RELATIONS

JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
EXERCISE

LEVEL - V

OH

H+
1.


CH3
CH2 CH3

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

OH H+
2.
?


CH2 CH3 CH2 CH2

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

H 2O
3 . M ajor product is ?
Cl
H 3 CO NO 2

(A) (B) OH
OH
H 3 CO NO 2
H3CO NO2

OH

(C) (D) OH
H3CO NO2
H3CO NO2
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
Cl

a Cl CH 3OH

4. b

c
O Cl

Which of the following statements is correct ?

(A) major product is formed at a . (B) major product is formed at b .
(C) major product is formed at c . (D)Reaction does not take place.

TsCl
HS OH A B
5. Pyridine

B is
SH
SH HO
S O

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

OH

H2C

OH PCC /CH2Cl2
6.
H3C
H3C

(A) H3C (B)

H3C

O O

(C) H3C (D) H3C

CH3 CH3

O
PBr3 Mg / Ether H3O+
7. C H CH OH A B C D
6 5 2

(A) C6H5CH2OCH2CH3 (B)C6H5CH(OH)CH2CH2OH

(C) C6H5CH2CH2CH2OH (D)C6H5CH2CH2 OCH3
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES

CH2
H+
8. OH ?

CH3 CH2 CH3 CH2

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

H3C
OH SOCl2
9. H3C
?
CH3

H3C OH H3C Cl H3C H3C

Cl
(A) H3C (B) H3C (C) H3C (D )H3C
CH3 CH3 CH3 CH3

10 . A C6H12O compound does not react with Br2 in CCl4, produces a flammable gas on treatment
with LiAlH4, and reacts with H2CrO4 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
CH3 x moles of HI CH3 y moles of HI
11.

Sum of x and y is
(A) 2 (B) 3 (C) 4 (D) 5

18
O H+/H2O
CH3
12.
H3C

Products formed are

18 18
18 H O H O
OH CH3 OH CH3
(A) & (B) &
H3C H3C

HO 18 HO
O O
(C) & (D) &
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

CH3
O O
AlCl3

CH 3
Product formed is?
13. 

CH(CH 3 ) 2

CH3 CH3 CH3

OH OH
O

(A)H3C (B)

O CH(CH3)2 CH(CH3)2

CH3 CH3
OH OH

(C) (D) H3C

CH(CH3)2 O CH3

Cl
OH
-
H 3C CH 3 OH /
+ ?
14.

NO 2

CH3 H3C O
O
(A) (B) NO 2
CH3 NO 2 CH3

O O
H3C
(C) (D)
H3C CH3 NO2 H2C CH3 NO2

15. 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.
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES

HO
H+
16 . ?
OH

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

O HO OH

17. Appropriate product among the following.

OH OH
D CDO D CHO
(A) (B)

D
OH O
ODC CHO D CHO
(C) (D)

CH3
OH
18. H+ (major)
?

CH3
CH3
CH3
(A) (B)

CH3 CH3

CH2 CH3
(C) (D)
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
19. A C7H14O optically active alcohol is oxidised by jones reagent to an optically inactive ketone
.The molecule is .
HO
OH
H3C OH O

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

OH
HO HO

O H + / H 2O
20. ?

O
O O

HO OH
(a) ( b) (c) CH3 (d)
OH
HO
HO

OH
(i)CHCl3 + KOH
21. ?
(ii)CH2I2 + NaOH
OH

OH OH O OH

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

HOOC OH OHC OH OHC O OHC OH

22. A chiral C5H10O ether reacts with hot HI to give a C5H10I2 product. Treatment of this with hot
KOH in ethanol produces 1,3-pentadiene. What is the structure of the original ether?
CH3 CH3
CH3 CH3
(A) (B) (C) (D)H3C
O O O O
23. A chiral C7H16O2 diol is oxidized by PCC in CH2Cl2 to an achiral C7H12O2 compound.
Which of the following would satisfy these facts?
H3C H3C H3C H3C
OH OH OH OH
H3C H3C
(A) H3C OH
(B) H3C OH
(C) H3C OH (D) H3C OH
H3C H3C H3C H3C
SOLUTIONSRELATIONS
JEE ADVANCED-VOL - VIII
AND COLLIGARIVE PROPERTIES
24. A chiral C5H10O alcohol is reduced by catalytic hydrogenation to an achiral C5H12O alcohol.The
original alcohol is oxidized by activated MnO2 to an achiral carbonyl compound (C5H8O)Which
of the following might be the chiral alcohol?
(A)1-penten-3-ol (B) 4-penten-2-ol
(C)3-methyl-2-buten-1-ol (D) 2-methyl-2-buten-1-ol
25. Which of the following ethers is unlikely to be cleaved by hot conc. HBr?

O O O O
CH3
(A) (B) (C) (D)

26. Phenol reacts with Phthalic anhydride in the presence conc. H 2 SO4 to give
(A) Methyl orange (B) Phenolphthaline (C) Aspirin (D) Methyl Blue
27.
- +
O Na

CO2 Ac2O
A B

 H3PO4
Identitify B in the sequence
(A) Methyl orange (B) Phenolphtheline (C) Aspirin (D) Methyl Blue
O

O HO
28.
OH x OH

In the above transaformation ‘X’ could be

(A) NaBH 4 C2 H 5OH H 3O  (B) N 2 H 4 OH  Glycol | 

(C) LiAlH 4 Et2O H 3O  (D) DIBAL  H THF H 3O 

HO OH O O

29.
H3C H3C H

The above transformation can be done by using

(A) Baeyer’s Reagent (B) Tollen’s reagent
(C) Pyridinium dichromate in CH 2Cl2 (D) Jone’s reagent
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

30. An unknown organic compound (A) having M.F. C3 H 8O3 reacts with an excess of acetyl chloride
gives an actyl derivative with M.Wt. 218. Then howmay hydroxyl groups are in ‘A’.
(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
CH2
CH3

