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JEE ADVANCED-VOL - VIII

1.

OH

JEE ADVANCED-VOL - VIII 1. OH H +  EXERCISE LEVEL - IV ALKYL HALIDES &

H +

JEE ADVANCED-VOL - VIII 1. OH H +  EXERCISE LEVEL - IV ALKYL HALIDES &

EXERCISE LEVEL - IV
EXERCISE
LEVEL - IV

ALKYL HALIDES & ARYL HALIDES

CH 3 CH 2 CH 3 (A) (B) (C) (D)
CH 3
CH 2
CH 3
(A)
(B)
(C)
(D)

2.

3

86

OH H + ?  CH 2 CH 2 CH 2 CH 3 (A) (B)
OH
H +
?
CH 2
CH 2
CH 2
CH 3
(A)
(B)
(C)
(D)
H 2 O
.
M ajor product is ?
Cl
H 3 CO
NO 2
(A) (B) OH OH H 3 CO NO 2 H 3 CO NO 2 OH
(A)
(B)
OH
OH
H 3 CO
NO 2
H 3 CO
NO 2
OH
(C)
(D)
OH
H 3 CO
NO 2
H 3 CO
NO 2
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JEE ADVANCED-VOL - VIII

4.

5.

6.

Cl a Cl CH 3 OH b O c Cl
Cl
a
Cl
CH 3 OH
b
O
c
Cl

Which of the following statements is correct ?

(A) major product is formed at a . (C) major product is formed at c
(A)
major product
is formed at a .
(C)
major product
is formed at c .
(B) major product is formed at b .
(D)Reaction does not take place.
TsCl
HS
OH
A
B
Pyridine
B is
SH
SH
HO
S
O
(A)
(B)
(C)
(D)
OH
H C
2
OH
PCC /CH 2 Cl 2
H C
3
H C
3
O (A) H C (B) 3 H C 3 O O (C) H C (D)
O
(A)
H C
(B)
3
H C
3
O
O
(C)
H C
(D) H C
3
3
CH 3
CH 3

7. C 6 H 5 CH 2

OH

PBr 3

H C 3 3 CH 3 CH 3 7. C 6 H 5 CH 2 OH

A Mg / Ether

3 CH 3 7. C 6 H 5 CH 2 OH P B r 3 A

B

O

CH 3 7. C 6 H 5 CH 2 OH P B r 3 A Mg

C

H 3 O +

H 5 CH 2 OH P B r 3 A Mg / Ether B O C

D

(A)

C 6 H 5 CH 2 OCH 2 CH 3

(B)C 6 H 5 CH(OH)CH 2 CH 2 OH

(C)

C 6 H 5 CH 2 CH 2 CH 2 OH

(D)C 6 H 5 CH 2 CH 2 OCH3

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ALKYL HALIDES & ARYL HALIDES

8.

CH 2 H + OH ? CH 2 CH 3 CH 3 CH 2 (A)
CH 2
H +
OH
?
CH 2
CH 3
CH 3
CH 2
(A) O
(B)
O
(C)
(D)
O
O
H C 3 OH SOCl 2 ? 9. H C 3 CH 3 H C
H
C
3
OH
SOCl 2
?
9. H
C
3
CH 3
H
C
H
OH
H
C
Cl H
C
3
3 C
3
3
Cl
(A) H
(B) H
C
(C) H
C
(D )
H
C
3 C
3
3
3
CH 3
CH 3
CH 3
CH 3

10 .

11.

12.

88

A C 6 H 12 O compound does not react with Br 2 in CCl 4 , produces a flammable gas on treatment with LiAlH 4 , and reacts with H 2 CrO 4 changing the color from orange to green. Which of the following compounds best agrees with these facts? (A)1-methylcyclopentanol (B) methoxycyclopentane (C)2-cyclopropyl-2-propanol (D) 2-cyclobutylethanol

O O CH 3 x moles of HI CH 3 y moles of HI Sum
O
O
CH 3
x moles of HI
CH 3 y moles of HI
Sum of x and y is
(A) 2
(B) 3
(C) 4
(D) 5
18 O
H + /H 2 O
CH 3
H C
3
Products formed are
18 O
18 O
H
H
CH 3
18 OH
OH &
CH 3
(A)
&
(B)
H C
H C
3
3
HO
18
O HO
(C)
O &
(D)
&

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JEE ADVANCED-VOL - VIII

13.

CH 3 O O AlCl 3 Product formed is? CH 3  CH(CH 3 )
CH 3
O
O
AlCl 3
Product formed is?
CH 3
CH(CH 3 ) 2
CH 3
CH 3
CH 3
OH
OH
O
H C
(A)
3
(B)
O CH(CH 3 ) 2
CH(CH 3 ) 2
CH 3
CH
3
OH
OH
H C
(C)
(D)
3
CH(CH 3 ) 2
O CH
3

14.

15.

