ANDHERI / BORIVALI / DADAR / CHEMBUR / THANE / MULUND/ NERUL / POWAI

IIT – JEE CRASH COURSE (ADV.) MARKS: 124

TIME: 75 MIN. DATE:
TOPIC: ALKYL & ARYL HALLIDE, ALCOHOL ETHERS & PHENOLS

SECTION–I (Multiple Choice Questions)

This section contains 06 multiple choice questions. Each question has 4 choices (A), (B), (C) and
(D) for its answer, out which ONLY ONE is correct. (+3,- 1)

1.
OH
D
CHClBrI
?
t--BuO

NH2

(A) O OH (B) O OH
C C
H H

NC NC
(C) O OH (D) O OH
C C
H D

Cl Cl
NC NC

2.
O O
(i) Mg(Hg) in benzene conc
+
A B
H3C (ii) H3O
CH H2SO4
3
Zn (Hg)
conc HCl

C
The product (C) in the above sequence of reactions will be

(A) (B)
H3 C
H3 C CH3 H3C

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 (C) CH3 (D)
H3C CH3

3. During the zeisel estimation of an aromatic ether  C 9 H12 O 3  ,1.68g produces 4.7 g of yellow ppt.
what is the structure of the ether?

(A) OCH3 (B) OCH3

OCH3 OCH3

CH2OH OCH3
(C) OCH3 (D) OH
CH2OH

HOH2C CH2OH H3C

OCH3

4.
OH CHO
OCH3
Br2
+
CH3O G Br
G
The rate of reaction is moderately affected by the nature of G. Choose the correct decreasing rate of
reaction with various substituents as G.
(A)  NO 2  Br  H  CH3  OCH3 (B) OCH3  CH3  H  Br   NO2
(C) OCH 3  Br   CH 3   H   NO 2 (D)  NO 2  OCH 3   Br   H  CH3

5. Find the product of the following reaction:

R R 
CH2
R O

(A) R O (B) R
and CH 3  CH  CH 2 R
R R
O R
(C) R (D) R
H
andH2C R
CH2
R R O R
O

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6. The following compounds on treatment with HI at 273 K give an alcohol and alkyl iodide which of
these form an alcohol that gives positive haloform reaction?
CH3 CH3 CH3
O CH CH3 CH3 CH O C CH3
2
CH3
(I) (II)
CH3
CH3 CH3CH2O C CH3
CH3CH2O CH CH3 CH3
(III) (IV)

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

SECTION-II (Multiple Choice Questions)

This section contains 06 multiple choice questions. Each question has 4 choices (A), (B), (C) and
(D) for its answer, out which ONE OR MORE is/are correct. (+4,- 2)

7. Which of the following reactions are correctly interpreted?

(A) CH3
H2O
 Hg  OAc 2 
NaHB4
 Product is a mixture of
diastereomers
CH3
(B) CH3 CH3 CH3 O

Ag
CH3 C C   C C CH3
OH Cl

CH3
(racemic mixture)
(C) CH3 CH3
Ts Cl CH3 CH 2SH
OH   A   SCH2CH3

(D)
Pt
O O  H 2   HO OH

8. Identify the correct statements:

(A) 1, 2, 1, 3 and 1, 4 dioxanes are used as solvents in reactions involving Grignard reagent
OCH3
CH3 CH 2 CH  CH  OH and CH3  CH H32C4 CH
O OH OCH3
(B) all give positive tollen’s
reagent test
(C) The alcohol which reacts most readily with Na metal will give fastest turbidity with lucas reagent
(D) Acylation of salicylic acid in basic medium occurs on phenolic oxygen
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9. Compound (X) C 4 H8O decolonizes Baeyers reagent. It undergoes hydrolysis in dil H 2SO4 to give
(Y) and (Z) where both (Y) and (Z) give positive iodoform test while only (Y) responds to Tollen’s
test but (Z) does not. Choose the correct statements of the following.
OH
(A) Y  
 CH3  CH  CH  CHO
(B) Z 
PCC/CH 2 Cl 2
Y
O3 / Zn /H 2 O
(C) X  Y  other product
HI aq.KOH
(D) X  Y  W W  Z