(A) (B)
H3C CH3 CH2

CH3

(C) (D)

32. Which method is usefull synthesis of ether

(A)

-
(B)H C O + (CH3)2SO4
3 Na
-
O + H3C
Na
(C) H3C + O SO2C6H5CH3
(D)(CH3)3CBr + CH 3CH2ONa

33. Which of the following alcohols donot give white turbidity on treatment with HCl/ZnCl2
CH3
N
H3C H3C OH
(A) (B) OH (C) (D)
OH
OH CH3
34. Which of the following gives positive victormayer test and yellow precipitate with NaOH / I2
OH NO 2
H3C H3C
(A) (B) (C) (D)H3C
H3C CH3 OH OH CH3
35. Which of the following is correctly matched
CH3
HI H3C O H+/H2O
(A)H3C O SN1 (B) CH3 SN1
CH3 CH3 CH3

H3C O HI
CH3 HI SN2
(C) (D) O SN1
CH3
SOLUTIONSRELATIONS
JEE ADVANCED-VOL - VIII
AND COLLIGARIVE PROPERTIES
36. In which of the following ring expansion / ring contraction takes place when protic acid is added
to the compound?
HO
OH
CH3
(A) (B)
CH3
OH

(C) (D) OH
H3C
37. Which of the following undergo reimer tiemann reaction?
OH CH3 OH NO2

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 faster than para cyano phenoxide With PhCH2Cl.
(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 4 / Et2O / H 3O 
O

O O-

(A) (B)
O
O

O O
O O

C) D)
CH
Cl HO
3

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 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 3 CHCl2 CH 3 COO H
CHO
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

COMPRAHENSION TYPE QUESITONS

Comprahension -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)

43. Which of the following product is not formed ?

OH

(A) (B) OH

OH

(C) HO (D)

44. The number of enantiomeric pairs formed during the raection 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 CO2 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.
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
45. What is the product (B) of the following reaction sequence ?
O

Br
Mg
A B
Et2O
Hydrolysis of B gives
OH

OH
(A) (B)

OH

(C) (D )
OH

OH

46.

Product formed is
OH O

OH OH
(A) (B)

Et Et
OH O

OH OH
(C) (D)

Et Et
Comprahension -3
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

Ring-opening reactions of epoxides can proceed by either SN2 or SN1 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 SN2 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 SN1 character, and the more substituted carbon is the site of attack. These
are both good examples of regioselective reactions. examine the basic, SN2 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 SN2 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 SN2 and SN1 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:

CH3CH2OH Product formed is?

47. O
NaOH

OH OH
(A) (B)

OCH2CH3 OCH2CH3

OH OH
(C) (D)

OCH2CH3 OH
- +
O CH O Na
48. Cl 3 The final product that is formed in the reaction is

HO OH

(A) H3CO (B) HO OCH3

O CH3
HO
CH3
(C) O O (D) Cl
O CH3
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES

O 1 EQV PhS 
O
49. The product formed after nucleohillic attack and
OH

mild hydrolysis is

O O
O O
(A) O (B) O

OH OH

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

OH OH
Comprahension- 4

Where E = electrophile, L.G. = Leaving Group

based on the above answer the following
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
50. Which of the following combinations give aryl arkyl ethers on heating

(A) O 2N Cl & +Na - O

(B) Cl & +Na - O

(C) Cl & +Na-O

Cl & +Na-O

(D)

O2N
51 . Which of the following does not give phenolic type compound on acidic hydrolysis .

O
O O

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

52. Which of the following products cannot be formed with out blocking reagent action on phenol ?
OH

OH
Br Br
COOH

(A) (B)

Br

OH
O

Br

(C) (D)
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
Comprahension- 5
Compound (A), C10H12O gives off hydrogen on treatment with sodium metal and decolourises Br2 in
CCl4 to give (B), C10H12OBr2. (A) on treatment with I2 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

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 A are incorrect ?

(A) In the presence of acidic medium Aforms a 5 membred ring.
(B) A has 2 geometrical isomers.
(C) A has 4 pairs of diasteereomers.
(D) A has 2 chiral centres
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

MATRIX MATCHING TYPE QUESTIONS

56. column 1 column 2
( pair of alchols ) ( Tests which can distinguish them)
HO
OH
(A) Ph Ph
(P) Iodoform test
and

OH

(B) and OH (Q)Victor mayor test

OH

(C) (R)Lucas test.

CH3CH2OH and
OH

(D) OH (S) sodium dichromate in acidic medium Under

and

normal conditions.

57. COLUMN -1 COLUMN - II

O
OH-
(A) (P)Involves carbocation formation
O

O Ph
H+,H2O
(B) (Q) Acyl cleavage
O
Conc.HI
(C) (R) Racemic mixture
O

HI
H3CO CHD

(D) O NO2 (S) Product gives iodoform test

 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
58. COLUMN I COLUMN II
H CH3
H


H  
O
(A) D (P) Isotopic effect
Cl P
O

Cl

CH3

Conc.H 2SO 4
D
(B) OH  (Q) Zaitsev’s product

OTs
R3N
H
(C) CH3 (R) Rearrangement
H

CH3
Conc.H2SO4
(D) Ph CH3 (S)Bimolecular elimination
OH


INTEGER TYPE QUESTIONS

OH

H+
59. The number of pi bonds in the final product is

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

H
H
HO O
HO
H H is
H OH

HO OH
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

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

62. on heating forms _____ membred transition state.