H

Cl OH OH - / CH 3 3 C + ? NO 2 CH 3
Cl
OH
OH - /
CH 3
3 C
+
?
NO 2
CH 3
H C
O
3
O
(A)
(B)
NO 2
CH 3
NO 2
CH 3
O
O
H C
3
(C)
(D)
H C
CH 3
NO 2
H C
CH 3
NO 2
3
2

Which of the statements is incorrect? (A)2,4,6 trimethyl phenol is less acidic than 2,4,6trinitrophenol. (B)2,6 dichlorophenol is stronger than 3,5 dichloro phenol (C)para nitro phenol is more acidic than meta nitro phenol. (D)para chloro phenol is less acidic then para flouro phenol.

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ALKYL HALIDES & ARYL HALIDES

16 .

HO H + ? OH O (A) (B) (C) (D) OH O HO
HO
H +
?
OH
O
(A)
(B)
(C)
(D)
OH
O
HO

17.

16 . HO H + ? OH O (A) (B) (C) (D) OH O HO 17.

Appropriate product among the following.

OH OH D CDO D CHO (A) (B) D OH O ODC CHO D CHO
OH
OH
D CDO
D
CHO
(A)
(B)
D
OH
O
ODC
CHO
D
CHO
(C)
(D)

18.

90

CH 3 OH H + (major) ? CH 3 CH 3 CH 3 (A) (B)
CH 3
OH
H +
(major)
?
CH 3
CH 3
CH 3
(A)
(B)
CH 3
CH 3
CH 2
CH 3
(C)
(D)

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JEE ADVANCED-VOL - VIII

19.

A C 7 H 14 O optically active alcohol is oxidised by jones reagent to
A C 7 H 14 O optically active alcohol is oxidised by jones reagent to an optically inactive ketone
.The molecule is .
HO
OH
O
H C
OH
3
(A)
(B)
(C)
(D)
OH
HO
HO

20.

O H + / H 2 O ? O O O OH HO (a) (
O H + / H 2 O
?
O
O
O
OH
HO
(a)
( b)
(c) CH 3
(d)
OH
HO
HO

21.

22.

OH (i)CHCl 3 + KOH ? (ii)CH 2 I 2 + NaOH OH OH OH
OH
(i)CHCl 3 + KOH
?
(ii)CH 2 I 2 + NaOH
OH
OH
OH
OH
O
(A)
(B)
(C)
(D)
O
HOOC
OH
OHC
OH
OHC
OHC
OH

A chiral C 5 H 10 O ether reacts with hot HI to give a C 5 H 10 I 2 product. Treatment of this with hot KOH in ethanol produces 1,3-pentadiene. What is the structure of the original ether?

CH 3 CH 3 CH 3 CH 3 H C (A) (B) (C) (D) 3
CH 3
CH 3
CH 3
CH 3
H C
(A)
(B)
(C)
(D)
3
O
O
O
O
23.
A chiral C 7 H 16 O 2 diol is oxidized by PCC in CH 2 Cl 2 to an achiral C 7 H 12 O 2 compound.
Which of the following would satisfy these facts?
C
C
H 3
H 3
H C
H C
3
3
OH
OH
OH
OH
H
H
3 C
3 C
H C
H C
(A)
C
C
H 3
(B)
H 3
(C)
3
(D)
3
OH
OH
OH
OH
H C
H C
C
C
H 3
H 3
3
3
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ALKYL HALIDES & ARYL HALIDES

24.

A chiral C 5 H 10 O alcohol is reduced by catalytic hydrogenation to an achiral C 5 H 12 O alcohol.The original alcohol is oxidized by activated MnO 2 to an achiral carbonyl compound (C 5 H 8 O)Which of the following might be the chiral alcohol?

(A)1-penten-3-ol

(C)3-methyl-2-buten-1-ol

(B) 4-penten-2-ol (D) 2-methyl-2-buten-1-ol

25.

26.

Which of the following ethers is unlikely to be cleaved by hot conc. HBr? O
Which of the following ethers is unlikely to be cleaved by hot conc. HBr?
O
O
O
O
CH 3
(A) (B)
(C)
(D)
Phenol reacts with Phthalic anhydride in the presence conc.
H SO
to give
2
4

27.

(A) Methyl orange (B) Phenolphthaline + O - Na CO 2 Ac 2 O A
(A) Methyl orange
(B) Phenolphthaline
+
O - Na
CO 2
Ac 2 O
A B
 H 3 PO 4

Identitify B in the sequence

(A) Methyl orange

(B) Phenolphtheline

(C)

Aspirin

(D)

Methyl Blue

(C)

Aspirin

(D)

Methyl Blue

28.

29.

92

O

O HO OH x
O
HO
OH
x

OH

In the above transaformation ‘X’ could be

(A) NaBH C H OH H O  4 2 5 3 (C) LiAlH Et
(A)
NaBH
C H OH
H
O 
4
2
5
3
(C)
LiAlH
Et O
H
O 
4
2
3
HO
OH
H C
3
 (B) N H OH 2 4 (D) DIBAL  H O O H C
(B)
N H
OH
2
4
(D)
DIBAL
 H
O
O
H C
H
3

Glycol |

THF H O

3

The above transformation can be done by using

(A)

Baeyer’s Reagent

(C)

Pyridinium dichromate in

CH Cl

2

2

(B) Tollen’s reagent

(D) Jone’s reagent

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JEE ADVANCED-VOL - VIII

30. An unknown organic compound (A) having M.F. C H O reacts with an excess of acetyl chloride gives an acetyl derivative with M.Wt. 218. Then howmay hydroxyl groups are in ‘A’.

