Alcohols, Ethers and phenol     2.

15 |

Solved Example
1. The final product obtained in the reaction (1) I and II (2) II and III
(3) III and I (4) II and IV
Sol. [1]
(I)

(1) (2)
(II)

(3) (4)

(III)
Sol. [1]
CH3 Neutral KMnO4
HO CH3 (IV) CH2=CH–CH3 oxidation
1. Hg(OAc)2/THF-H2 O/20 sec
2. NaBH4 (6 min) CH3–COOH+H–COOH
+ – Acetic acid Formic acid
Hydration (addition of H /OH ) takes place accord-
OCH3 OCH
ing to Markownikoff rule. 3
≈
4. CO2H H3O
2. Which of the following compounds does not give (A) (B)
D
alcohol on reaction with RMgX?

Product (B is)
(1) O2/H≈ (2) OH O

(3) HC∫N/H≈ (4) (1) (2)

Sol. [3]
OH OH
O
(3) (4)

Sol. [2]

H3CO OCH3 HO OH
CO2H CO2H
≈
3. Which one/ones of the following reactions will yield H3O –H2O
2-propanol? Choose the right answer from (I), (II),
(III) and (IV) unstable

(I) O O
COOH D
(II) –CO2

b keto acid
(III)
5. Dehydration of alcohol to alkene by heating with
(IV) conc. H2SO4 the initiation step is ____ followed with
_____ mechanism.
 |
2.16    Organic Chemistry Module II

(1) Elimination of water, free radical CH3

(2) Formation of an ester, free radical PBr3 Mg/Et2O (i) CH3–CH–CHO
8. OH (X) (Y) + (Z)
(3) Protonation of alcohol, carbocation (ii) H3O
(4) Protonation of alcohol, carbanion
Sol. [3] (I) Y is (II) Y is

(III) Z is
6. Ethylene glycol on treatment with Pl3 mainly gives:
(1) Ethylene (2) Ethylene iodide
(3) Ethyl iodide (4) Ethane
Sol. [1]
(IV) Z is
CH2–OH CH2–I CH2
PI3
CH2–OH CH2–I –I2 CH2 Select the correct code for given reaction
unstable
(1) I and III (2) II and IV
7. In which of the following reactions, alcohol is formed (3) I and IV (4) II and III
as product gives positive iodoform test? Sol. [4]

PBr3 Mg/Et2O
(1) OH Br Mg/Br

(X) (Y)
CH
(2)
CH3–CH–CHO NAR
+
H3O
(3) CH3
CH–CH–CH3

(4) OH
(Z)
Sol. [2]
O Ph CH3
Ph–MgBr I2 KOH 18
conc. HI
CH3–C–CH3 + CH3–C–CH3 –ve test 9. CH3–O–C–CH3
H OH/H
OH CH3
(tertiary alcohol)
Product of above reaction is:
MeMgBr I2 KOH +ve
CH3–CH2–CH=O + CH3–CH2–CH–CH3
H OH/H test
OH (1)
(Secondary alkanol)
O
Ph–MgBr Ph–MgBr
H–C–O–Et + Ph–CH=O + Ph–CH–Ph
H OH/H H OH/H
OH (2)
I2 Ω KOH

–ve test

O Ph
Ph–MgBr
(3)
I2ΩKOH
CH3–C–O–Et + CH3–C–Ph –ve test
H OH/H
OH
 |
Alcohols, Ethers and phenol     2.17

Sol. [4]
(4)

Sol. [2]
When one of the alkyl of ether is 3° alkyl then
breaking of C–O bond takes place by SN1 path.
  In SN1 reaction, breaking site towards the most
stable carbocation 12. When sodium benzenesulphonate is fused with solid
sodium hydroxide and subsequently acidified with
dilute sulphuric acid, the product formed is:
(1) benzene (2) sodium phenoxide
(3) thiophenol (4) phenol
Sol. [4]
10. Consider the following sequence of reaction

PhCH3(excess) + Cl2 A B C

A+C D. Product D is:

(1) PhCH2OPh (2) PhCH2OCH2Ph O

18 H≈
13. Ph–C–OH + EtOH D (P) major product, Product
(3) PhCH2CH2Ph (4) (P) is–

Sol. [2]
(1) (2)

