KKHK

PREVIOUS YEAR
PROBLEM SOLVING
IIT JEE MAIN + ADVANCED
ORGANIC CHEMISTRY
BY
NAVNEET JETHWANI
AROMATIC
CHEMISTRY
ETOOSINDIA
INDIA’S NO. 1 ONLINE COACHING
Plot No. 38, Near Union Bank of India, Rajeev Gandhi Nagar,
Kota, Rajasthan – 324005 Mob. : 9214233303
ETOOSINDIA N.J. SIR
JEE MAINS
1. The reaction of chloroform with alcoholic KOH and p-toluidine forms : [AIEEE-2003]
(1) H3C CN (2) H3C N2Cl
(3) H3C NHCHCl2 (4) H3C NC
Ans. (4)
OH
– +
O Na
2. + CHCl3 + NaOH
CHO
The electrophile involved in the above reaction is [AIEEE-2006]
(1) dichlorocarbene (:CCl2) (2) trichloromethyl anion (C Cl3)
+ +
(3) formyl cation (CHO) (4) dichloromethyl cation (CHCl 2)
Ans. (1)
3. Fluorobenzene (C6H5F) can be synthesized in the laboratory [AIEEE-2006]
(1) from aniline by diazotisation followed by heating the diazonium salt with HBF4
(2) by direct fluorination of benzene with F2 gas
(3) by reacting bromobenzene with NaF solution
(4) by heating phenol with HF and KF
Ans. (1)
4. Presence of a nitro group in a benzene ring [AIEEE-2007]
(1) activates the ring towards electrophilic substitution
(2) renders the ring basic
(3) deactivates the ring towards nucleophilic substitution.
(4) deactivates the ring towards electrophilic substitution.
Ans. (4)
5. The reaction of toluene with Cl2 in presence of FeCl3 gives predominantly : [AIEEE-2007]
(1) Benzoyl chloride (2) Benzyl chloride
(3) o–and p–Chlorotoluene (4) m–Chlorotoluene
Ans. (3)
6. The electrophile, E  . attacks the benzene ring to generate the intermediate -complex. Of the following, which
-complex is of lowest energy ? [AIEEE-2008]
NO2 NO2 NO2
H
H
+ E
(1) (2) + E (3) + (4) +
H
E
H E
Ans. (1)
Plot No. 38, Near Union Bank of India, Rajeev Gandhi Nagar, Page # 2
ETOOSINDIA N.J. SIR
7. Phenol, when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid, gives :
[AIEEE-2008]
(1) o-nitrophenol (2) p-nitrophenol (3) nitrobenzene (4) 2,4,6-trinitrobenzene
Ans. (1)
8. Toluene is nitrated and the resulting product is reduced with tin and hydrochloric acid. The product so obtained is
diazotised and then heated with cuprous bromide. The reaction mixture so formed contains : [AIEEE-2008]
(1) mixture of o– and p-dibromobenzenes (2) mixture of o- and p-bromoanilines
(3) mixture of o- and m-bromotoluenes (4) mixture of o- and p-bromotoluenes
Ans. (4)
9. Phenol is heated with a solution of mixture of KBr and KBrO3. The major product obtained in the above reaction is
[AIEEE-2011]
(1) 2-Bromophenol (2) 3-Bromophenol (3) 4-Bromophenol (4) 2, 4, 6 -Tribromophenol
Ans. (4)
10. Ortho-Nitrophenol is less soluble in water than p- and m- Nitrophenols because : [AIEEE-2012]
(1) o-Nitrophenol is more volatile steam than those of m- and p-isomers.
(2) o-Nitrophenol shows Intramolecular H-bonding
(3) o-Nitrophenol shows intermolecular H-bonding
(4) Melting point of o-Nitrophenol is lower than those of m- and p-isomers.
Ans. (2)
11. A compound with molecular mass 180 is acylated with CH3COCl to get a compound with molecular mass 390. The
number of amino groups present per molecule of the former compound is : [JEE(Main)-2013]
(1) 2 (2) 5 (3) 4 (4) 6
Ans. (2)
12. Compound (A), C8H9Br, gives a white precipitate when warmed with alcoholic AgNO3. Oxidation of (A) gives an acid
(B), C8H6O4. (B) easily forms anhydride on heating. Identify the compound (A). [JEE(Main)-2013]
CH2Br
CH2Br C2H5 CH2Br
(1) (2) (3) (4)
Br CH3
CH3 CH3
Ans. (4)
13. The gas leaked from a storage tank of the Union carbide plant in Bhopal gas tragedy was :- [JEE(Main)-2013]
(1) Methylisocyanate (2) Methylamine (3) Ammonia (4) Phosgene
Ans. (1)
ETOOSINDIA N.J. SIR
14. Sodium phenoxide when heated with CO2 under pressure at 125°C yields a product which on acetylation produces
C. [JEE(Main)-2014]
ONa
125° H+
+ CO2 B C
5 atm Ac2O
The major product C would be :
OH OCOCH3 OCOCH3 OCOCH3