OH

H+
63. The number of dehydration products are ___

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

OH

H+

65. The number of moles of dichromate used in oxidation of RCH2OH to RCO2H is ______
66. The number of moles of Manganate ion used in oxidation of cyclopentene to cyclopent( 1 . 2 )diol
is__
67 . The number of moles of HIO3 formed during periodic oxidation of cyclohexa (1,2,3) triol ____
68. The number of compounds that undergo ring expansion on reaction with H2SO4 is

OH
OH OH OH

OH

HO OH
OH
OH

OH
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES

STATEMENT 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.
(A) STATEMENT–1 is True, STATEMENT–2 is True; STATEMENT–2 is a correct explanation
for STATEMENT–1
(B) STATEMENT–1 is True, STATEMENT–2 is True; STATEMENT–2 is NOT a correct
explanation for STATEMENT–1
(C) STATEMENT–1 is True, STATEMENT–2 is False
(D) STATEMENT–1 is False, STATEMENT–2 is True

69. STATEMENT–1 : > rate of dehydration.

OH OH

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

NO 2
OH
O
Basic medium
70. STATEMENT–1 :
+
O 2N

Cl

STATEMENT–2 : reaction proceeds by electrophillic aromatic substitution.

H H
14 (1)TsCl CH3
71. STATEMENT–1 : H3 C HO
OH (2)H2O 14
H3C CH3

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

O O 18
18
+ H O
O O Ph
Ph H / H 2O
72. STATEMENT–1 : H3C H3C H + Ph
Ph Ph
Ph

O
18
O
Ph
STATEMENT–2 : Hydrolysis of H3C involves unimolecular mechanism.
Ph
Ph
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
HO O HO O

73. STATEMENT–1 : is more acidic then

HO O HO O
HO O

STATEMENT–2 : Conjugate base of is more stable

HO O
CH 3
O 2N
74. STATEMENT–1 : Cl undergoes inversion in DMSO with hydroxide ion
Br
STATEMENT–2 : The reaction proceeds by SN2 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 - V - KEY
SINGLE ANSWER TYPE QUESTIONS
01.B 02.A 03.B 04.C 05.B 06.B 07.C 08.A
09. B 10. D 11. B 12.D 13.A 14.A 15.D 16.A
17.A 18.A 19.C 20.B 21.C 22.B 23.B 24.A
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 37.A,B
38.A,B,C 39. A,B,C,D 40. A,B 41. B,C
COMPRAHENSION QUESTIONS
42. d 43. d 44. b 45. a 46.c 47. a 48. c 49. a
50. a 51. a 52. c 53. a 54. a 55. d
MATRIX MATCHING QUESTIONS
56. A-P,S, B-P,R , C-Q,R, D-QRS 57. A-Q,S , B-P, R ,S, C-P,S , D-R,P
58. A-P, B-R, C- P,Q,S, D-R
INTEGER TYPE QUESTIONS
59.7 60.3 61.2 62.6 63.4 64.9 65.2 66.2
67.2 68.3
STATEMENT TYPE QUESTIONS
69.D 70.C 71.D 72.D 73.A 74.A 75.B 76.A
77.C 78.B
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES

HINTS
OH +
CH2 +
CH
01.

+ +
CH2 CH CH2 CH2
OH
02.

03. intermediate is more stable leading to B

H 3 CO NO 2

Cl Cl

Cl Cl

04.
O O

SH TsO

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

proceeds via SN2 mechanism

06.

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

+
CH CH3 CH3
08. OH O
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

O
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
12. O

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..
HO
+
C +
16. C
HO O
17. Reimer tiemann mechanism .

CH3 CH3
+
C
+
CH2 CH3
18.

O O

19.
HO O

OH
20.
OH HO

21. reimer-tiemann reaction and nucleophillic substitution of phenoxide with alkyl halide.
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
I
CH3 CH3
H 2C
CH3
22. O
I

H3 C H3 C
OH O
H3 C H3 C
H3 C H3 C
OH O
23.
H3 C H3 C
(2S,4S)-3,3-dimethylpentane-2,4-diol

HO
24.
1-penten-3-ol
25. oxygen is in conjugation with 2 phenyl rings ,does not undergo cleavage

26. Formation of phenolphthalein

27. Kolbe’s reaction forward by acylation
28. Only LiAlH 4 redcues COOH group.
29. Conceptual
30. No. of OH groups = difference in molecular weight / 42
31. Cyclohexene only gives same product.

32. (CH3)3CBr + CH 3CH2ONa 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 undergoSN1 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.
1-chloromethyl -4 - methyl - 1,3 -cyclopentadiene is solvolysed in aqueous acetone
based on the above wsolve the following questions.
39. conceptual
40. Reimer-Teiman reaction
41. According to Reimer-Teiman reaction
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

42.

43. Cannot be formed hint :

44. OH OH and HO
HO

COMPRAHENSION-2
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 .

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

formed does not react with grignard reagent.

COMPRAHENSION-3
47. read comprahension
48. 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
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
COMPRAHENSION -4

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

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

O
O
O
HO 3 S
HO 3S
B r o m i n a t io n
s u l p h o n a t io n
52.

SO 3H
SO 3H O

O
OH
H O 3S Br
desulphonation Br

hydrolysis

S O 3H

COMPRAHENSION -5
(For Q.NOs. 53-55)
12
hint : D.B.E. of (A) = 10 – +1=5
2
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 — CHCH3 (R = alkyl/aryl group)

OH
CH = CHCHCH3 CHBrCHBrCH(OH)CH3
Br2
Hence (A) = OH CCl4
(B)

CH = CHCHCH3 CH = CHCOOH
I2
CHI3 +
OH NaOH Iodoform

(A) (C)
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
(A) has a chiral carbon and exists in two enantiomeric forms:
CH = CHC6H5 CH = CHC6H5

H OH HO H

CH3 CH3

(A) has two geometrical isomers:

C6H5 H
CH(OH)CH3 CH(OH)CH3
C=C C=C
H H C6H5 H

(cis) (trans)

56. Conceptual
57. Conceptual
58. Conceptual
OH

H+
59.

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

61. 2
62. 6

63.