(3) (4)
Sol. [2]

– SN2
Ph–CH2–O–CH2–Ph
Ph–CH2–Cl+Ph–CH2–O
(A) (C) 14. Consider the reaction:
Williamson synthesis

11. Identify the product C in the given reaction.
(1)

(2)
(1) CH3–COOH (2) CH3–CH2–NH–OH

(3)
(3) (4) CHI3+HCOO–
(4)
 |
2.18    Organic Chemistry Module II

Sol. [4] Sol. [3]

Coupling reaction predominantly takes place at the Benzene sulphonyl chloride (Ph–SO2Cl) is known as
para position. Hinsberg reagent.

O
15. Benzenediazonium chloride can be converted into COOH
NaBH4 LiAlH4
phenol by treating it with 18. (B) Me (A)
(1) H3PO3, H2O, CuCl (2) H2O, heat The products (A) and (B) are:
(3) Alcohol, heat (4) HBF4, and NaNO2/Cu
(A) (B)
Sol. [2]

(1)

16. Cold KMnO4
A
CrO3
B, A and B are: (2)
OH AcOH

(1)
(3)

(2)

(4)
(3)

Sol. [3]
NaBH4 is a weak reducing reagent. So it reduces only
carbonyl group while reduction of –COOH group
does not happen and it remains unaffected.
(4)   LiAlH4 is strong reducing reagent; so it can reduce

both and –COOH groups.

Sol. [1] 19. The structure of the compound that gives tribromo
3°(OH) derivative on treatment with bromine water is:
Cold KMnO4 CrO
OH 3
OH
OH AcOH
OH oxidation O
Hydroxylation 2°(OH) (1) (2)
(A) (B)
Oxidation of 3°-alcohol does not take place and
2°-alcohol oxidised into ketone.
17. Phenol on reacting with Hinsberg’s reagent gives: (3) (4)
(1) Sulphone (2) Sulphanilic
(3) Sulphonic ester (4) Sulphonal
 Alcohols, Ethers and phenol     2.19 |
Sol. [4] (3) m-Hydroxy benzoic acid
(4) p-Hydroxy benzyl alcohol
Sol. [1]
OH OH OH OH
Q
HCN/HCl/H2O OH/D +
Gattermann Cannizaro
aldehyde reaction Q
synthesis CH=O CH2–OH COO

≈
H

OH OH
20. .
Lucus reagent +
White turbidity

X gives white turbidity with Lucas reagent instantly.

X and Y both turn blue litmus solution red. Y can CH2–OH COOH
be: (X) (Y)

(1) p-Hydroxy benzoic acid Both are phenolic so that (X) and (Y) give litmus
(2) p-Hydroxy benzaldehyde test.

Exercise 1
CHCH3 CH=CH2 CH2CH2–OH (1) Primary alcohol (2) Secondary alcohol
1. B A (3) Aldehyde (4) Ketone
OH
C
4. Which ‘A’ gives blue colour in the reaction?
(i) HNO2
CH2CH3 ‘A’ blue colour
(ii) NaOH
OH
(1) CH3CH2NO2 (2) (CH3)2CHNO2
Select schemes A, B, C, respectively, out of
I. Acid catalysed hydration (3) (CH3)3CNO2 (4)
II. HBO
III. Oxymercuration–demercuration 5. Which of the following pairs cannot be distinguished
(1) I in all cases (2) I, II, III by using Lucas reagent?

(3) II, III, I (4) III, I, II (1)

2. The reaction
O (2)
n-C2H7ONa
CH3–C–OC2H5 + n-C3H7OH
(3)
CH3COOC3H7(n) + C2H5OH is known as:

(1) Esterification (4)

(2) Double decomposition
(3) Transesterification 6.
(4) None of these
3. A compound ‘X’ with molecular formula C3H8O can
be oxidised to a compound ‘Y’ with the molecular
formula C3H6O2, ‘X’ is most likely to be: (1) (2)
 |
2.20    Organic Chemistry Module II

(3) unchanged methyl propionate

(4) both propionic acid and methyl propionate
(3) (4)
12.