COOCH3 COOH COCH3
(1) (2) (3) (4)
COOH
COCH3
Ans. (3)
15. The following reaction [Jee Main (Online) 2014]
OH
OH
Anhyd.
+ HCl + HCN
ZnCl2 CHO
is known as
(1) Perkin reaction (2) Kolbe’s reaction
(3) Gattermann reaction (4) Gattermann-Koch Formylation
Ans. (4)
16. Chlorobenzene reacts with trichloro acetaldehyde in the presence of H2SO4 [Jee Main (Online) 2014]
O
Cl
H2SO4
2 +H C CCl3
The major product formed is
Cl
(1) Cl CH Cl (2) Cl C Cl
Cl Cl
Cl
(3) Cl C Cl (4) Cl CH Cl
CH2Cl CCl3
Ans. (4)
ETOOSINDIA N.J. SIR
17. In a set of reaction p-nitrotoluene yielded a product E [Jee Main (Online) 2014]
CH3
Br2 Sn/HCl NaNO2 CuBr
B C D E
FeBr3 HCl HBr
NO2
The product E would be :-
CH2Br CH3 CH3 CH 3

Br Br Br Br
(1) (2) (3) (4)
Br
Br Br Br
Ans. (2)
18. In the reaction [JEE(Main)-2015]
E + N2
CuCN/KCN
the product E is:
CN COOH
CH3
(1) (2) (3) (4) H3C CH3
CH3 CH3
Ans. (1)
19. In the following sequence of reactions: [JEE(Main)-2015]
KMnO4 SOCl2 H2/Pd
Toulene A B BaSO4 C
the product C is:

(1) C6H5CH2OH (2) C6H5CHO (3) C6H5COOH (4) C6H5CH3
Ans. (2)
20. Consider the reaction sequence below :- [Jee Main (Online) 2016]
OCH3
Succinic anhydride Clemmenson's

A X X is :
AlCl3 reduction
ETOOSINDIA N.J. SIR
OH OH
OCH3
H3CO
(1) (2)
OH OH
OCH3
H3CO
(3) (4)
Ans. (4)
21. Fluorination of an aromatic ring is easily accomplished by treating a diazonium salt with HBF4. Which of the
following conditions is correct about this reaction ? [Jee Main (Online) 2016]
(1) Only heat (2) NaNO2/Cu (3) Cu2O/H2O (4) NaF/Cu
Ans. (1)
22. The major product expected from the following reaction is : [Jee Main (Online) 2017]
CH2OH O
HO2C
NH2
HCl(g)/CCl4
OH
O O
O O
HO2C HO2C
(1) (2)
Cl OH
O
O CH2OH O
O
HO2C
NH2 NH2
(3) (4)
OH Cl
Ans. (3)
ETOOSINDIA N.J. SIR
23. Which of the following compounds will significant amount of meta product during mono-nitration reaction ?
[JEE Main 2017]
OH OCOCH3 NH2 NHCOCH3
(1) (2) (3) (4)
Ans. (3)
24. Which of the following compounds will not undergo Friedel Craft’s reaction with benzene ?
[Jee Main (Online) 2017]
COCl
Cl Cl
(1) Cl (2) (3) (4)
O
Ans. (1)
JEE ADVANCED
Subjective Type Questions
AlCl3
1. + (CH3)2CHCH2Cl (A) [JEE 1992]
C(CH3)
Ans.
(i) Br2, Heat, Light

2. C6H5C2H5 [JEE 1994]
(ii) NaCN
CHBrCH3 CHCNCH3
NaCN
Ans.
2-phenylpropane nitrilile
3. An organic compound (A) C8H6 on treatment with dilute sulphuric acid containing mercuric sulphate gives a
compound (B), which can also be obtained from a reaction of benzene with an acid chloride in the presence of
anhydrous aluminium chloride. The compound (B), when treated with iodine in aqueous KOH, yields (C) and a
yellow compound (D). Identify (A), (B), (C) and (D) with justification. Show how (B) is formed from (A) ?
[JEE 1994]
C CH COCH3 COOK
Ans. (A) (B) (C)
4. Toluene reacts with bromine in the presence of ultravoilet light to give benzyl bromine while in presence of FeBr3 it
gives p-bromotoluene. Give explanation for the above observations. [JEE 1996]
ETOOSINDIA N.J. SIR
5. Show the steps to carry out the following transformations : [JEE 1998]
(a) Ethylbenzene  benzene (b) Ethylbenzene 2-phenylpropionic acid
[O]
(a) Ethylbenzene  Soda lime
Ans.   Benzene
2
X KCN HOH
(b) Ethylbenzene 2-phenylpropionic acid
h
6. alcoholic KOH, heat [JEE 1998]