OH2

64.
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
65. 3RCH2OH + 2Cr2O72- + 16H+ 3RCO2H + 4Cr3+ + 11H2O

OH

66. OH + 2MnO2 + 2OH-

+ 2MnO4- + 4H2O

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

69. Stability of carbocation at bridge head is unstable.

70. Reaction proceeds via nucleophillic aromatic substitution or addition elemination mechanism.

H H
14 (1)TsCl 14
CH3
H3 C
71. HO
OH (2)H2O
H3C CH3

+ H O
H O 18
O Ph Ph
18
O + C
+
Ph H3C
72. H3C Ph
Ph
Ph

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

73.
O
-O -O O O O O
O

74. Even though carbon chlorine bond is weaker then carbon chlorine bond , bromine in conjugation does not
undergo SN reaction .
75. In protic solvents alkyl halide frms carbocation ,an electrophile,participates in electrophillic aromatic
substitution.
76. Repeated waldin inversionon the reactant and ist product gives racemic mixture.

77. Hint : Phenoxide ion is less basic then ethoxide.

78. parachloro phenoxide is resonance stablised by P  d conjugation.

JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

LEVEL - VI

SINGLE ANSWER QUESTIONS

1. Which of the following gives the product below on heating with anhydrous AlCl3 / CS 2

H3C OH

CH3 O
O

O O
(A) (B)

H3C

O
OH OH

(C) (D)
CH3
H3C O O

2.

Which of the statements regarding is incorrect.

(A) If both alkyl groups are aromatic then products are formed by SN 1 mechanism

(B) SN2 cleavage occurs at a faster rate with HI than HCl

(C) If both alkyl groups are primary .in polar protic solvent undergoes SN 2 mechanism.

(D) R=primary ,R1=tertiary , cleavage take places by S N 1 .

 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
3. Epoxy resins use a polymer made from bisphenol A and epichlorohydrin in basic medium.Which
of the Statements are incorrect.

CH3
HO OH
CH3
Cl
bisphenol A epichlorohidrin

(A)Reaction proceeds via SN2 .

(B) The nucleophile attacks from hindered side.
(C)Chirality of carbon in epichlorihidrin is retained.
(D)in each step two SN2 reactions take place.

4.

Identitify A .

18 18
OH OH

OH OH
(A ) (B) 18
OH

CH3 CH3

18
OH OH

18
18 OH
OH
(C) (D) OH
OH

CH3 CH3
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
5. Predict the product for the following reaction
NH2
OH H
HNO2

H
O O O
O H
H H

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

H H H H
OH H
+

6
O
O O

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

O O
O O

H3C
CH3
(1)Hg(OAc)
2
7 OH (2)NaBH Product formed is
4
H3C

O CH3
CH3 CH3 CH3
O CH3 CH3 CH3 O
O CH3
(A) (B) (C) H C (D)
3
H3C
H3C
HO CH3

TsOH

8. OH  product formed is

H3C CH3
CH3 CH3 HO CH3 HO CH3

CH2
(A) (B) OH (C) (D)
H3C
O H3C CH2 H3C CH3 H3C CH3
H3C
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
9. The highest rate of hydrolysis of the following compounds is
O O O O
H3C H3C
(A) (B)
H2N H3C O
O O O O
H3C H3C
(C) (D)
F
10. Which of the following transformations are correct in acidic medium?

OH
CH3 CH3

(A) (B) H / 

O CH3
CH3 H+ CH3
OH OH
H+ CH3
CH3 CH
(C) CH3 (D) 3 CH3
CH3 O CH3 CH3
HO CH3

HO

CH3 H+ CH2
11. Which of the following graphs is suitable

e
e
n n
e e
r r
g g
y y
(A) (B)

reaction coordinate reaction coordinate

e
n e
n
e
e
r r
g g
y y
(C) (D)

reaction coordinate reaction coordinate

JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
12. Which of the follwoing would give tertiary alcohol when it reacts with an excess of
CH 3 MgBr followed by hydrolysis

O
O-

(A) (B)
Cl
O
O

(C) (D) All of these

13. Which of the follwoing compund would give secondary alcohol when reacts with an excess of
phenyl megnisium bromide followed by hydrolysis.
O

(A) O (B)

H
O

(C) O (D) C6 H 5  CH 3CN

14. Glycerol reacts with an excess of HI to give

A) Allyliodide (B) 1, 2, 3, - triiodopropane
(C) Isopropyl iodide (D) Acrolein
O O
|| 16 18 || A
15. Fischer esterification is represented as follws R  C  O  H  R ' O H  R  C  O  R ' H O
2

here  R  CH 3 , R '  C2 H 5  in the above reaction A/2 is equal to

A) 8 (B) 9 (C) 6 (D)12
16

O
CH3 Cl S Me
H O
OH   CH3COONa

18
OH / H 2 O (Ester hydrolysis)
 
(1) (2) (3)

D
18
(X) Acidification
(P)  CH 3 COOH (4)

The product P
(A) is the retended form of (X) (B) is the inverted form of (X)C
(C) has no chiral carbon (D) is a meso compound
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
17 The end product of the following reaction is

CH2

rearrangement H
14  (1)
 
(2)

OH
14
(A) 14 O (B) OH

CH3
14
(C) O (D)
14 O

18. The major products of following reactions sequence are:

OH
OH

H 2SO4 LiAlH4 H
(1)
 (I) (2)
 (II) 
(3)
 (III)
Ph
Ph

O O
Ph
(A) I  (B)
Ph I
Ph Ph
Ph Ph
Ph
(C) III  (D) III 
Ph
19. Identify the possible structure of X and Y (MORE THAN ONE CORRECT)
COOH
KMnO 4 / OH / 
 

C9 H12 O resolution
  d
(X or Y)

K 2 Cr2 O7 / H 2 SO4
  Blue green salt + other products

OH
CH3
CH3
Ph Ph CH3
(A) (B) OH
(X)
(Y)