3

8

3

(A) 2 (B) 3 (C) 4 (D) 5 MULTIPLE CORRECT ANSWER TYPE QUESTIONS 31. HBO
(A) 2
(B) 3
(C) 4
(D) 5
MULTIPLE CORRECT ANSWER TYPE QUESTIONS
31. HBO and Oxymercuration -Demercuration , and acid catalysed hydration will not give the same
product in
CH 2
CH 3
(A) H C
(B)
CH
3
CH
2
3
CH 3
(C)
(D)
32. Which method is usefull synthesis of ether
(A)
-
(B) H C
O
(CH 3 ) 2 SO 4
Na +
3
-
O
H C
Na + +
3
(C) H C
(D) (CH 3 ) 3 CBr
+
CH 3 CH 2 ONa
3
O
SO 2 C 6 H 5 CH 3
33. Which of the following alcohols donot give white turbidity on treatment with HCl/ZnCl 2
CH 3
N
3
OH
3
(A) H C
(B)
(C)
(D) H C
OH
OH
OH
CH 3
34. Which of the following gives positive victormeyer test and yellow precipitate with NaOH / I 2
OH
NO 2
H C
3
3
(A) H C
(B)
(C) H C
(D) H C
3
OH
OH
CH 3
CH
3
3
35. Which of the following is correctly matched
CH 3
HI
H + /H 2 O
H C
O
3
O
S N 1
CH 3
S N 1
(A) H C
3
(B)
CH 3
CH 3
CH 3
H C
O
3
HI
HI
CH 3
S N 2
O
(C)
(D)
S N 1
CH 3
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ALKYL HALIDES & ARYL HALIDES

36. In which of the following ring expansion / ring contraction takes place when protic acid is added to the compound?

HO OH CH 3 (A) (B) CH 3 OH (C) (D) OH H C 3
HO
OH
CH 3
(A)
(B)
CH 3
OH
(C)
(D)
OH
H C
3
37. Which of the following undergo reimer tiemann reaction?
OH
CH 3
OH
NO 2
O
(A)
(B)
(C)
(D)

38. Which of the following statements is (are) correct?

(A) Nitration of phenol is faster than phenyl acetate. (B) Reaction of phenoxide ion is
(A)
Nitration of phenol is faster than phenyl acetate.
(B)
Reaction of phenoxide ion is faster than para cyano phenoxide With PhCH 2 Cl.
(C)
Base cataltsed hydrolysis of p-nitrophenyl acetate is faster than phenyl acetate.
(D)
Acid catalysed esterification of phenol is faster than p-nitro phenol.
39. Which of the follwoing compounds would give alcohol on reduction by
LiAlH
/ Et O / H O 
4
2
3
O
O -
O
(A)
(B)
O
O
O
O
O
O
C)
D)
Cl
C H
3
H O
HO

40. Select the correct statemnts from the follwoing

(A) P-methoxy phenol is more reactive than P-nitro phenol towards Reimer-Tieman reacton. (B) Phenol gives
(A)
P-methoxy phenol is more reactive than P-nitro phenol towards Reimer-Tieman reacton.
(B)
Phenol gives ortho isomer predominantly than para isomer in Reimer-Tieman reacton.
(C)
The electrophile involved in R.T.R is Cl  .
(D)
Para cresol is less reactive than phenol in R.T.R.
41. Which of the follwoing speces would you expect to obtain when P-creaol is subjected to Reimer-
Tieman reacton.
OH
OH
O
O
CHO
(A)
(B)
(C)
(D)
CH
CHCl
CH
COOH
2
CHO
3
3

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COMPREHENSION TYPE QUESITONS
COMPREHENSION TYPE QUESITONS

COMPREHENSION -1 1-chloromethyl -4 - methyl - 1,3 -cyclopentadiene is solvolysed in aqueous acetone based on the above solve the following questions.

42. Which of the intermediates is not possible? (A) (B) (C) (D)
42. Which of the intermediates is not possible?
(A)
(B)
(C)
(D)

43. Which of the following product is not formed ?

OH (A) (B) OH OH (C) HO (D)
OH
(A)
(B)
OH
OH
(C) HO
(D)

44. The number of enantiomeric pairs formed during the reaction is

(A)1

(B) 2

(C) 3

(D) 4

COMPRAHENSION - 2 The alkali metals (Li, Na, K etc.) and the alkaline earth metals (Mg and Ca, together with Zn) are good reducing agents, the former being stronger than the latter. Sodium, for example, reduces elemental chlorine to chloride anion (sodium is oxidized to its cation), as do the other metals under varying conditions. In a similar fashion these same metals reduce the carbon-halogen bonds of alkyl halides. The halogen is converted to halide anion, and the carbon bonds to the metal (the carbon has carbanionic character). Halide reactivity increases in the order: Cl < Br < I .These reactions are obviously substitution reactions, but they cannot be classified as nucleophilic substitutions, as were the earlier reactions of alkyl halides. Because the functional carbon atom has been reduced, the polarity of the resulting functional group is inverted (an originally electrophilic carbon becomes nucleophilic).Reactions of organolithium and Grignard reagents reflect the nucleophilic (and basic) character of the functional carbon in these compounds.The nucleophilic carbon of these reagents also bonds readily with electrophiles such as iodine and carbon dioxide. The polarity of the carbon-oxygen double bonds of CO 2 makes the carbon atom electrophilic, shown by the formula in the shaded box, so the nucleophilic carbon of the Grignard reagent bonds to this site.