C6H5CH2CHClC6H5 (A) + (B)
Ans. C6H5CH = CHC6H5
(Cis and trans forms)
7. Normally, benzene gives electrophilic substitution reaction rather than thus electrophilic addition reaction although
it has double bonds. Explain. [JEE 2000]
(liq.) Br2 / Fe
8.   [JEE 2000]
Ans.
9. How would you synthesis 4 methoxyphenol from bromobenzene in NOT more than five steps ? State clearly the
reagents used in each step and show the structures of the intermediate compounds in your synthesis scheme.
[JEE 2001]
Br ONa OMe OMe
NaOH Conc. H2SO4 NaOH

Ans. heat high pressure Me2SO4
OMe OMe SO3H
H3O+
ONa OH
10. Carry out following conversions in 3 or less steps. [JEE 2003]
COOH COOH
COOH COOH
Conc. H2SO4 HBF4 / KHF2
Ans.
heat heat
F
ETOOSINDIA N.J. SIR
11. 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-chlorobenzoic acid. Give structures of A and B. [JEE 2003]
O OH
C CH2 CHO C CH CHO
Ans.
Cl Cl
(A) (B)
Keto Enol
Enol form is more stable due to extended conjugation

12. 7-bromo-1, 3, 5-cycloheptatriene is ionic compound, whereas 5-bromo-1, 3-cyclopentadiene can’t ionise even in the
presence of Ag , Explain why ? [JEE 2004]
13. Give reasons : [JEE 2005]
H3C
Br C2H5OH(aq.)
CH3
C2H5OH(aq.)
(a) (i) acidic solution (ii) Br neutral
CH3 CH3
F F
NaOH(aq.) NaOH(aq.)
F (liberated) F is not liberated
(b) (i) O2N (ii) H3C
CH3 CH2NO2
O O O
N N N NO2 NO2
Conc. HNO3 NO2 Conc. HNO3
(c) (i)
+ (ii)
Conc. H2SO4 Conc. H2SO4 NO2
NO2
CH3
Ans. (a) (i) H5C6 C OC2H5 + HBr (acid) ; (ii) no reaction due to partial double bond character
CH3
OH
(b) (i) + F— is liberated ; (ii) Biomolecular mechanism is not possible in (ii) case
O2N
CH3
(c) (i) Due to presence of lone pair of nitrogen atom NO group is electron donating acid ortho, para directing.
(ii) NO2 group is electron withdrawing and meta directing.
ETOOSINDIA N.J. SIR
CH3
Brown fumes and NaBr + MnO2 Conc. HNO3
14. B A C (intermediate) D (Explosive product)
pungent smell
Find A, B, C and D. Also write equations A to B and A to C. [JEE 2005]
CH3
O2N NO2

Ans. (A) H2SO4 (B) Br2 (C) NO2
(D)
NO2
15. Among the following the number of reaction(s) that produce(s) benzaldehyde is [JEE (Advance)-2015]
I. II.
III. IV.
Ans. (4)
Objective Type Questions

16. The chlorination of toluene in presence of ferric chloride gives predominantly : [JEE 1986]
(A) Benzyl chloride (B) m-chlorotoluene (C) Benzal chloride (D) o-and p-Chlorotoluene
Ans. (D)
17. Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halide due to
(A) The formation of less stable carbonium ion (B) Resonance stabilization [JEE 1990]
(C) Longer carbon-halogen bond (D) The inductive effect
Ans. (B)
18. The most basic compound among the following is : [JEE 1990]
(A) Benzylamine (B) Aniline (C) Acetanilide (D) p-Nitro aniline
Ans. (A)
19. Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH gives :
[JEE 1990]
(A) o-Cresol (B) p-Cresol (C) 2,4-Dihydroxytoluene (D) Benzoic acid
Ans. (D)
ETOOSINDIA N.J. SIR
20. Choose the correct statement from the ones given below for two aniline in : [JEE 1993]
+ 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 non aromatic.
(C) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons
(D) II is an acceptable canonical structure.
Ans. (C)
21 Most stable carbonium ion is : [JEE 1995]
(A) p–NO2 – C6H4 – +CH2 (B) C6H5+CH2
(C) p – Cl – C6H4 – +CH2 (D) p – CH3O – C6H4 – +CH2
Ans. (D)
22. Arrange in order of decreasing trend towards SNAE reactions : [JEE 1995]
(I) Chlorobenzene (II) Benzene
(III) Anilinium chloride (IV) Toluene
(A) II > I > III > IV (B) III > I > II > IV (C) IV > II > I > III (D) I > II > III > IV
Ans. (C)
23. Among the following statements on the nitration of aromatic compounds, the false one is : [JEE 1997]
(A) The rate 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.
Ans. (C)
24. Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO3 and conc. H2SO4. In the nitrating
mixture HNO3 acts as a : [JEE 1997]
(A) Base (B) Acid (C) Reducing agent (D) Catalyst
Ans. (A)
25. The most unlikely representation of resonance structure of p-nitrophenoxide ion is : [JEE 1998]
O O O O
O– + O– O– + O– +
+
N N N N
(A) (B) (C) (D)

