reactions of diazonium salts :
NH2
(X) (2) Selective reduction :
(1) NHN=NPh NO2 NH2
.J
N N Coupling NH4HS
Na2S
H R
N NO2 NO2
(X)
PhN NCl (3) Etard Oxidation :
(2) N N = NPh O
N
CH3 CrO2Cl2
CH3 CH
(CrO2Cl 2 etard reagent)
(4) Rosenmund Reduction :

O O
H2
C Cl CH
Pd-BaSO4
4
----------------------------------------------------------------------------------------------------
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
CH
O (p) + O AlCl3
P
.J
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
----------------------------------------------------------------------------------------------------
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.

AlCl3
(A) C6H5Br + (CH3CO)2 O Br CO CH3
.S
CH3 CH3
CO CH3
AlCl3
(B) + CH3COCl
CH CH
H3C H3C
CH3 CH3
CH3 CH3
.J
AlCl3
(C) + CH3COCl
CO CH3
CH CH
H3C H3C
CH3 CH3
N
AlCl3
(D) C6H5NO2 + EtCl no reaction
6
----------------------------------------------------------------------------------------------------
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, COH, SO3H give
Explain poor yield in friedel craft alkylation. Explain.
Q.14 Strong e releasing group NH2 donot not
IR
H or give friedel craft alkylation. Explain
Q.2 +
BF3
OH CH3
CH3Cl/ AlCl3
H or Q.15 + +
Q.3 +
AlCl3
.S Cl
AlCl3 +
Q.4 +
AlCl3
Q.5 + CH3 CH2 CH2 Cl Write the major product for these reactions.
O
AlCl3 AlCl3
.J
Q.6 + Q.16 + RCCl

Cl
H or O O
Q.7 + AlCl3
AlCl3 Q.17 + CH3C CCH3
O O
AlCl3 O
N
Q.8 +

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
----------------------------------------------------------------------------------------------------
DPP NO -03 Time: 15 minutes
Q.1 Compare the rate of nitration NHCCH3
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 OC E
N2O5 C6H6 C6D6 C6T6
IR
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 NH2 (hint: protection of para position)
.S
HNO3 /H2SO4 OH

Q.12 Fe+2/H2O2
NO2 Zn/dust
51% CH3
NH2 NH2
Br2/Fe
.J
NO2 Q.13 A
+ +
NO2 Br2/h
B
47% 2% OH
OH Br2/CS2/5C
NH2 O O Q.14
N
Br
CH3C CCH3 OH
O Br2/H2O Br Br
Q.4
Br
HNO3 /H2SO4 H3O
(A) (B) (D)+(C
I2
O Q.15 (A)
HNO3
Q.5 CNH 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
----------------------------------------------------------------------------------------------------
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 CH O

2.H2O 1. 2 + O
(b) Stephen Reduction O OH
SnCl2 CH = NH
HO
HCl
O Phenolphthalein
CH 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 CH2CH=CH2
H3O
Ph C 200C
H

OH NH2 OH
Br2 /H2O Q.3 Br2 /H2O

CH2CH=CH2
Q.2
.J
SO3H SO3H Mechanism:

NH2 (1)
CH2
SO3H Br2 /H2O O CH
O CH2 O
Q.4 CH2
CH CH2CH=CH2
CH2
N
OH
SO3H Tautomer
Br2 /H2O
Q.5 OH
CH2CH=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
----------------------------------------------------------------------------------------------------
O CH2 CH = CH2 Mechanism:
1.
Q.2 O O
O C CH3
+
CH3COAlCl3
AlCl3
O CH2 CH = CH = CH2
Q.3
OAlCl2
O

CH3C + + Cl +
O CH2 CH = CH2
D D E.A.S.
Q.4

OH OAlCl2
D
H2O
CH3
O CH2 CH = CH2 C C
IR
O CH3 O CH3
Q.5 O
OCCH3
Fries Rearrangement 1. AlCl3 /
Q.1
O 2. H2O
O C CH 3 OH O
.S 1. AlCl3 OCCH3