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JEE ADVANCED-VOL - VIII

45.

What is the product (B) of the following reaction sequence ?

ALKYL HALIDES & ARYL HALIDES

O Br Mg A B Et 2 O Hydrolysis of B gives OH OH (A)
O
Br
Mg
A
B
Et 2 O
Hydrolysis of B gives
OH
OH
(A)
(B)
OH
O
(C)
(D )
OH
OH

46.

of B gives OH OH (A) (B) OH O (C) (D ) OH OH 46. Product

Product formed is

OH O OH OH (A) (B) Et Et OH O OH OH (C) (D) Et
OH
O
OH
OH
(A)
(B)
Et
Et
OH
O
OH
OH
(C)
(D)
Et
Et

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COMPRAHENSION -3 Ring-opening reactions of epoxides can proceed by either S N 2 or S N 1 mechanisms, depending on the nature of the epoxide and on the reaction conditions. If the epoxide is asymmetric, the structure of the product will vary according to which mechanism dominates. When an asymmetric epoxide undergoes solvolysis in basic methanol, ring-opening occurs by an S N 2 mechanism, and the less substituted carbon is the site of nucleophilic attack. Conversely, when solvolysis occurs in acidic methanol, the reaction occurs by a mechanism with substantial S N 1 character, and the more substituted carbon is the site of attack. These are both good examples of regioselective reactions. examine the basic, S N 2 case first. The leaving group is an alkoxide anion, because there is no acid available to protonate the oxygen prior to ring opening. An alkoxide is a poor leaving group, and thus the ring is unlikely to open without a ‘push’ from the nucleophile. Like in other S N 2 reactions, nucleophilic attack takes place from the backside, resulting in inversion at the electrophilic carbon. The best way to depict the acid-catalyzed epoxide ring-opening reaction is as a hybrid, or cross, between an S N 2 and S N 1 mechanism. First, the oxygen is protonated, creating a good leaving group. Then the carbon-oxygen bond begins to break and positive charge begins to build up on the more substituted carbon . answer the folllowing based on the above:

47.

O
O

CH 3 CH 2 OH

folllowing based on the above: 47. O CH 3 CH 2 OH NaOH Product formed is?

NaOH

Product formed is?

OH OH (A) ( B ) OCH 2 CH 3 OCH 2 CH 3 OH
OH
OH
(A)
( B )
OCH 2 CH 3
OCH 2 CH 3
OH
OH
(C)
(D)
OCH 2 CH 3
OH
-
+
O CH O Na
48. Cl
3
The final product that is formed in the reaction is
OH HO (A) H 3 CO (B) HO OCH 3 O CH 3 HO CH
OH
HO
(A) H 3 CO
(B) HO
OCH 3
O
CH 3
HO
CH 3
O
(C) O
(D) Cl
O
CH 3
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JEE ADVANCED-VOL - VIII

49.

O O O
O
O
O

1EQV PhS

JEE ADVANCED-VOL - VIII 49. O O O 1 EQV PhS  OH ALKYL HALIDES &

OH

ALKYL HALIDES & ARYL HALIDES

The product formed after nucleohillic attack and

mild hydrolysis is O O O O (A) (B) O O OH OH O O
mild hydrolysis is
O
O
O
O
(A)
(B)
O
O
OH
OH
O
O
O
O
(C)
(D)
O
O
OH
OH

COMPRAHENSION- 4

OH OH O O O O (C) (D) O O OH OH COMPRAHENSION- 4 Where E

Where E = electrophile, L.G. = Leaving Group based on the above answer the following

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JEE ADVANCED-VOL - VIII

50. Which of the following combinations give aryl alkyl ethers on heating Cl (A) O
50. Which of the following combinations give aryl alkyl ethers on heating
Cl
(A) O 2 N
& +Na - O
Cl
(B)
& +Na - O
Cl
(C)
& +Na - O
Cl
& +Na - O
(D)
O 2 N

51 .

Which of the following does not give phenolic type compound on acidic hydrolysis . O
Which of the following does not give phenolic type compound on acidic hydrolysis .
O
O
O
(A)
O (B)
(C)
(D)

52. Which of the following products cannot be formed without blocking reagent action on phenol ?

OH OH Br Br COOH (A) (B) Br OH O Br (C) (D) Narayana Junior
OH
OH
Br
Br
COOH
(A)
(B)
Br
OH
O
Br
(C)
(D)
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COMPRAHENSION- 5

ALKYL HALIDES & ARYL HALIDES

Compound (A), C 10 H 12 O gives off hydrogen on treatment with sodium metal and decolourises Br 2 in CCl 4 to give (B), C 10 H 12 OBr 2 . (A) on treatment with I 2 in NaOH gives iodoform and an acid (C) after acidification. Give the structures of (A) to (C) and also of all geometrical and optical isomers of (A). Answer the following based on the above.