–
O– O – O
O
Ans. (C)
ETOOSINDIA N.J. SIR
26. Benzenediazonium chloride on reaction with phenol in weakly basic medium gives : [JEE 1998]
(A) Diphenyl ether (B) p-hydroxyazobenzene
(C) Chlorobenzene (D) Benzene
Ans. (B)
27. A solution of (+) -1-chloro-1-phenylethane in toluene racemises slowly in the presence of small amount of SbCl5,
due to the formation of : [JEE 1999]
(A) Carbanion (B) Carbene (C) Free-radical (D) Carbocation
Ans. (D)
28. Amongst the following the strongest base is : [JEE 2000]
(A) C6H5NH2 (B) p-O2NC6H4NH2 (C) m-O2NC6H4NH2 (D) C6H5CH2NH2
Ans. (D)
29. Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds
CH3
(I) (II)
Cl NO2
(III) (IV)
(A) I > II > III > IV (B) IV > III > II > I (C) II > I > III > IV (D) II > III > I > IV
Ans. (C)
(CH3)2NH (i)NaNO2 HCl 0°-5°C

30. F NO2 A B [JEE 2003]
DMF (ii) H2 /Catalytic Reduction
H3C
(A) O2N NH2 (B) N NH2
H3C
H3C H3C
(C) N NO2 (D) N NO2
H2C H3C
NH2
Ans. (B)
ETOOSINDIA N.J. SIR
31. Following compound reacts with Br2/Fe to produce : [JEE 2004]
Br2 /Fe
 
(A) (B)
(C) (D)
Ans. (A)
32. Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of sodium
acetate ? [JEE 2005]
–+
(A) CH3 CO ONa (B) CH3 + SO3
– +
(C) CH3 + SO3 Na + CH3COOH (D) CH3 SO2OCOCH3 + NaOH
Ans. (C)
33. CH3NH2 + CHCl3 + KOH  Nitrogen containing compound + KCl + H2O. Nitrogen containing compound is
[JEE 2006]
—   —
(A) CH3 – C  N (B) CH3 – NH – CH3 (C) CH3  N  C (D) CH 3 N  C
Ans. (D)
34. AlCl3 (i) O2/  [JEE 2006]

+ Cl — CH2CH2 — CH3 P + Q + Phenol
(ii) H3O
ETOOSINDIA N.J. SIR
The major products P and Q are
(A) and CH3CH2CHO (B) and CH3COCH3
(C) and CH3COCH3 (D) and CH3CH2CHO
Ans. (C)
35. In the following reaction,
O
N conc. HNO
3
    X
H conc. H2SO 4
the structure of the major product ‘X’ is [JEE 2007]

O2N
O O
(A) NO2
(B)
N
N
H
H
O O
(C) N (D) O N N
2
H H
NO2
Ans. (B)
36. The major product of the following reaction is [JEE-2008]
(A) (B) (C) (D)
Ans. (A)
ETOOSINDIA N.J. SIR
37. The compounds P, Q and S [JEE 2009]
O
COOH OCH3 C
O
HO H 3C
S
P Q
were separately subjected to nitration using HNO3 / H2SO4 mixture. The product formed in each case respectively,
is
O
COOH OCH3
C
O
(A) HO H 3C
NO2 NO2 O2N
OCH3 O
COOH
C
(B) HO NO2 H 3C O
NO2 NO2
O NO2
COOH
OCH3 C
(C) HO O
H 3C NO2
NO2
O
COOH OCH3
C
O NO2
(D) HO H 3C
NO2 NO2
Ans. (C)
38. In the following carbocation, H/CH3 that is most likely to migrate to the positively charged carbon is :
[JEE 2009]
H H
1 2 + 4 5
H3C C C C CH3
3
HO H CH3
(A) CH3 at C – 4 (B) H at C – 4 (C) CH3 at C – 2 (D) H at C – 2
Ans. (D)
ETOOSINDIA N.J. SIR
O (1) NaOH/Br2
C T
39. In the reaction H3C O [JEE 2010]
NH2
(2) C
Cl
The structure of the Product T is :
O
C O NH
(A) H3C (B)
O C C CH3
O
O
(C) H3C NH (D) H3C C O
C NH C
O
Ans. (C)
40. Among the following compounds, the most acidic is [JEE 2011]
(A) p-nitrophenol (B) p-hydroxybenzoic acid
(C) o-hydroxybenzoic acid (D) p-toluic acid
Ans. (C)
41. The major product of the following reaction is : [JEE-2011]
(A) (B)
(C) (D)
Ans. (A)
ETOOSINDIA N.J. SIR
42. Amongst the compounds given, the one that would form a brilliant colored dye on treatment with NaNO2 in dilute
HCl followed by addition to an alkaline solution of -naphthol is : [JEE-2011]
(A) (B) (C) (D)
Ans. (C)
43. The major product(s) of the following reaction is (are) : [JEE (Advance)-2013]
OH
Br
Br Br
SO3H
P Q R S
(A) P (B) Q (C) R (D) S
Ans. (B)
44. In the reaction shown below, the major product(s) formed is/are : [JEE 2014]
NH2
acetic anhydride
NH2 product (s)
CH2Cl2
H
CH3 NH2
N
H
O + CH3COOH + CH3COOH
N CH3
(A) NH2 (B)
O O
O
H
+
N CH3 NH3CH3COO
H H
O
N CH3 + H2O N CH3
(C) (D)
O O O O
Ans. (A)
ETOOSINDIA N.J. SIR
45 Match the four starting materials (P, Q, R, S) given in List - I with the corresponding reaction scheme (I, II, III, IV)
provided in List - II and select the correct answer using the code given below in lists. [JEE 2014]
List - I List - II
(P) H H (1) Scheme I
+
(i)KMnO4, HO, heat (ii) H, H2O
(iii) SOCl2 (iv) NH3
? C7H6N2O3
OH
(Q) (2) Scheme II