10. Which of the following can give E 1 CB reaction

(A) OH (B) H
CH 3 CH CN Cl C CF3
Cl
(C) O OH (D) HCF2  CCl3

H3C CH3
CH3

11. Identify the correct statements

(A) Isobutene reacts faster than propene with HCl
(B) The total number of stereoisomer obtained when 1, 6 – dimethyl cyclohexene reacts with HBr in
presence of peroxide is 8.
(C)
Cl F

undergoes SNAr2 faster than

NO2 NO2
(D) The decreasing leaving group ability follows the order NH 3  PH3  AsH3  SbH 3

12. Which of the following paths is/are feasible for preparation of divinylether

(A) H C ONa +H C
2 X
2
(B) H C OH + HO conc
2 X
H 2SO 4

Low temperature
(C) i  Hg OCOCF3 2
CH 2  CH 2 
 ii  CH 2 CH OH 
 iii  NaBH 4
(D) ClCH 2 CH 2 OH   i  conc H 2SO 4
 ii  NaNH 2 

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 SECTION – III (Paragraph Type)
This section contains 2 multiple choice questions relating to 1 paragraph. Each question has four
choices (A), (B), (C) and (D) out of which ONLY ONE is correct. (+3,- 1)

PARAGRAPH FOR QUE. NOS. 13 & 14

13. The compound (C) is

(A) OH (B) Cl
Cl OH

Cl Cl
Cl Cl
(C) OH (D) Both (A) and (B)
Cl

Cl
Cl

14. The compound (E) is

(A) OH OH (B) OH Cl
Cl Cl Cl Cl

Cl Cl Cl Cl
Cl Cl Cl OH
(C) OH OH (D) Both (A) and (C)
Cl Cl

Cl Cl Cl
Cl

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 PARAGRAPH FOR QUE. NOS. 15 & 16

15. Identify the correct statements:-

(A) The products (F) and (G) are structural isomers
(B) The products (F) and (G) are geometrical isomers
(C) The compound (D) is
CH3
O
CH3

H3C CH3
(D) The compound (I) is
OH

16. The reaction and mechanism involved in formation of (H) from (A) respectively are:-
(A) Elimination reaction, E1 (B) Elimination reaction, E1CB
(C) Williamsous synthesis SN 2 (D) Williamsous synthesis SN1

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 PARAGRAPH FOR QUE. NOS. 15 & 16

HBr
C8 H13 Br     B  C
Meso R acemate
(A)
t-BuONa

t-BuOH
Br2
Br
(A)  

C8 H12 Br

COOEt

COOEt

(F) 
O3 / Zn/ H 2 O G 
17. Compound (G) is

(A) O (B) O
COOEt
COOEt

COOEt
COOEt O
O
(C) O (D) O O

COOEt COOEt
COOEt COOEt
O
O O

18. Compound (D) is

(A) CH3 (B) CH2

CH2 CH2
(C) CH2 (D) CH3

CH3
CH3

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 SECTION – IV (Integer Answer Type)
This section contains 08 questions. The answer to each of the questions is a single digit integer,
ranging from 0 to 9. The correct digit below the question number in the ORS is to be bubbled.
(+4, 0)

19.
O O

 i AlCl
2 + O O 
3
 ii  HCl  A    B
Zn  Hg  / conc HCl
O O
C  D
H3 PO4

 E  F
Zn  Hg  / conc HCl

G
The number of benzene rings in (G) is:

20. The total number of   bonds present in the intermediate meisenheimer complex of the following
reaction is
Cl NR2


R2 N H  HCl
 
H3C CH3 H3C CH3
CN CN

21.
O O CH3
O
H3C O
O O
H3C O
O CH3
Cl
O O O OHO

H3C
The ratio of the number of moles of Grignard reagent consumed by the above compound to the
number of moles of ethanol formed in the reaction will be

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22. The total number of moles of HIO 4 needed for the oxidation of
OH
O OH
OH
is :
OH
OH
OH CH3