53. Compound A is OH (A) (B) HO HO (C) (D ) O H
53. Compound A is
OH
(A)
(B)
HO
HO
(C)
(D )
O H
54. Compound B is Br Br Br Br (A) (B) HO HO Br Br (C)
54. Compound B is
Br
Br
Br
Br
(A)
(B)
HO
HO
Br
Br
(C)
(D ) HO
Br
HO

55. Which of the following statements regarding Aare incorrect ?

(A)

In the presence of acidic mediumAforms a 5 membred ring.

(B)

Ahas 2 geometrical isomers.

(C)

A has 4 pairs of diasteereomers.

(D)

A has 2 chiral centres

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JEE ADVANCED-VOL - VIII

 

MATRIX MATCHING TYPE QUESTIONS

56.

column 1 ( pair of alchols )

(A) P h OH and OH HO Ph

(A) Ph

OH

and

OH

HO

(A) P h OH and OH HO Ph

Ph

 
 

(P) Iodoform test

(B)

and OH OH

and

and OH OH

OH

OH

(Q)Victor mayor test

 

(C)

CH 3 CH 2 OH

and

CH 3 CH 2 OH and

(R)Lucas test.

OH and OH

OH

and

OH and OH

OH

 

(D)

 

normal conditions.

57.

COLUMN -1

COLUMN - II

O

(A)

O OH -

O

O OH -
O OH -

OH -

O OH -
 

O

Ph

O H+,H 2 O
O H+,H 2 O

O

H+,H 2 O

O H+,H 2 O
 

(B)

 

(Q) Acyl cleavage

 
O Conc.HI
O Conc.HI

O

Conc.HI

O Conc.HI

(C)

 

(R)

Racemic mixture

 
CHD O NO 2
CHD
O
NO 2

HI

H 3 CO

 

(D)

(S)

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3 CO   (D) (S) Narayana Junior Colleges column 2 ( Tests which can distinguish them)

column 2 ( Tests which can distinguish them)

(S) sodium dichromate in acidic medium Under

(P)Involves carbocation formation

Product gives iodoform test

101

JEE ADVANCED-VOL - VIII

58.

COLUMN I H CH 3 H H O D (A) Cl P O
COLUMN I
H
CH 3
H
H
O
D
(A)
Cl
P
O

Cl



(B)

(C)

CH 3

3 H H O D (A) Cl P O Cl   (B) (C) CH 3

H

Conc.H 2 SO 4

Cl P O Cl   (B) (C) CH 3 H Conc.H 2 SO 4 D

D

OH

OTs H CH 3
OTs
H
CH 3

H

R 3 N

3 H Conc.H 2 SO 4 D OH  OTs H CH 3 H R 3

ALKYL HALIDES & ARYL HALIDES

COLUMN II

(P) Isotopic effect

(Q)

Zaitsev’s product

(R)

Rearrangement

(D) CH 3 Conc.H 2 SO 4 Ph CH 3 (S)Bimolecular elimination  OH INTEGER
(D)
CH 3
Conc.H 2 SO 4
Ph
CH 3
(S)Bimolecular elimination
OH
INTEGER TYPE QUESTIONS

59.

OH

elimination  OH INTEGER TYPE QUESTIONS 59. OH H + The number of pi bonds in

H +

The number of pi bonds in the final product is elimination  OH INTEGER TYPE QUESTIONS 59. OH H + 60.The number of moles of Periodic

60.The number of moles of Periodic acid used in oxidation of

102

H H HO O HO H H H OH OH HO
H
H
HO
O
HO
H
H
H
OH
OH
HO

is

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ALKYL HALIDES & ARYL HALIDES

JEE ADVANCED-VOL - VIII

61. During the reaction of Benzene diazonium chloride with para-cresol the substitution occurs at position of p-cresol.

62.

63.

the substitution occurs at position of p-cresol. 62. 63. O on heating forms membred ring transition

O

the substitution occurs at position of p-cresol. 62. 63. O on heating forms membred ring transition

on heating forms

membred ring transition state.

62. 63. O on heating forms membred ring transition state. OH H + The number of

OH

H +

O on heating forms membred ring transition state. OH H + The number of dehydration products

The number of dehydration products are

64. The number of intermediates + transition states passible during the following reaction is

OH H +
OH
H +
65. 66. 67 . The number of moles of dichromate used in oxidation of RCH
65.
66.
67 .
The number of moles of dichromate used in oxidation of RCH 2 OH to RCO 2 H is
The number of moles of Manganate ion used in oxidation of cyclopentene to cyclopent( 1 . 2 )diol
is
The number of moles of HIO 3 formed during periodic oxidation of cyclohexa (1,2,3) triol
68. The number of compounds that undergo ring expansion on reaction with H 2 SO 4 is
OH
OH
OH
OH
OH
HO
OH
OH
OH
OH

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103

JEE ADVANCED-VOL - VIII

ALKYL HALIDES & ARYL HALIDES

(A)

(B)

(C)

(D)

69.

70.

71.

72.