OH
(i)Sn/HCl, CH3COCl, (iii) conc. H2SO4

(iv) HNO3 (v)dil. H2SO4 , heat (vi) HO
? C6H6N2O2
NO2
(R) (3) Scheme III
(i)red hot iron, 873 K(ii) fuming HNO3, H2SO4, heat

(iii) H2S.NH3 (iv) NaNO2, H2SO4 (v)Hydrolysis
? C6H5NO3
NO2
(S) (4) Scheme IV
CH3
(i)conc. H2SO4, 60°C

(ii) conc. HNO3, conc. H2SO4 (iii) dil. H2SO4heat
? C6H5NO4
Code :
P Q R S
(A) 1 4 2 3
(B) 3 1 4 2
(C) 3 4 2 1
(D) 4 1 2 3
Ans. (C)
ETOOSINDIA N.J. SIR
46. In the following reactions, the major product W is [JEE (Advance)-2015]

NH2 OH
NaNO2, HCl , NaOH

V W
0°C
OH
(A) N=N OH (B) N=N
HO
OH
N=N
(C) (D) N=N
Ans. (A)
47. In the following reactions, the product S is [JEE (Advance)-2015]
H3C
i. O3 NH3
R S
ii. Zn, H2O
H3C H3C N
N
(A) (B)
N
N
(C) (D)
HC
3 HC
3
Ans. (A)
48. The product (s) of the following reaction sequence is (are) : [JEE (Advanced) 2016]
NH2 (i) Acetic anhydride/pyridine

(ii) KBrO3/HBr
+
(iii) H3O , heat
(iv) NaNO2/HCl, 273-278 K
(v) Cu/HBr
Br Br Br
Br
Br Br Br Br
(A) (B) (C) (D)
Br
Br Br
Ans. (B)
ETOOSINDIA N.J. SIR
49. The major product U in the following reactions is

+
CH2 = CH–CH3,H radical initiator, O2
T U
high pressure, heat
H H
O H3C CH3 O CH2
O O O O H
(A) CH3
(B) O O H (C) CH2
(D)
Ans. (B)
50. The major product of the following reaction is [JEE (Advanced) 2017]
OH
i) NaNO2, HCl, 0°C

ii) aq. NaOH
NH2
ONa+ OH
(A) (B)
N2Cl Cl
OH
N=N OH
(C) (D)
N=N
Ans. (C)
Multiple Choice type Questions