Alcohol (Y) gives Lucas test immediately. Thus, (X)

7. and (Y) are, respectively:
(1) CH3COOC2H5; (CH3)3(COH)
(2) HCOOC3H7; C2H5CH(CH3)OH
(3) C2H5COOCH3; (C2H5)3COH
(1) (2) (4) HCOOC3H7; CH3(CH2)3OH
13. The enzymes A, B and C in the reaction sequence
are:
(3) (4) None A B C
(C6H10O5)n C12H22O11 C6H12O6 C2H5OH

(1) Invertase, Maltase, Zymase

8. A + Ac2O (B)
(2) Diastase, Maltase, Zymase
(acetic anhydride)
(3) Maltase, Zymase, Invertase
Molecular formula of A increases by C8H8O4. (4) Diastase, Zymase, Maltase
Number of OH group present in A are:
14. A carbon compound A forms B with sodium metal
(1) 3 (2) 4 and again A forms C with PCl5, but B and C form
(3) 5 (4) 6 diethyl ether. Therefore A, and B and C are:
9. A. A is (1) C2H5OH, C2H5ONa, C2H5Cl
(2) C2H5Cl, C2H5ONa, C2H5OH
(3) C2H5OH, C2H6, C2H5Cl2
(4) C2H5OH, C2H5Cl, C2H5ONa
(1) (2)
15. In order to obtain diethyl ether from ethanol and
sulphuric acid, the latter is taken:
(1) In equal amount of sulphuric acid
(3) (4) CH3–CH=O (2) In slightly lesser amount of sulphuric acid
(3) In excess amount of sulphuric acid
(4) In far lesser amount of sulphuric acid
10. Which of the following reagents would carry out of
CH3
the following transformation ? (D = 2H)
16. The synthesis of Ph–C–OH cannot be achieved by:
O OH
? C2H5
CCH3 CCH3
O
D ≈
H /H2O
(1) PhMgBr + CH3–C–C2H5
(1) NaBD4 in CH3OH (2) LiAlH4, then D2O
O
(3) (NaBD4 in CH3OD (4) LiAlD4, then D2O H≈/H2O
(2) C2H5MgBr + Ph–C–CH3
11. Methyl propionate, CH3CH2COOCH3, is heated
with aqueous H2SO4 in 18O labelled water. When O
≈
the equilibrium is achieved, the labelled oxygen will (3) CH3MgBr + Ph–C–CH2CH3
H /H2O
be present in:
(1) methyl alcohol O
(2) Propionic acid H≈/H2O
(4) PhMgBr + CH3–C–Cl
 |
Alcohols, Ethers and phenol     2.21

17. Which of the following is the final product in the 22. Which of the following is the best method for making
reaction between benzoyl chloride and phenyl mag- isopropyl methyl ether?
nesium bromide? (1) CH3I + (CH3)2CHOH
(2) CH3I + (CH3)2CHO–
(1) (2) (3) (CH3)2CHI + CH3O–
(4) (CH3)2CHCl + CH3OH
(3) C6H5COOH (4) (C6H5)3COH 23. Which sequence of steps describes the best synthesis
18. The order of solubility of of 2-methyl-3-pentanone?
O

(1) (1) 1-Propanol + (CH3)2CHMgBr, diethyl ether
in water is: (2) H3O+
(1) I > II > III (2) I < II < III (3) PCC, CH2Cl2
(3) II > III > I (4) II > I > III (2) (1) 1-Propanol + Na2Cr2O7, H2SO4, H2O, heat
O O (2) SOCl2
O HO (3) (CH3)2CHCl, AlCl3
19. OCH3 OCH3
(3) (1) 1-Propanol + PCC, CH2Cl2
(2) (CH3)2CHLi, diethyl ether
Above conversion can be achieved by– (3) H3O+
(1) LiAlH4 (2) NaBH4
+
(4) Na2Cr2O7, H2SO4, H2O, heat
(3) H3O (4) PCC (4) (1) 2-Propanol + Na2Cr2O7, H2SO4, H2O, heat
≈
CrO3/H (2) CH3CH2CH2Li, diethyl ether
20. (A) (B) CHI3+ Salt of acid
C4H10O (3) H3O+
Reactant (A) is: (4) PCC, CH2Cl2
(1) (2) 24.