OH OH CH3 OH
CH3 OH CH3
CH3 Ph Ph
Ph
(C) (Y) (D) H
CH3 (Y)
(X) (X)
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

20. Observe the following reactions

H 3C O HI
CH3   X (Alchol)  Y (Alkyl halide)
I)
CH3

CH 3
O CH 3 
HI
W S
H 3C
II)
CH 3

(R1 )
III) X   (S)
(R 2 )
IV) Y  (W)
The reagents R1 and R2 can be respectively.
(A) NaI/Acetone, aq. AgNO3 (B) aqueous KOH, HI
(C) aq. AgNO3, NaI/Acetone (D) HI, aqueous KOH

21. the major product is :

OCH 3 OC 2 H 5 I

A) B) C2 H 5O  CH 3 C) D)

NO 2 NO2 C2 H 5

CH 3  CH 2  CH 2  CH  CH 3

22. H

 H 2O
  F  
Br2 / CCl4
 C5 H10 Br2  G 
OH

How many structures of (G) is possible ? ( including all stereoisomers)

A)2 B)6 C)3 D)5
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES

OH

O2 N NO2
 NaHCO
  3

23. The products of above reaction will be :

NO 2

oNa oN a

O2 N NO 2 O2 N NO 2

 CO 2  H 2 O  Na 2CO3
A) B)

NO 2 NO 2

OH COOH

HOOC NO2 O2 N NO 2
 NaNO2  N aO H
C) D)

NO2 NO 2

H O
24. 3  product


The major product of the above reaction is

A) OH B)
OH HO HO O OH

OH

C) D)
HO H HO OH
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
CH 3

O2 / H 2O 
Cl2 / AlCl3 

25.    P 

Q  HCHO P and Q are respectively:

CH 3 Cl
CH 3 OH

and
A) B) and
OH Cl Cl
Cl
CH 3 CH 2  CHO CH 3 CHO

C) and D) and
Cl Cl
Cl Cl
26. Predict major product of the following reaction
HBr Na
        
excess C H
2 5 2O 
A) B) C) D)

MORE THAN ONE CORRECT ANSWER TYPE

27. Which of the statements is true regarding below reaction

O H3O+
CH 2

CH3
(A) The number of intermediates formed are 3.
(B) Configuration at epoxy carbon does not change.
(C) Twostereogenic centres are formed in the final product .
(D) Reaction is 5th order.
28. Which of the following statements is correct regarding the following reaction ?

(A) A = (B) A =
O

(C) B= ( D) B=
O
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
29. Consider para sulphonyl benzene diazonium reacting with para amino phenol
OH OH OH

 a
mildly basic Weakly acidic
 b

NH2 NH2 NH2

which of the following statements are correct:
(A) coupling is an electrophillic substitution.
(B) under basic conditions diazonium attacks at alpha position.
(C) under weakly acidic conditions diazonium attacks at b position
(D) Ifsulphonyl group is replaced with methyl groyp coupling takes place
30. One compound of the pair will react more rapidly than the other .Identitify correct order
CH 3
CH 3
CH 3

(A) O O H 2SO 4 in CH 3CN

<

MeO HO

(B) > H2SO4 in CH3CN

O OH O OMe
H3C H3C
>
(C) H C H3C H2SO4 in CH3CN
2
CH3 O CH3
O
H3C

O >
O HBr in CH 3 CN
(D) CH 3 CH 3
H3C H3C

31.

CH3 CH3

(A) HO (B) HO
D H
CH3

(C) (D)
D
OH
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

32. Which of the following esterification reactions are unimolecular?

CH3 O
O
+ H+ / H 2 O
A) H3C + H3C OH
H / H2 O B) H3C + H3C

CH3 OH OH
OH
O CH3 HO O OH
+
H / H2 O
C)
H3C
+ H3C OH
D) + H+ / H 2 O
OH CH3 O OH HO

OH (1) CH3CO3H

(2) OH-
33
CH2
CH3
Products formed in step 1 and 2 are
OH OH
O O

(A) (B)
CH3 CH3

O O OH

(C) OH (D)
CH3 CH3

HO Cl
Me (1) NaOH
34. Et Products formed in two steps are
(2) H O
Et H 2

O OH
Et H Me OH

(A) (B) major product

Et Et
Et
Me H

OH OH
H Me HO H

(C) Minor product (D)

Et Et Et Et
OH Me
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
Comprahension -1

Dialkyl ethers react with very few reagents other than acids. The only reactive sites that molecules of a
dialkyl ether has to another reactive substance are the C H bonds of the alkyl groups and the O group of
the ether linkage. Heating dialkyl ethers with very strong acids (HI, HBr, and H2SO4) causes them to
undergo reactions in which the carbon–oxygen bond breaks . When mixed ethers are used, the alcohol
and alkyl iodide that form depend on the nature of the alkyl groups .Mechanism is by an SN2 reaction or
S N1 .

35. What is the correct order of reactivity towards conc.HI assuming SN2 type cleavage?

H3C CH3 H3C CH3 H3C CH3

H3C O
CH3 CH3 O O CH3
H3C O CH3 CH3 CH3 CH3

I II III IV

(A) I > IV > III > I (B)I > III > IV > II (C) II > I > IV > III (D)IV > II > III > I

Dil . H 2 SO4
A+B

36.
O

A gives positive test with FeCl3.

B gives positive lucas test in a few seconds. Which is ‘B’.

(A) HO (B) OH

(C) HO (D ) OH
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

H3C 18
O2N O Dilute HI
18
37. O

product formed in the reaction is ?