51. Reaction of R–CO–NH2 with a mixture of Br2 and KOH gives R–NH2 as the main product. The intermediates involved
in this reaction are : [JEE 1992]
(A) R–CO–NHBr (B) RNHBr (C) R–N=C=O (D) R.CO.NBr2
Ans. (A, C)
52. When nitrobenzene is treated with Br2 in presence of FeBr3 the major product formed is m-bromonitrobenzene.
Correct statements are : [JEE 1992]
(A) The electron density on meta carbon is more than on ortho and para position.
(B) The intermediate carbonium ion formed after initial attack of Br+ attack the meta position is least destabilized.
(C) Loss of aromaticity when Br+ attacks at the ortho and para positions and not at meta position.
(D) Easier loss of H+ to regain aromaticity from the meta position than from ortho and para position.
Ans. (A,B)
ETOOSINDIA N.J. SIR
53. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with : [JEE 1998]
(A) SO2Cl2/h (B) SOCl2 (C) Cl2/h (D) NaOCl
Ans. (A,C)
54. Toluene, when treated with Br2/Fe, gives p-bromotoluene as the major product, because the CH3 group :
(A) is para directing (B) is meta directing [JEE 1999]
(C) activates the ring by hyperconjugation (D) deactivates the ring
Ans. (A,C)
OH
NaOH(aq)/Br2
55. In the reaction the intermediate(s) is (are) – [JEE 2009]
O O O O
Br
(A) (B) (C) (D)
Br Br Br
Br Br
Ans. (A,B,C)
56. In the following reaction, the product(s) formed is(are) [JEE (Advance)-2013]
OH
CHCl3
?
OH–
CH3
P Q
R S
(A) P (major) (B) Q (minor) (C) R (minor) (D) S (major)
Ans. (B, D)
ETOOSINDIA N.J. SIR
57. The reactivity of compound Z with different halogens under appropriate conditions is given below –
[JEE 2014]
OH Mono halo substituted derivative when X2 = I2

X2
di halo substituted derivative when X2 = Br2
C(CH3)3 tri halo substituted derivative when X2 = Cl2
The observed pattern of electrophilic substitution can be explained by –

(A) The steric effect of the halogen
(B) The steric effect of the tert-butyl group
(C) The electronic effect of the phenolic group
(D) The electronic effect of the tert-butyl group
Ans. (A, B, C)
58. The correct statement(s) about the following reaction sequence is(are) [JEE (Advance)-2016]
i) O CHCl3 / NaOH
Cumene (C9H12) ii) H 2O+ P  Q (major) + R (minor)
3
NaOH
Q PhCH2Br S
(A) R is steam volatile

(B) Q gives dark violet coloration with 1% aquesou FeCl2 solution
(C) S gives yellow precipitate with 2, 4-dinitrophenylhydrazine
(D) S gives dark violet coloration with 1% aqueou FeCl2 solution
Ans. (B, C)
59. Among the following, reaction(s) which gives(give) tert-butyl benzene as the major product is(are)
[JEE (Advance)-2016]
Br
Cl
(A) (B)
NaOC2H 5 AlCl3
OH
(C) (D)
H2SO4 BF3OEt2
Ans. (B, C, D)
ETOOSINDIA N.J. SIR
ASSERTION & REASON

60. Statement - 1 : Bromobenzene upon reaction with Br2 / Fe gives 1, 4-dibromobenzene as the major product.
and
Statement - 2 : In bromobenzene, the inductive effect of the bromo group is more dominant than the mesomeric
effect in directing the incoming electrophile. [JEE 2008]
(A) Statement - 1 is True, Statement - 2 is True ; Statement - 2 is a correct explanation of Statement - 1.
(B) Statement - 1 is True, Statement - 2 is True ; Statement - 2 is NOT a correct explanation of Statement - 1.
(C) Statement - 1 is True, Statement - 2 is False.
(D) Statement - 1 is False, Statement - 2 is True.
Ans. (C)
61. Statement - 1 : Aniline on reaction with NaNO2 / HCl at 0°C followed by coupling with -naphthol gives a dark blue
coloured precipitate.
and
Statement - 2 : The colour of the compound formed in the reaction of aniline with NaNO2 / HCl at 0° followed by
coupling with -naphthol is due to the extended conjugation. [JEE 2008]
(A) Statement - 1 is True, Statement - 2 is True ; Statement - 2 is a correct explanation of Statement - 1.
(B) Statement - 1 is True, Statement - 2 is True ; Statement - 2 is NOT a correct explanation of Statement - 1.
(C) Statement - 1 is True, Statement - 2 is False.
(D) Statement - 1 is False, Statement - 2 is True.
Ans. (D)
COMPREHENSION
Paragraph - 1 (62 - 64)
RCONH2 is converted into RNH2 by means of Hofmann Bromamide Degradation. [JEE 2006]
O O O
Cl Cl Cl
NH2 NH Br N Br
(i) (ii) (iii)

O—M+ O
O
C
N Cl
N Cl
H2N Cl
H
(v)
(vi) (iv)
In this reaction, RCONHBr is formed from reaction which has derived its name. Electron donating group at phenyl
activates the reaction. Hofmann degredation reaction is an intramolecular reaction.
62. How can the conversion of (i) to (ii) be brought about ?
(A) KBr (B) KBr + CH3ONa (C) KBr + KOH (D) Br2 + KOH
Ans. (D)
ETOOSINDIA N.J. SIR
63. Which is the rate determining step in Hofmann bromamide degradation ?