104

STATEMENT TYPE QUESTIONS > rate of dehydration. OH OH NO 2 OH O Basic medium
STATEMENT TYPE
QUESTIONS
>
rate of dehydration.
OH
OH
NO 2
OH
O
Basic medium
+
O 2 N
Cl
H
H
(1)TsCl
14
CH 3
H
C
3
HO
OH
(2)H 2 O
14
H C
CH 3
3
O
O
18
18
H
O
O
H + / H 2 O
O
Ph
Ph
+
H C
H C
H
3
3
Ph
Ph
Ph
Ph
O
18
O
Ph
involves unimolecular mechanism.
H C
3
Ph
Ph
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mechanism. H C 3 Ph Ph Narayana Junior Colleges This section contains 4 reasoning type questions.

This section contains 4 reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.

STATEMENT–1 is True, STATEMENT–2 is True; STATEMENT–2 is a correct explanation

for STATEMENT–1

STATEMENT–1 is True, STATEMENT–2 is True; STATEMENT–2 is NOT a correct

explanation for STATEMENT–1

STATEMENT–1 is True, STATEMENT–2 is False

STATEMENT–1 is False, STATEMENT–2 is True

STATEMENT–1 :

STATEMENT–2 :Rate of dehydration is directly proportional to stability of carbocation

STATEMENT–1 :

STATEMENT–2 : reaction proceeds by electrophillic aromatic substitution.

STATEMENT–1 :

STATEMENT–2 : Reaction proceeds via inversion of configuration in SN2

STATEMENT–1 :

STATEMENT–2 : Hydrolysis of

ALKYL HALIDES & ARYL HALIDES

JEE ADVANCED-VOL - VIII

73. STATEMENT–1 :

HO O HO O
HO
O
HO
O

is more acidic then

STATEMENT–2 : Conjugate base of

HO O HO O
HO
O
HO
O
HO O HO O
HO
O
HO
O

is more stable

74. STATEMENT–1 :

O 2 N

CH 3 Cl
CH 3
Cl

Br

undergoes inversion in DMSO with hydroxide ion

STATEMENT–2 : The reaction proceeds by SN 2 mechanism.

75. STATEMENT–1 :In protic solvents phenoxide ion is alkylated primarily at C-alkylation whereas in polar aprotic solvents O-alkylation with alkyl halide .

STATEMENT–2 : C-alkylation products are more stable then O-alkylation products.

76. STATEMENT–1 :Optically active 2-iodo octane looses its optical activity with NaI in acetone

STATEMENT–2 : Repeated walden inversionon the reactant and its product gives racemic mixture

77. STATEMENT–1 :Phenol undergoes kolbe’s reaction while cyclohexanol does not.

STATEMENT–2 :Phenoxide ion is more basic then ethoxide

78. STATEMENT–1 :Para chloro phenol is more acidic then para flouro phenol.

STATEMENT–2 :negative inductive Effect if flourine is greater then in chlorine

LEVEL - IV - KEY

SINGLE ANSWER TYPE QUESTIONS

01.B

02.A

03.B

04.C

05.B

06.B

07.C

09.

B

10. D

11. B

12.D

13.A

14.A

15.D

17.D

18.A

19.C

20.B

21.C

22.B

23.B

25.D

26. B

27. C

28.C

29. C

30. B

ONE OR MORE THAN ONE ANSWER QUESTIONS

31.A,B,D

32.A,B,C

33.A,C

34.A,C

35.A,B,C

36.A,B,C,D

38.A,B,C

39. A,B,C,D

40. A,B

41. B,C

 

COMPREHENSION QUESTIONS

 

42.

d

43. d

44. b

45. a

46.c

47. a

48. c

50.

a

51. a

52. c

53. a

54. a

55. d

08.A

16.A

24.A

37.A,B

49. a

MATRIX MATCHING QUESTIONS

56.

58.

A-P,S, B-P,R , C-Q,R, D-QRS

A-P, B-R, C- P,Q,S, D-R INTEGER TYPE QUESTIONS

57. A-Q,S

, B-P, R ,S, C-P,S , D-R,P

59.7

60.3

61.2

62.6

63.4

64.9

65.2

67.2

68.3

 

STATEMENT TYPE QUESTIONS

 

69.D

70.C

71.D

72.D

73.A

74.A

75.B

77.C

78.B

66.2

76.A

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105

JEE ADVANCED-VOL - VIII

ALKYL HALIDES & ARYL HALIDES

01.

02.

03.

04.

05.

06.

07.

08.

106

& ARYL HALIDES 01. 02. 03. 04. 05. 06. 07. 08. 1 0 6 LEVEL IV
LEVEL IV HINTS CH + + CH 2 CH + CH 2 CH 2 intermediate
LEVEL IV HINTS
CH +
+
CH 2
CH +
CH 2
CH 2
intermediate is more stable leading to B
NO 2
CH 3
O
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OH + CH 2
OH
+
CH 2

OHto B NO 2 CH 3 O Narayana Junior Colleges OH + CH 2 H 3

to B NO 2 CH 3 O Narayana Junior Colleges OH + CH 2 OH H
to B NO 2 CH 3 O Narayana Junior Colleges OH + CH 2 OH H

H 3 CO

Cl Cl Cl O O
Cl
Cl
Cl
O
O
SH TsO
SH
TsO

Cl

tosyl chloride makes hydroxide a poor leaving group into good leaving group and reaction

proceeds via SN2 mechanism

good leaving group and reaction proceeds via SN2 mechanism Alkyl bromide reacts with Mg to form