(3) (4)
(1)
Q
CH3C C CH3l H2/Pd/BaSO4
21. CH3–CH–CH2 (X) (Y) (Z)
(2)
O
Which one in not correct
(3)
(1)

(4)
(2)
25. The major product formed in the reaction is:

(3)

H
(4) Z is CH3–CH–CH2–C=C
(1) (2)
OCH3 H CH3
 |
2.22    Organic Chemistry Module II

29.
(3) (4)

What is false about this reaction–

H3C
LiAlH4/H≈ (1) one compound is phenol which is less acidic than
26. H C A, A is
3 other compound
O
(2) one compound is phenol and other is methanol
(1) (2) CH3CH2CH2CH2OH (3) reactant is anisole
(4) this reaction occur through SN2 reaction
30. A compound of molecular formula C7H8O is
insoluble in water and dilutes sodium bicarbonate
(3) (4) No reaction but dissolves in dilute aqueous sodium hydroxide
and gives a characteristic colour with aqueous FeCl3.
On treatment with bromine water, it readily gives
precipitate of C7H5OBr3. The structure of ‘A’ is:

27. major A

and B are: (1) (2)

(1)

(3) (4)

(2)

31. Which of the following can give purple colour with

neutral FeCl3?

(3)

(4)
(1) II and IV (2) I and III
(3) II and III (4) III and IV
32. Ortho-nitrophenol is steam volatile, whereas
para-nitrophenol is not. This is due to
28. (1) the presence of intramolecular hydrogen boding
in o-nitrophenol.
(2) the presence of intermolecular hydrogen bonding
Compound is: in o-nitrophenol.
(3) the presence of intermolecular hydrogen bonding
(1) (2)
in p-nitrophenol.
(4) None of these.
(3) (4) 33. Phenol cannot be converted into salicylic acid by
heating with:
 |
Alcohols, Ethers and phenol     2.23

(1) CO2 (under pressure) and alkali 38. The bromination of salicylic with bromine water
(2) CCl4 and alkali gives
(3) CHCl3 and alkali
(4) HCN/HCl, followed by oxidation
34. 4-Hydroxybenzenesulphonic acid is treated with bro- (1) (2)
mine water. The product formed is:
(1) 2, 4, 6-tribromophenol
(2) 3, 5-dibromo-4-hydroxybenzenesulphonic acid
(3) 3-bromo-4-hydroxybenzenesulphonic acid
(4) 2, 6-dibromophenol (3) (4)
35. In the Liebermann nitroso reaction, changes in the
colour of phenol occur as:
(1) Brown or red-green-red-deep blue 39. Identify the nature of product of in the following
(2) Red-deep blue-green reaction:
(3) Red-brown-white
(4) White-red-green
36. Which of the following is the major product from
given sequence?

(1) (2)

(1) (2)

(3) (4)

(3) (4)

40.
37. Which of the following would undergo most rapid
hydrolysis with aqueous NaOH to furnish the
corresponding hydroxyl derivatives? Identify the structure of ‘P’

(1) (2)
(1) (2)

(3) (4) (3) (4)

 |
2.24    Organic Chemistry Module II

Exercise 2

(3) 2lCH2CH2l
(4) CH3CH2l+CH3CH2OH
1.

5. (A), Product (A) is:

(I) x = 3
(II) A will show geometrical isomerism
(III) B is optically active
(IV) C is optically inactive
Select correct statement
(1) (2)
(1) (I), (II), (IV) (2) (I), (II), (III)
(3) (II), (III), (IV) (4) (I), (II), (III), (IV)

2. A; A (major product) is:

(3) (4)

(1) (2)
6.

(3) (4) Give the product (C) in the above reaction

(1) 2-Methoxy hex-4-yne
3. A chiral C7H16O2 diol is oxidised by PCC in CH2Cl2 (2) 4-Methoxy hex-2-yne
to an achiral C7H12O2 compound. Which of the fol-
(3) 5-Methoxy hex-2-yne
lowing would satisfy these facts?
(4) None of these
7. Which describes the best stereochemical aspects of
(1) (2) the following reaction?