(A) Formation of (i) (B) Formation of (ii) (C) Formation of (iii) (D) Formation of (iv)
Ans. (D)
64. What are the constituent amines formed when the mixture of (i) and (ii) undergoes Hofmann bromamide
degradation ?
15
CONH2 CONH2
D (i) (ii)
15 15
(A) NH2 , NH2 , NH2 , NH2
D D
15 15 15
(B) NH2 , NH2 (C) NH2 , NH2
15
(D) NHD ,
Ans. (B)
Paragraph - 2 (65 - 67)
Riemer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to the hydroxyl
group. This reaction involves electrophilic aromatic substitution. This is a general method for the synthesis of
substituted salicyladehydes as depicted below. [JEE 2007]
OH O Na OH
CHO CHO
aq. HCl
[I]
[Intermediate]
CH3 CH3 CH3
(I) (II) (III)
65. Which one of the following reagents is used in the above reaction ?
(A) aq. NaOH + CH3Cl (B) aq. NaOH + CH2Cl2 (C) aq. NaOH + CHCl3 (D) aq. NaOH + CCl4
Ans. (C)
ETOOSINDIA N.J. SIR
66. The electrophile in this reaction is

(A) : CHCl (B) +CHCl2 (C) : CCl2 (D) . CCl3
Ans. (C)
67. The structure of intermediate I is
O Na O Na O Na O Na

CH2Cl CHCl2 CCl3 CH2OH
(A) (B) (C) (D)
CH3 CH3 CH3 CH3
Ans. (B)
Paragraph - 3 (68-69)
P & Q are isomers of dicarboxylic acid C4H4O4. Both decolourize Br2/H2O, On heating P forms the cyclic anhydride.
Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one from S, T and U.
[JEE 2013]
COOH COOH COOH
H OH H OH HO H
H OH HO H H OH
COOH COOH COOH

(S) (T) (U)
68. In the following reaction sequences V and W are, respectively -
H2 /Ni
Q 
V
+ V AlCl3(anhydrous) 1. Zn–Hg/HCl
2. H3PO4
W
O CH2OH
and and
(A) (B)
CH2OH
O O
(V) (W) (V) (W)
O HOH2C
and
and
(C) (D) CH2OH
CH2OH (W)
O (V)
(V) (W)
Ans. (A)
ETOOSINDIA N.J. SIR
69. Compounds formed from P and Q are respectively

(A) Optically active S and optically active pair (T, U)
(B) Optically inactive S and optically inactive pair (T, U)
(C) Optically active pair (T, U) and optically active S
(D) Optically inactive pair (T, U) and optically inactive S
Ans. (B)
Paragraph - 4 (70 - 71) [JEE (Advance)-2015]
In the following reactions
Pd-BaSO4 i. B2H6
C8H6 C8H8 X
H2 ii. H2O2 NaOH, H2O
H2O
HgSO4, H2SO4
i. EtMgBr, H2O
C8H8O + Y
ii. H , heat
70. Compound X is
O OH
(A) CH3 (B) CH3
OH
COH
(C) (D)
Ans. (C)
71. The major compound Y is
CH3 CH3
(A) (B)
CH2 CH3
CH3
CH3
(C) (D)
Ans. (D)
Paragraph - 5 (72 - 73)

Treatment of compound O with KMnO4/H+ gave P, which on heating with ammonia gave Q. The compound Q on treatment
with Br 2/NaOH produced R. On strong heating, Q gave S, which on further treatment with ethyl 2-bromopropanoate
in the presence of KOH followed by acidification, gave a compound T.
ETOOSINDIA N.J. SIR
(O)
72. The compound R is
NH2 Br
(A) (B) Br
NH2
O
O O
NHBr
NBr
(C) NHBr (D)
O O
73. The compound T is
(A) Glycine (B) Alanine (C) Valine (D) Serine
Paragraph - 6 (74 - 75)

The reaction of compound P with CH3MgBr (excess) in (C2H5)2O followed by addition of H2O gives Q. The com-
pound Q on treatment with H2SO4 at 0°C gives R. The reaction of R with CH3COCl in the presence of anhydrous
AlCl3 in CH2Cl2 followed by treatment with H2O produces compound S. [Et in compound P is ethyl group]
(H3C)3C
CO2Et
Q R S
74. The reactions, Q to R and R to S are

(A) Friedel-Crafts alkylation and Friedel-Crafts acylation
(B) Dehydration and Friedel-Crafts acylation
(C) Friedel-Crafts alkylation, dehydration and Friedel-Crafts acylation
(D) Aromatic sulfonation and Friedel-Crafts acylation
Ans. (C)
ETOOSINDIA N.J. SIR
75. The product S is