Alkyl bromide reacts with Mg to form grignard reagent.R part of grignard reagent acts a as nucleophile leading to epoxide ring opening.

grignard reagent.R part of grignard reagent acts a as nucleophile leading to epoxide ring opening. CH

CH + CH 3 OH

grignard reagent.R part of grignard reagent acts a as nucleophile leading to epoxide ring opening. CH

ALKYL HALIDES & ARYL HALIDES

O

JEE ADVANCED-VOL - VIII

Cl S O 09. 10. OH 11. aryl ethers require only 1 mole while the
Cl S
O
09.
10.
OH
11. aryl ethers require only 1 mole while the other compound requires 2
H
H
18
18 O
O +
18
O
12.

13. fries rearrangement . The hydroxyl group directs the incomming electrophile at para position with respect to it.

14. aryl halides undergo nucleophillic aromatic substitution in the presence of strong -R group at ortho , para position .

15. para chloro phenol more acidic then para flouro phenol since para chloro phenoxide has larger number of resonance stablised structures due to presence of d orbital

16.

HO + C
HO
+
C
C + HO O
C +
HO
O

17. Reimer tiemann mechanism .

18.

19.

20.

CH 3 + CH 2
CH 3
+
CH 2
CH 3 + C CH 3
CH
3
+
C
CH 3
O O HO O
O
O
HO
O
O OH OH HO
O
OH
OH
HO

21. reimer-tiemann reaction and nucleophillic substitution of phenoxide with alkyl halide.

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107

JEE ADVANCED-VOL - VIII CH 3 22. O H C 3 OH H C 3
JEE ADVANCED-VOL - VIII
CH 3
22.
O
H
C
3
OH
H
C
3
H
C
3
OH
23.
H
C
3

I

CH 3 I H C 3 O H C 3 H C 3 O H
CH 3
I
H
C
3
O
H
C
3
H
C
3
O
H
C
3

(2S,4S)-3,3-dimethylpentane-2,4-diol

24.

HO

HO

1-penten-3-ol

ALKYL HALIDES & ARYL HALIDES

H

2 C

24. HO 1-penten-3-ol ALKYL HALIDES & ARYL HALIDES H 2 C CH 3 25. oxygen is

CH 3

25. oxygen is in conjugation with 2 phenyl rings ,does not undergo cleavage

26. Formation of phenolphthalein

27. Kolbe’s reaction forward by acylation

redcues COOH group.

28.

29. Conceptual

30. No. of OH groups = difference in molecular weight / 42

31. Cyclohexene only gives same product.

Only

LiAlH

4

32. (CH 3 ) 3 CBr

+

CH 3 CH 2 ONa

4 32. (CH 3 ) 3 CBr + C H 3 C H 2 O N

gives elemination.

33. Reaction with lucas reagent involves formation of stable carbocation.Soecies that cannot form stable carboaction donot give white turbidity.

34. iso alcohols are oxidised to methyl ketones or acetaldehyde gives haloform reaction.Victormayer test is given by alcohols.

35. Ethers in which both alkyl groups bonded are primary in acidic medium do not form carbocations and hense donot undergoS N 1 REACTIONS.

36. Ring expansion takes place if a carbocation is formed out side the ring.

37. reimer tiemann reactions occur via formation of phenoxide intermediate.If it isnt formed no reaction.

38. Acetate group on phenol decreases avaliability of electron density on benzene Cyano group decreases nucleophilicity of phenoxide ion. Base attack on carbonyl carbon in ester increases if electrophilicity of that carbon increeases. During esterification alchol is nucleophile attacking.Electron withdrawing group on alchol decreases its nucleophilicity ,rate of esterification decreases.

39. conceptual

40. Reimer-Tieman reaction

41. According to Reimer-Teiman reaction

108

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ALKYL HALIDES & ARYL HALIDES

42.

ALKYL HALIDES & ARYL HALIDES 42. 43. Cannot be formed hint : 44. OH COMPRAHENSION-2 OH
ALKYL HALIDES & ARYL HALIDES 42. 43. Cannot be formed hint : 44. OH COMPRAHENSION-2 OH
ALKYL HALIDES & ARYL HALIDES 42. 43. Cannot be formed hint : 44. OH COMPRAHENSION-2 OH

43.

Cannot be formed hint :

HALIDES & ARYL HALIDES 42. 43. Cannot be formed hint : 44. OH COMPRAHENSION-2 OH and
HALIDES & ARYL HALIDES 42. 43. Cannot be formed hint : 44. OH COMPRAHENSION-2 OH and
44. OH COMPRAHENSION-2
44.
OH
COMPRAHENSION-2
OH and
OH and
43. Cannot be formed hint : 44. OH COMPRAHENSION-2 OH and H O JEE ADVANCED-VOL -

HO

JEE ADVANCED-VOL - VIII

44. OH COMPRAHENSION-2 OH and H O JEE ADVANCED-VOL - VIII HO 45. grignard reagent formed
44. OH COMPRAHENSION-2 OH and H O JEE ADVANCED-VOL - VIII HO 45. grignard reagent formed

HO

45. grignard reagent formed attacks cyclic ether by SN2 mechanism .Carbon nucleophile attacks at less stearically hindred side as steraic hinderence increases grignard reaction does not occur .