18
OH
O2N

(A) (B) 18
18 OH
HO

OH

O2N

(C) (D)
OH
18
OH

COMPRAHENSION - 2
Diane diol worked for several days to prepare compounds shown.She labelled and slept.When she got up
all lables had slipped.Her friend Glycol said that They could be easily distuingished by two experiments.
Which of the m were optically active .
How many products were obtained when each is treated with periodic acid.
after experimentation Diane found the following results
1. Compounds A,E,F were optically active and B ,C and D were optically inactive.
2.One product was obtained from the reaction of A,B and D with periodic acid .
3.Two products were obtained from the reaction of F with periodic acid.
4. C and e didnt react with periodic acid.
The structures of the compounds were

CH3
CH3 CH2CH3
CH3
CH3 CH3
H OH
H OH H OH
H OH
H OH H OH
CH2
CH2 H OH
HO H
H OH HO H
HO H
H OH CH2CH3
CH2CH3
CH3 CH3
CH3
CH3 II III
I IV VI
V
answer the following based on the above observations;
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
38. Which structure could be suggested for A
(A) II (B) III (C) IV (D)VI
39. Which structure could be compound F
(A) II (B)III (C)IV (D)VI
40. On the basis of the observations which compounds cannot be distinguished ?
(A) compounds C and F (B)Compounds B and D
(C) compounds B and C (D)Compounds D and E

Comprahension-3
Br

1.Mg 1.MCPBA
2.PhMgBr Conc.H2SO4 D MCPBA
A B C
3.H2O Heat
2 .ethylene
oxide conc.H2SO4 ,heat
3.H2O
41. Which of the statements regarding formation of compound A is correct ?
(A) Epoxide ring opening is by trimolecular reaction.
(B) A has a chiral carbon.
(C) A gives positive test with neutral ferric chloride.
(D)Adeclourises dichromate solution in acidic medium
42. Which of the statements are correct regarding C?
(A) C does not respond to lucas test.
(B) C is an enantiomeric mixture.
(C) C is transformed to D via E2 reaction.
(D) C cannot be obtained by grignard reaction .
43. Which of the following is correct
O

(A)Final product = (B)

C

OH

(C) (D) A
B

Comprahension - 4
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

Lucas reagent FeCl 3

no reaction gives intense color
A C 8 H 8O 3 

not steam distilled gives positive test with

tollens reagent

answer the following based on the above

44 Compound A is ?

CHO CHO CHO

CHO

OH

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

OH OMe

OMe
OMe OH OH
45. Compound F is ?

COOH CHO

Br Br

(A) (B)
OH Br OMe

OMe OH
Br CHO

Br Br Br

(C) (D)
Br OMe OH

OH OMe
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
46. Compound C is
COOH

COOH
OMe

(A) (B)

MeO OMe
OMe
COOH CHO

(C) (D)
OMe OMe

OMe OMe

Comprahension - 5
P is an alcohl which on heating with Al2 O3 forms an alkene Q. Q on ozonolysis produces R
and S. When the mixture of R and S is heated with NaOH, a redox reaction takes place and a
mixture of an acid salt and alcohol is formed.

47. The alcohol(P) is obtained by:

CH
H 3C  C  CH 2  CH 3  CH 3 MgBr 3
A) 
B) |
O CH 3  C H  CH 2  CH  O  CH 3 MgBr

CH CH
3 3
| |
CH 3  CH  CH 2 MgBr  CH 2  O CH 3  CH  CH 2  COCl  CH 3 MgCl
C) | D) |
CH CH
3 3

48. The compound (Q) is:

CH
3
CH |
3
A) | B) CH 3  C|  CH  CH  CH 3
CH 3  C  CH  CH 3 CH
3

CH CH
3 3
| |
C) CH 3  C|  CH 2  CH  CH 2 D) CH 3  C|  CH  CH 2
CH CH
3 3
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS
49. The compounds R and S are:

CH
3
CH |
3 CH 3  C  CH  O, CH 3CH  O
A) | B) |
CH 3  C  O, CH 2  0
CH
3

CH CH
3 3
| |
CH 3  C  CH  O  CH 2  O CH 3  C  CH 2  CH  O  CH 2  O
C) | D) |
CH CH
3 3

MATRIX MATCHING QUESTIONS

50. COLUMN I COLUMN II

( Reaction with an Excess HI ) (Nature of reaction (Products))
OCH3
CH3
(A) (P) More than 4 moles of HI Consumed
OCH3

OCH3
OCH3
(B) (Q) Product reacts with Na
OCH3

OPh
OPh
(C) (R) product formed contains secondary halide.
OPh

OH

OH
(D) (S) methyl iodide is one of the product
OH
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
51. COLUMN I COLUMN II
(REACTION ) (PRODUCT)

OH

HCl
(A) H3C (P) Carbocation rearrangement

H
O LiAlH 4

(B) (Q) Diastereomers formed

Me H

Et OH-
(C) N (R)2 Stereocenters in product
H
Cl
O CH3OH , H+
(D) (S)Inversion of configuration.
HO OH

INTEGER TYPE QUESTIONS

52. The number of compounds in which isotopic oxygen is retained by olefinic bond on reaction with
hydroiodic acid is ________
18 18
O O

O
18 O
18

18 O
O O
18 18 O
18

1 2
53. Acidification results in cleavage of bond at____ carbon.
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

54.
O

The number of oxygens that undergo tautomeristioon acid reaction .

55. On heating in follwoing compound an allyl group will migrate to which possition.

6
5 1

4 2
3

O
O
56. + AlCl3 / CS2
 

O O

products .
How many products could except to at time in the above reaction.
57. Howmany of the following compounds are more acedic than phenol.