HO3S
H3COC
(H 3C)3C O CH3
(H3C)3C H3C CH3
(A) (B)
COCH3
H3C CH3
COCH3 (H3C)3C
(H3C)3C CH3
(C) (D)
COCH3
Ans. (D)
Paragraph - 7 (76 - 78)

Columns 1, 2 and 3 contain starting materials, reaction conditions, and type of reactions, respectively.
Column I Column 2 Column 3
(I) Toluene (i) NaOH/Br2 (P) Condensation
(II) Acetophenone (ii) Br2/h (Q) Carboxylation
(III) Benzaldehyde (iii) (CH3CO)2O/CH3COOK (R) Substitution
(IV) Phenol (iv) NaOH/CO2 (S) Haloform
76. The only CORRECT combination in which the reaction proceeds through radical mechanism is
(A) (IV) (i) (Q) (B) (III) (ii) (P) (C) (II) (iii) (R) (D) (I) (ii) (R)
Ans. (D)
77. For the synthesis of benzoic acid, the only CORRECT combination is
(A) (II) (i) (S) (B) (I) (iv) (Q) (C) (IV) (ii) (P) (D) (III) (iv) (R)
Ans. (A)
78. The only CORRECT combination that gives two different carboxylic acid is
(A) (IV) (iii) (Q) (B) (II) (iv) (R) (C) (I) (i) (S) (D) (III) (iii) (P)
Ans. (D)
ETOOSINDIA N.J. SIR
MATCH THE COLUMN

79. Match the reactions in Column -I with appropriate options in Column - II. [JEE 2010]
Column - I Column - II
NaOH/H2O OH
+
N2Cl + +
OH N N
(A) –
(P) Racemic mixture
– –
OH OH O
H2SO4
(B) H3C C C CH3 C CH3 (Q) Addition reaction
CH3 CH3 C
CH3
CH3
CH3
O OH
1. LiAlH4
C +
CH
(C) CH3 2. H3O CH3 (R) Substitution reaction
Base S
(D) HS Cl (S) Coupling reaction
(T) Carbocation intermediate

Ans. (A)  R, S, T ; (B)  T ; (C) P, Q ; (D) R

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PREVIOUS YEAR

(1) H3C CN (2) H3C N2Cl

(3) H3C NHCHCl2 (4) H3C NC

The electrophile involved in the above reaction is [AIEEE-2006]

(1) dichlorocarbene (:CCl2) (2) trichloromethyl anion (C Cl3)

The major product C would be :

OH OCOCH3 OCOCH3 OCOCH3

The major product formed is

The product E would be :-

CH2Br CH3 CH3 CH 3

18. In the reaction [JEE(Main)-2015]

the product E is:

(1) (2) (3) (4) H3C CH3

the product C is:

Succinic anhydride Clemmenson's

OH OCOCH3 NH2 NHCOCH3

(1) (2) (3) (4)

(i) Br2, Heat, Light

Ans. (A) (B) (C)

6. alcoholic KOH, heat [JEE 1998]

Br ONa OMe OMe

NaOH Conc. H2SO4 NaOH

OMe OMe SO3H

10. Carry out following conversions in 3 or less steps. [JEE 2003]

Enol form is more stable due to extended conjugation

Find A, B, C and D. Also write equations A to B and A to C. [JEE 2005]

Objective Type Questions

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

(CH3)2NH (i)NaNO2 HCl 0°-5°C

31. Following compound reacts with Br2/Fe to produce : [JEE 2004]

34. AlCl3 (i) O2/  [JEE 2006]

The major products P and Q are

(A) and CH3CH2CHO (B) and CH3COCH3

(C) and CH3COCH3 (D) and CH3CH2CHO

the structure of the major product ‘X’ is [JEE 2007]

36. The major product of the following reaction is [JEE-2008]

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

37. The compounds P, Q and S [JEE 2009]

The structure of the Product T is :

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

(Q) (2) Scheme II

(i)Sn/HCl, CH3COCl, (iii) conc. H2SO4

(R) (3) Scheme III

(i)red hot iron, 873 K(ii) fuming HNO3, H2SO4, heat

(S) (4) Scheme IV

(i)conc. H2SO4, 60°C

46. In the following reactions, the major product W is [JEE (Advance)-2015]

NaNO2, HCl , NaOH

(A) N=N OH (B) N=N

NH2 (i) Acetic anhydride/pyridine

49. The major product U in the following reactions is

i) NaNO2, HCl, 0°C

Multiple Choice type Questions

OH Mono halo substituted derivative when X2 = I2

C(CH3)3 tri halo substituted derivative when X2 = Cl2

The observed pattern of electrophilic substitution can be explained by –

(A) R is steam volatile

ASSERTION & REASON

(i) (ii) (iii)

63. Which is the rate determining step in Hofmann bromamide degradation ?

66. The electrophile in this reaction is

O Na O Na O Na O Na

CH3 CH3 CH3 CH3