46. grignard reagent is unstable in the presence of acidic hydrogen .

formed does not react with grignard reagent.

O O
O
O

COMPRAHENSION-3

47.

48.

read comprahension

epoxides undergo SN2 reaction .Alkoxide formed becomes a good incomming group and c-cl bond becomes a good leaving group.

O O OH 49. O Narayana Junior Colleges
O
O
OH
49.
O
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MgBr

109

JEE ADVANCED-VOL - VIII

COMPRAHENSION -4

ALKYL HALIDES & ARYL HALIDES

50.

51.

52.

aryl halides with -R groups at ortho para positions undergo nucleophillic aromatic substitutions.The reaction represents SN reaction.

ring expansions do not take place if existinfg ring is already stable.

O O O O O O H O 3 S H O 3 S B
O
O
O
O
O
O
H O 3 S
H O 3 S
B r o m i n a t io n
s u l p h o n a t io n
S O 3 H
S O 3 H
O
O O HO 3 S Br desulphonation hydrolysis SO 3 H COMPREHENSION -5 (For Q.NOs.
O
O
HO 3 S
Br
desulphonation
hydrolysis
SO 3 H
COMPREHENSION -5
(For Q.NOs. 53-55)
12
hint : D.B.E. of (A) = 10 –
+ 1 = 5
2

OH

53-55) 12 hint : D.B.E. of (A) = 10 – + 1 = 5 2 OH

Br

Since (A) decolouries bromine water and adds only a molecule of bromine, (A) should have a double bond. D.B.E. of A = 5; it should also have a benzene ring. (A) gives positive iodoform test and should have structure of the type

R — CHCH 3

(R = alkyl/aryl group)

OH

CHBrCHBrCH(OH)CH 3 CH = CHCHCH 3 Br 2 Hence (A) = OH CCl 4 (B)
CHBrCHBrCH(OH)CH 3
CH = CHCHCH 3
Br 2
Hence (A) =
OH
CCl 4
(B)
CH = CHCOOH
CH = CHCHCH 3
I
2
CHI 3
+
OH
NaOH
Iodoform

(A)

110

(C)

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ALKYL HALIDES & ARYL HALIDES

(A) has a chiral carbon and exists in two enantiomeric forms:

H

CH = CHC 6 H 5 OH
CH = CHC 6 H 5
OH

CH 3

HO

CH = CHC 6 H 5 H
CH = CHC 6 H 5
H

CH 3

(A) has two geometrical isomers:

C 6 H 5 C = C H
C 6 H 5
C = C
H

(cis)

CH(OH)CH 3

H

H C = C C 6 H 5
H
C = C
C 6 H 5

(trans)

CH(OH)CH 3

H

JEE ADVANCED-VOL - VIII

56.

Conceptual

 

57.

Conceptual

58.

Conceptual

59.

O H H +
O H
H +

60.

Only 1 , 2 cis diols participate in oxidation leading to ring cleavage

61.

2

62.

6

63.

63.
63.
63.
63.
 
 

64.

OH 2

OH 2

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111

JEE ADVANCED-VOL - VIII

65.

3RCH 2 OH + 2Cr 2 O 7 2- + 16H +

VIII 65. 3RCH 2 OH + 2Cr 2 O 7 2 - + 16H + ALKYL

ALKYL HALIDES & ARYL HALIDES

3RCO 2 H + 4Cr 3+ + 11H 2 O

66. 67. Conceputal
66.
67.
Conceputal

+ 2MnO 4 - + 4H 2 O

OH

O 66. 67. Conceputal + 2MnO 4 - + 4H 2 O OH OH + 2MnO

OH

+ 2MnO 2 + 2OH-

68.

after forming carbocation if carbocation is outside the ring then ring expansion takes place.

69.

70.

Stability of carbocation at bridge head is unstable.

Reaction proceeds via nucleophillic aromatic substitution or addition elemination mechanism.

71.

H

14

3

H

C H C 3
C
H C
3

(1)TsCl

OH (2)H 2 O
OH
(2)H 2 O

HO

H

14 CH 3 CH 3
14
CH 3
CH 3

72.

73.

74.

75.

76.

77.

78.

112

H

+

O 18 O Ph H C 3 Ph Ph
O
18 O
Ph
H C
3
Ph
Ph
H O 18 H C 3
H O
18
H C
3
O + Ph Ph + C
O
+ Ph
Ph
+
C

Ph

-O

O - -O O -O O - -O -O O O -O O O O
O -
-O
O -O
O -
-O
-O
O
O
-O
O
O
O
O
O

Even though carbon bromine bond is weaker then carbon chlorine bond , bromine in conjugation does

not undergo SN reaction .

In protic solvents alkyl halide frms carbocation ,an electrophile,participates in electrophillic aromatic substitution.

Repeated waldin inversionon the reactant and ist product gives racemic mixture.

Hint : Phenoxide ion is less basic then ethoxide.

parachloro phenoxide is resonance stablised by P d conjugation.

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