23. The number of molecules among the following which give haloform reaction:
O O O O O
CH3 C O C CH3 , CH3 C C OH , CH3 C Cl
O O Cl O
CH3 C OCH3 , CH3 C NH2 , CH3 CH C CH3 ,
O O OH O
CH3 , ,
C C CH3 CH C CH3 CH3 CH C CH3
Cl OH

24.
H3 C CH3
NBS

h


Total number of products obtained (excluding stereoisomers)

25. The total number of product including minor product and stereoisomers possible in the following
reaction are:
CH3

H

CH3 
OH

26. The number of ethers among the following which can be prepared using Williamsons synthesis are:
O O
H3C CH3
CH 2  CH  O  CH  CH 2
CH3
CH3 CH3 O CH3
O CH3
H3 C O CH3 O CH3
H3 C
O CH3
CH3
CH3
O 2N

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 SECTION - V (Matrix Match Type)
This section 1 Question. Each question has four statements Given in Column - I and four statements
in Column – II. Any given statement in Column – I can have correct matching with one or more
statement (s) given in column II. (+8, 0)

27. Match the column:-

Column – I Column – II
(A) NO2 (P) SArE 2

3
EtO

2
Br 1
Cl
(B) OH (Q) Reaction at position – 1
3
2 Br2

Fe

1

NO2
(C) OCH3 (R) Reaction at position – 2

3 HNO
 3
H 2 SO4

2
1
Br
(D) 1 (S) Reaction at position – 3
2
Br2

Fe

3

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28.
Column – I Column – II
(A) CH3 (P) SN 2 reaction on treatment with alcoholic
CH3 C Cl NaSH
CH2CH3
(B) Br (Q) E 2 reaction on treatment with alcoholic KOH

(C) Cl (R) SN Ar reaction on treatment with fused NaOH

H3 C CH2-CH2Cl

(D) CH3 (S) SN1 reaction with aq- KOH

Br

H3C CH3

29.
Column – I Column – II
(A) COOH (P) CO 2 gas will be evolved on addition of
HO3S NaHCO3

OH
CH2-OH
(B) OH (Q) H 2 gas will be evolved on addition of Na
metal

(C) C CH (R) H 2 O will be formed on addition of NaOH

CH2OH
(D) OH (S) NH3 gas will be evolved on addition of
NaNH 2

OH
OH

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30.
Column – I Column – II
(A) CH3 (P) Saytzeff alkene is the major product
Ph H  
CH3O K
 
Ph Br
CH3
(B) CH3 (Q) Hofmann’s alkene is the major product
Br
 
C2 H 5 O K
 

(C) (R) Stereo specific reaction

OH


+
N
Me
Me
(D) CH3 (S) A single stereoisomer will be obtained
 
C2H 5O K
 
F

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 ANDHERI / BORIVALI / DADAR / CHEMBUR / THANE / MULUND/ NERUL / POWAI
TOPIC: (ANSWER KEY)

1. (D)
t  BuO
CHClBrI  C
H Cl
carbene
Carbenes with phenols show Reimer – Tiemann reaction, with 1o amines carbylamine reaction and
with alkenes a cycloaddition reaction
2. (B)
  
i Mg Hg in benzene

 ii  H O 
3

H3C OO CH3
H3C OH OHCH3
Pinacol
Pinacol-pinacolone conc H2SO4
rearrangement

Zn  Hg 
H3C  HC
conc.HCl 3

H3C H3C O
3. (A)
In zeisels method of estimation of ethers. The ether is treated with HI and then the iodide with
AgNO3 to give a yellow ppt of AgI
R  OR  HI  ROH  RI
RI  AgNO3  AgI 
Yellow ppt
Mol weight of C9 H12O3  168
1.68
No. of moles taken   0.01mole .
168
4.7
No. of moles of AgI produced   0.02moles
235