SH OH -
OH O O OH
N+

HO
1) 2) 3) 4) 5)

Cl

OH OH OH

6) 7) 9) H 2 CO3
8)

N+
O O- Cl
N
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
58. Howmany of the following compounds are soluble in aqeous solution of NaHCO3
1) Phenol 2) Cyclohexanol 3) 2, 4- di nitro phenol
4) Benzoic acid 5) Benzene sulphonic acid 6) P-cresol
7) P-methoxy phenol 8)   naphthol 9) N-methyl aniline.
59. Howmany of the following compounds are dissolve in aqeous solution of NaOH
1) Phenol 2) P-cresol
3) Benzoic acid
4) Benzene sulphonic acid 5) Aniline 6) P-toluedine
7) Picric acid 8) Squaric acid
60. How many of the following compounds would give turbidity with lucas reagent without heating.
1) Benzyl alcohol 2) Allyl alcohol 3) Cyclohexanol
4) 2-methyl - 2 - proponol 5) Neopentanol 6) Phenol
7) O-Cresol 8) Cylopropyl methyl carbionol 9) P-Nitro benzyl alcohol
61. Howmany of the following compounds would give Iodoform test
1) s CH 3  CO  CH 2  CO  OCH 3 2) C6 H 5  CO  CH 2  CO  C6 H 5

3) CH 3  CHCl  CH 2  CH 3 4) CH 3  CHNH 2  CH 3

5) CH 3  CO  CH 2 I 6) CH 3  CO  O  CO  CH 3

7) CH 3  CO  O  CH 3 8) CH 3  CO  Cl

9) CH 3  CHOH  CH 2  CH 3 10) CH 3  CO  CH 2  CHOH  CH 3

ASSERTION & 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.
(A) ASSERTION is True, REASON is True; REASON is a correct explanation for ASSERTION
(B) ASSERTION is True, REASON is True; REASON is NOT a correct explanation for ASSERTION
(C) ASSERTION is True, REASON is False
(D) ASSERTION is False, REASON is True
OH O

62. ASSERTION :
OH O

Anthraquinol Anthrone

REASON: Aromaticity in three rings gives more stability than two rings
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

63. ASSERTION : Cyclohexa - 2,4-dieneone does not give positive test for ketones
REASON: Eneol form of Cyclohexa - 2,4-dieneone is more stable and it undergoes tautomerism
64. ASSERTION : Phenol has lower boiling point then water.
REASON: Water forms more number of hydrogen bonds
65. ASSERTION : o-Hydroxybenzaldehyde is less soluable in water than p-Hydroxybenzaldehyde .
REASON: Intra molecular hydrogen bonding in o-HydroxybenzaldehydeDecreases extent of intermolecular
hydrogen bonding with water
66. ASSERTION : Rate of Et her formation with methanol at c-1 more than at c-2 in
H OH

H O
HO
2
HO
1 OH
H OH

H H
REASON: Carbocation At C1 more resonance stablised then at C2
OH
OH

O2 N NO 2
Conc.HNO3
(Major)
67 .ASSERTION : Conc.H 2 SO4

NO2

REASON : Nitric acid , a strong oxidizing agent oxidises Phenol in to para benzoquinone
68. ASSERTION: Phosphorus tribromide is often preferred as a reagent for the transformation of an
alcohol to the corresponding alkyl bromide.
REASON :The net result is conversion of 3 mol of alcohol to alkyl bromide by 1 mol of phosphorus
tribromide.
69. ASSERTION : Intermolecular dehydration is not useful for the preparation of unsymmetrical
ethers from primary alcohols
REASON : The reaction leads to a mixture of products.

70. ASSERTION : Bond angle at oxygen in etehers is greater than ideal tetrahedral angle .
REASON :Stearic hindrance between alkyl groups increases bond angle .

OH
O OH

COO-

+ CO2 ra ther then

71. ASSERTION :

COO-

REASON : Salicylate ion is a weaker base than para hydroxy benzoate due to stablization by intramolecular
hydrogen bonding.
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES

LEVEL - VI - KEY
SINGLE ANSWER TYPE QUESTIONS
01.B 02.A 03.B 04.B 05. D 06.A 07.C 08.A
09. D 10. D 11. A 12. D 13. C 14. C 15. B 16. B
17. A 18. D 19. D 20. D 21. A 22. B 23. A 24. B
25. B 26. C
MULTIPLE ANSWER QUESTIONS
27.A,C 28.C,B 29.A,B,C 30.A,C 31.B,C 32.B,C 33.A,B,C
34.A,B,C,D
COMPRAHENSION TYPE QUESTIONS
35. b 36. b 37. b 38. b 39. c 40.b 41. d 42. b
43. a 44. a 45. c 46. c 47. c 48. d 49. c
MATRIX MATCHING TYPE QUESTIONS
50.A-Q,S B-P,Q,R,S C-Q,R D-PQ, R 51. A - P, Q,R B-Q,R C - Q,R S D- P,Q,R
INTEGER TYPE QUESTIONS
52.6 53.2 54.1 55.3 56. 4 57.6 58.3 59.6
60.4 61.6
ASSERTION & REASION TYPE QUESTIONS
62.D 63.A 64.A 65.A 66.A 67.A 68.A 69.A
70.A 71.A

HINTS & SOLUTIONS

O
O

AlCl3
O

OH
01. H3C
Fries rearrangement.Oxygen is ortho para directing
electrophile is directed towards para position

O
due to conjugation of lone pair with phenyl ring
02. bond cleavage does not occur
03. Conceptual

18
18 + OH
O CH3
H

OH
18 + H
04. O
18
H2O H3C OH
CH3
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

NH2 + O
N2
HO H HO HO H H
H
HNO2
05. +

H H H H

OH
OH
C+
06. C+
O O
07. Intra molecular oxymercurisation demercurisation. Since 6 membred ring is more stable then 5 membred
ring c is the major product formed.

HO CH3 CH3
+
C
TsOH
08. OH
OH 

H3C CH3 H3C CH3

09. Hydrolysis is via carbocation intermediate.Negative inductive effecting groups decrease the stability of the
carbocation.
10. in d epoxy ring is cleaved that gives raise to an electrophillic carbon.Double bond serves as nucleophillic
donor.