2.
3.H2O 1. AlCl3 /
CCH3 Q.2
2. H2O
O
.J
N
10
----------------------------------------------------------------------------------------------------
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
OCH3
IR
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 (D) p-Tolyl
.S 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)
(C) CH2CH2CH2CH3
.J
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
CCH2COH (Benzoyl acetic acid) A in the above reaction is :
(A) NH2CONH2 (B) ClCONH2
(C) CH3CONH2 (D) CH2(Cl)CONH2
N
(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
----------------------------------------------------------------------------------------------------
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
Q.27 Ring nitration of dimethyl benzene results in the
.S
involving sulphonation, which of the following
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
Q.18 Which of the following carbocations is expected (C) (D) None of these
.J
to be most stable ?
CH3 CH3 CH3 CH3 CH3
+ H
(A) (B) (C) +
+ H (D) + Y Q.28 If p-methoxy toluene is nitrated, the major
Y product is :
H Y H Y
CH3 CH3
N
Q.19 Which of the following carbocations is expected NO2

to be most stable ? (A) (B)
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
(I) C6H5CH3 (II) C6H5COOH (A) (B)
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
----------------------------------------------------------------------------------------------------
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 OCOCH3
3
?
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 Crafts reaction of bromobenzene with
R R
CH3Cl
.J
(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 + product. The
Cl
Q.1 Benzene reacts with n-propyl chloride in the
product is :
presence of anhydrous AlCl3 to give
(A) Lindane (B) DDT
predominantly :
(C) Tefflon (D) Ethaneperchlorate
(A) n-Propylbenzene (B) Isopropylbenzene
(C) 3-Propyl-1-chlorobenzene
(D) Cumene
13
----------------------------------------------------------------------------------------------------
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
density at meta-position
.J
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
Q.7 Electrophilic attack of NO
2 at meta position is
N
(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
(C) O C R (D) CH3
NH2 NO2 NMe3 Q.15 False statement is/are :
(A) Although benzene contains three double
(A) (B) (C) (D) bonds, normally it does not undergo addition
reaction
(B) m-chlorobromobenzene is an isomer of m-
bromochlorobenzene
14
----------------------------------------------------------------------------------------------------
(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
Cl
orients the incoming electrophilic group to the
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
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
IR
double bonds in it :
(A) Formation of a triozonide Cl
(B) Hydrogenation of benzene to cyclohexane NO2
(C) Formation of C6H6Cl6 by addition of chorine
(iv) + CH3CH2ONa D
(D) Formation of nitrobenzene on heating
benzene with a mixture of concentrated nitric NO2
acid and sulphuric acid
Cl
Q.18 Which of the following are classified as
.S
aromatic? NO2
(A) 1,2, 3-Triphenylcyclopropenium cation (v) + C6H5CH2SNa E
(B) Cyclooctatetraenyl dianion
(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
.J
( ii ) CuBr
(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
N
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.
Q.6 In each of the following reactions, an amine or a

EXERCISE III lithium amide derivative reacts with an aryl
halide. Give the structure of the expected
Q.1 Write the most stable resonating structure for the
product and specify the mechanism by which it
cyclohexadienyl anion formed by reaction of
is formed.
methoxide ion with o-fluoronitrobenzene.
15
----------------------------------------------------------------------------------------------------
+
Br NH3 NH3
+
(a) + LiN
Br (I) (II)
NO2
+ (A) II is not an acceptable canonical structure
(b)
N because carbonium ions are less stable than
ammonium ions
NO2 H
(B) II is not an aceptable canonical structure
Q.7 1,2,3,4,5-Pentalfluoro-6-nitrobenzene reacts because it is non aromatic
readily with sodium methoxide in methanol at
room temperature to yield two major products, (C) II is not an acceptable canonical structure
each having the molecular formula C7H3F4NO3. because the nitrogen has 10 valence
Suggest reasonable structures for these two electrons
compounds. (D) II is an acceptable canonical structure
EXERCISE IV(A) Q.7 Most stable cabonium ion is : [JEE 1995]

Q.1 The chlorination of toluene in presence of ferric +
(A) p NO2 C6H4 CH2
chloride gives predominatly : [JEE 1986]
IR
+
(A) Benzyl chloride (B) m-chlorotoluene (B) C6H5 CH2
(C) Benzal chloride (C) p Cl C6H4 +CH2
(D) o-and p-chlorotoluene +
(D) p CH3O C6H4 CH2
Q.2 Aryl halides are less reactive towards
nucleophilic substitution reaction as compared to Q.8 Arrange in order of decreasing trend towards SE
alkyl halide due to [JEE 1990] reactions : [JEE 1995]
(A) The formation of less stable carbonium ion
(I) Chlorobenzene (II) Benzene
.S
(B) Resonance stabilization
(C) Longer carbon-halogen bond (III) Anilinium chloride (IV) Toluene
(D) The inductive effect (A) II > I > III > IV (B) III > I > II > IV
Q.3 The most basic compound among the following (C) IV > II > I > III (D) I > II > III > IV
is : [JEE 1990]
(A) Benzylamine (B) Aniline
Q.9 Among the following statements on the nitration
(C) Acetaniline (D) p-nitro aniline
of aromatic compounds, the false one is :
Q.4 Chlorination of toluene in the presence of light [JEE 1997]
and heat followed by treatment with aqueous
.J
NaOH gives : [JEE 1990] (A) The rate of benzene is almost the same as
(A) o-cresol (B) p-cresol that of hexadeuterobenzene
(C) 2,4-dihydroxytoluene (D) Bezoic acid (B) The rate of nitration of toluene is greater than
that of benzene
Q.5 When nitrobenzene is treated with Br2 in (C) The rate of nitration of benzene is greater
presence of FeBr3 the major product formed is than that of hexadeuterobenzene
m-bromonitrobenzene. Statements which are
(D) Nitration is an electrophilic substitution
N
related obtain the m-isomer are : [JEE 1992]