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4. (B)
OH
Br

Br
 G
H3C
CH3O G + OH
O

HC OH
Br

+
CH3O

G
H 
CHO

G
5. (D)
The reaction involved is claisen Rearrangement
R O R O

R R H2C R R H3C

R O

R CH2
R
6. (B)
CH 3 CH 3 CH 3
HI
CH3  CH  O  CH  CH 3 
273K
 CH 3  CH  CH 3  CH 3  CH  I
OH
CH 3 CH3
CH3  CH  O  C  CH 3 3 
HI
273K
 CH 3CH  CH3  CH3  C  I
OH CH3
CH3 CH 3
HI
CH3  CH 2  O  CH  CH 3 
273K
 CH 3  CH 2 I  CH3  CH  OH
CH 3  CH 2  O  C  CH 3 3 
HI
273K
 CH 3CH 2 OH   CH 3 3 CI

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7. (BD)
CH3 CH3 OH
OMDM
(A)  OH + CH3
CH3 H CH3
CH3 H
CH3 CH3 CH3 CH3
Ag 
(B) CH3 C C  H3C
 AgCl C C
OH Cl OH

O CH3
CH3 CH3
CH3 C C
H 
+ C
  O
H

CH3
CH3
(both the enantiomers are
obtained)
CH3 CH3 CH3

OH OTs SCH2CH3
TsCl CH3 CH 2SH
(C)    
8. (D)
(A) 1, 2 – dioxane being a peroxide is not a very stable compound

Tautomerium
(B) CH 3  CH 2  CH  CH  OH   CH 3CH 2CH 2CHO gives tollen’s reagent test.

O OH
Hemiacetals responds to Tollen’s reagent test
OCH3
acetals do not respond to
CH3  CH 2 4  CH Tollens test
OCH3
(C) Acidic strength in alcohols is 1o  2o  3o
O
OH ONa O C R
COOH basic
COONa COONa

Medium
(D) NaOH O
C
R Cl
 NaCl

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9. (ABD)
CH 2  CH  O  CH 2  CH 3 
H O/H 
 CH 2  CH  OH  CH3CH 2 OH
2

X  Z
 Y
CH3CHO
10. (BD)
E1CB occurs on alkyl halides with electron withdrawing groups on   carbon
11. (AB)
H3C H3C
H  o
(A) CH2  CH
3 3
H3C H3C 
H
H3C CH   H3C CH
H3C2 2o 3
H3C Me
(B) HBr Me Br

peroxide

12. (D)
conc H 2SO 4
2Cl  CH 2 CH 2 OH 413K
 ClCH 2CH 2 OCH 2CH 2Cl
NaNH 2
CH 2  CH  O  CH  CH 2
13. (C)
14. (A)
Sol. 13& 14

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15. (B)
16. (C)
Sol. 15&16.

17. (B)
18. (B)
Sol. 17 & 18
Br Br
CH2 Me Me
HBr
   +
Me Me Me
Br Br Br
(meso) (C)
(B) optically active

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 t-BuONa
t-BuOH
COOEt
CH2 COOEt
EtOOC
CH2 COOEt
(D) (F)
O3 | Zn | H 2O

O
COOEt

COOEt
O
19. (3)
O O

A=
HOOC COOH
O
COOH
B=

HOOC
O

C=

HOOC COOH
COOH
D=

HOOC

E=

O O
O

F=

G=

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20. (4)
Cl Cl NHR2

NHR2
H3C CH3 H3C CH3
C C
N N
intermediate
 Cl
NR2 NHR2


H
 
H3C CH3H3C CH3
CN CN
21. (7)
No. of moles of Grignard reagent used will be 14 and number of moles of ethylalcohol formed are 2.
22. (6)
OH
O OH
OH
OH
OH
OH CH3
23. (5)
Cl O O O OH
CH3COCOOH , CH3 CH C CH3 , CH3 C C CH3 , CH C CH3
O Cl
and CH3 CH C CH3 respond to haloform reaction
OH
24. (4)
Br
Me Me Me Me Me Me

Br
Br
Br
Me

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25. (7)
CH3
CH3 CH3 CH3 CH3
CH3 CH3 CH3
CH3 CH2
CH3 CH3

26. (4)
27. ( A  Q; B  P, R;C  P,S; D  P, Q )
28. ( A  Q,S; B  R; C  P, Q; D  Q,S )
29. ( A  P, Q, R,S; B  Q, R,S; C  Q,S; D  Q,S )
30. ( A  P, R,S; B  Q, R,S;C  Q; D  Q, R,S )

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