H
H +
HO O
+
CH3 CH3 CH CH3
H+ CH3 CH3 +
C
+
CH
11.
CH2

12-20. Conceptual and factual

OH O OCH 3
2
SN
 C2 H 5ONa   CH 3  I  
21.
NO2 base NO2 NO2
acid
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
22. F  CH 3 .CH 2 .CH  CH .CH 3 . For ‘G’ check all possible isomers for C5 H10 Br2

OH
O2 N NO2

23. more acidic than H 2CO3 . Hence decomposes NaHCO3

NO2
24. Addition of water across C = C followed by hydrolysis of ether group.
25. Chlorination of toulene followed by aireal oxidation
26. Cleavage of ether group followed by Wurtz reaction

MORE THAN ONE CORRECT

27. In acid

OH
OH OH
H
+
O H H
+ O + OH
C O
H H3C
H3C H
CH3

28. In trans chlorohydrin OH group and Cl are at axial positions , anti ,to each other , epoxide can be formed
In cis chlorohydrin OH group and Cl are cis to each other H and Cl are anti to each other ,
dehydrohalogenation takes place. This leeds to enol that tautomerises to ketone.

Cl

OH

H
OH-

29. At acid pH (< 6) an amino group is a stronger activating substituent than a hydroxyl group (i.e. a phenol).
At alkaline pH (> 7.5) phenolic functions are stronger activators, due to increased phenoxide base
concentration.
coupling can take place only in the presence of electron withdrawinf group.Methyl group decreases
electrophilicity .
30. (a) The 3-ethylpentyl ether is more rapidly cleaved. Bridgehead 3¡-cations are unstable.
(b) The cyclic acetal on the right is more rapidly cleaved.
(c) The enol ether on the right is more rapidly cleaved.
(d) The methyl ether cleaves more rapidly. SN2 attack of bromide anion on a protonated intermediate.
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

CH 3 CH 3
CH 3
CH 3
D
Duterium shift
+ +
31. + CH H C
O D HO
H HO D
H OH
D

CH3
CH3

+
CH
D HO
OH
H

32. Where ever tendency to form stable carbocation exists There unimolecular reaction takes place
33.

OH OH
OH (1) CH3CO3H
O O
+
CH 2
CH 3 CH 3
CH 3

OH
O OH
O OH-

SN2
CH3
CH3

H O HO H
O
Et H Me
Me

Et Et
Et
34. Et Cl Me Et OH

H 2O
HO H OH OH
Me Me OH HO H
Et = =
Et Et Et Et
Et OH
H Me
intra molecular hydrogen bonding
makes above conformation stable
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
COMPRAHENSION -1
35. Conceptual
36. A is phenol and B is a secondary alcohol
37. When mixed ethers are used, the alcohol and alkyl iodide that form depend on the nature of the alkyl groups
.Mechanism here is by SN1 .

H3C 18
OH
O2N

H18
O

COMPRAHENSION - 2
(38-40)

CH3
CH3 CH2CH3
CH3
CH3 CH3
H OH
H OH H OH
H OH
H OH H OH
CH2
CH2 H OH
HO H
H OH HO H
HO H
H OH CH2CH3
CH2CH3
CH3 CH3
CH3
CH3 II III
I IV VI
V

Periodic acid only cleaves cis glycols. Compounds possesing plane of symmetry are optically inactive even
though they have assymmetric carbons.
COMPRAHENSION -3
(Q.No. 41-43)
Br

B
OH
A

OH

D
C
JEEASD MAINS
ALCOHOLS, - VOL &
ETHERS - IPHENOLS

Final product

Comprahension - 4 (Q.No. 44 & 45)

since COOH is a good leaving group on bromination ipso subtitution takes place.
Hint for the paragraph:

CHO COOH Br
CHO

OH
OMe OMe Br OMe

OMe OMe OH
OMe

Bromination is known to occur with a good leaving group in phenols if present either at ortho position or at
para position.
47. Conceptual
48. Conceptual
49. Aldehydes having no  -hydrogen undergo Cannizarro’s reaction
.
INTEGER TYPE

18
O
18 O
52. O O O
18 18 18

.since oxygen is conjugated to a double bond ,it isin resonance with it and cleavage does not
O
18
take place.
53. Cleavage at 2 leads to aromaticity.
 RELATIONS
JEE ADVANCED-VOL
SOLUTIONS - VIII
AND COLLIGARIVE PROPERTIES
54. only olefinic oxygens in conjugation undergo tautomerisation

6
5 1
55. ans: 3
4 2
3

claisen rearrangement occurs via 6membred transition state. Tautomerism is not possible at 1 and 5
positions. tautomerisation anly takes place at 3
56. Conceptual
57. Presence of electron releasing groups on the benzene ring of phenol decreases acidic character and presence
of withdrawing groups on the benzene ring increases acidic character.
58. Acids stronger than carbonic acids decomposes NaHCO 3
59. Compounds containing acidic hydrogens desolves in NaOH.
60. Aliphatic Primary alcoholsdo not give turbidity with lucas reagent without heating.
61. Compounds containing methylketonic group or those can give compounds containing methylketonic group
on oxidation give iodoform test.
62. Ketoenaltutomerism
63. Equilibrium in keto - enol tautomerism is favoured whereever stability of isomer is more favoured
since eneol is more stable , compound does not ecist on keto form,
64. More number of hydrogen bonds implies greater intermolecular forces .less volatility , more boiling point
65. Intermolecular forces increases soluability.
H OH

H O
HO
2
66. HO
1
H OH
H
H

67. Conceputal
68. ans : A Hint : The mechanism for the reaction involves attack of the alcohol group on the phosphorus
atom, displacing a bromide ion and forming a protonated alkyl dibromophosphite
69. primary alchols give mixture of products.

O
bo nd pair rep ulsions
are greate r the n
70. lon e p air lon e p air
rep ulsion s

O O

71. H