reaction
(A) The electron density on meta carbon is
more than on ortho and para position
(B) The intermediate carbonium ion formed Q.10 Nirtobenzene can be prepared from benzene by
+
after initial attack of Br attack the meta using a mixture of conc. HNO3 and conc. H2SO4.
position is least destabilized In the nitrating mixture HNO3 acts as a :
(C) Loss of aromaticity when Br+ attacks at the [JEE 1997]
ortho and para positions and not at meta (A) Base (B) Acid
position
+ (C) Reducing agent (D) Catalyst
(D) Easier loss of H to region aromaticity form
the meta position than from ortho and para
position Q.11 Benzyl chloride (C6H5CH2Cl) can be prepared
from toluene by chlorination with : [JEE 1998]
Q.6 Choose the correct statement from the ones (A) SO2Cl2h (B) SOCl 2
given below for two aniline in : [JEE 1993] (C) Cl2h (D) NaOCl
16
----------------------------------------------------------------------------------------------------
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
(A) CH3 COONa (B) CH3
IR
(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 :

[JEE 2000]
.J
(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]
CH3 Cl NO2
N
(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 05C 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
----------------------------------------------------------------------------------------------------
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
NaNO2/HCl at 0C followed by coupling with -
IR
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;
.SSTATEMENT-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.
Q.3 An organic compound (A), C8H6 on treatment
.J
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 and a yellow compound (D). Identify (A), (B), (C)
N
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
----------------------------------------------------------------------------------------------------
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
F
Q.10 A compound C9H7O2Cl exists in keto form A and
IR
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
cyclopentadiene cant ionise even in the pungent smell
.S
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
NaOH( aq.)
(ii) F is not liberated
N
H3C
CH2NO2
19
----------------------------------------------------------------------------------------------------
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
----------------------------------------------------------------------------------------------------
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 Benzene has resonance stabilization due to delocalization of -electrons. Also during electrophilic addition
.S
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
H O
3
.J
ONa OH
Alternative rout
Br Br Br Br
conc.H SO
2 4 NaOH NaOH

Me 2SO 4 high pressure
N
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
----------------------------------------------------------------------------------------------------
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
(A) H2SO4, (B) Br2, (C) NO

N
Q.13 2 , (D)
NO2
22
----------------------------------------------------------------------------------------------------

Aromatic Compounds

Transféré par

Informations du document

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Aromatic Compounds

Transféré par

Droits d'auteur :

Formats disponibles

IIT-JEE ChEmistry by N.J.

sir ORGANIC chemistry

Directive Influence in substituted Benzene

e donating groups activating e with drawing groups deactivating

CH3 (b) (c)

(5) (6) (c) (d)

N N (4) PhN NCl

(CrO2Cl 2 etard reagent)

(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.

Q.14 Strong e releasing group NH2 donot not

Q.6 + Q.16 + RCCl

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

(A) COCH3 (B) COOH

Q.19 Which of the following carbocations is expected NO2

(C) Bromination of nitrobenzene and subsequent (A)

Q.34 Which chloroderivative of benzene among the

(C) Me2N Cl (D) Cl

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

CH3 CH3 SO3H COOH (D) Ortho-and para-directing groups decrease

(B) All ortho-para directing groups excepting

Q.19 Match the column : Cl NH2

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

sodium ethoxide in ethanol gave a single

Q.6 In each of the following reactions, an amine or a

EXERCISE IV(A) Q.7 Most stable cabonium ion is : [JEE 1995]

related obtain the m-isomer are : [JEE 1992]

Q.16 Amongst the following the strongest base is :

(B) and CH3COCH3

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

(D) and CH3CH2CHO

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

SO3H ONa OMe

(ii) NO2 group is electron withdrawing and meta directing

(A) H2SO4, (B) Br2, (C) NO

Vous aimerez peut-être aussi