(3) (4)
(1) Inversion of configuration occurs at the carbon
4. What product(s) are expected from the following undergoing substitution.
reaction? (2) Retention of configuration occurs at the carbon
undergoing substitution.
(3) Racemisation occurs at the carbon undergoing
?
substitution.
(4) The carbon undergoing substitution is not
(1) 2CH3CH2l sterogenic.
(2) 2lCH2CH2OH 8. What is the structure of the major product when
phenol is treated with bromine water?
 |
Alcohols, Ethers and phenol     2.25

(1) (2) (1) (2)

(3) (4)

(3) (4)
9. Suggest a suitable oxidising reagent for the following
conversions:

OH ? H
(A) Me Me
O
Me Me

? 12.
(B)
OH O
Final product is:
Me Me Me Me

(1) MnO2 in (A) and CrO3 (in glacial acetic acid)

in (B)
(2) CrO3 in (A) and MnO2 in (B) (1)
(3) both are correct
(4) both are incorrect

O–COCH3
10. COOH
(2)
H 2C
X = moles of HI consumed.
Value of x is: O Br
(1) 2 (2) 4
OH
(3) 5 (4) 6 Br Br
11. Observe the following reaction carefully. Select the
correct answer regarding the major product formed (3)
and the relative reactivity of compound X with respect
to ethene for the following reaction. O CH3

OH
O
OH
Br2(leq.)/CCl4 Br C
x=
OH
(4)

CH=CH2
O CH3
 |
2.26    Organic Chemistry Module II

16. Compounds X and Y both have the same molecular

formula C4H8O, and they give the following results
13. ‘P’, the product with some characteristic tests:
Tests Compounds X Compound Y
‘P’ is– Bromine Decolourise No reaction
Na Metal Bubbles No reaction
Chromic acid Orange to green No reaction
(1) (2) Lucas reagent Slow reaction No reaction
Which of the following structures for X and Y are
consistent with the test results?

(1)

(3) (4)
(2)

(3)
CH3 (x) CH3 (y)
14. C–CH2–CH3 C–CH2–CH3
CH3 CH3
OH O (4)

3° alchol

17. Reaction I:
CH3
CH–CH–CH3
CH3
OH
2° alchol Reaction II:
Find missing reagents
(1) x = LiAlH4, y = NaBH4
(2) x = LiAlH4/AlCl3, y = LiAlH4
Products A and B are respectively
(3) x = LiAlH4, y = LiAlH4/AlCl3
(4) x = H2/Ni, y = H2/Pt (1)
15. The given compound is prepared by–

(2)

(1) (3)

(2) (4)

18. Which is/are correct Statements?

(3)
(A)

(4)
 Alcohols, Ethers and phenol     2.27 |
NaOH
CH3 CH3 CH3OH
(B) C C (3) (4)
H CH3
O
21. In the reaction, CH3CH2ONa + CH3CH2OSO2CH3
Nucleophile attacks here
the product formed is:
(C) This is only affected in reduction to 2° alcohol
(1) CH3CH2OCH3
(2) CH3CH2OCH2CH3
(3) CH3CH2OSO2OCH2CH3
(4) CH3CH2OSO2OCH3

(D) These bonds are 22. Major product?

(1) (2)
affected in esterification
(1) A and D (2) A and B (3) (4) None of these
(3) A, B and C (4) A, B, C and D

19. Reaction (I) (A) (major)

23.

Reaction (II) (B) (major) The products X and Y are

Reaction (III) (C) (major) (1) (2)

Product obtained in above reactions (I), (II) & (III)

is: (3) (4)
(1) A = B, but C is different
(2) A = C, but B is different 24. The product ‘P’ of the following reaction is:
(3) B = C, but A is different
(4) A = B = C all product are identical
20. The best choice of reactant(s) for the following con- (P)
version is:

?
(1)

CH3
(1) OH (2)
OH (2)
 |
2.28    Organic Chemistry Module II

(3) (1)

(2)
(4)
(3)

(4)
25. Y; Identify Y in this reaction.

29.

(1) (2)

(1) (2)

(3) (4)

(3) (4)

30. A C7H14O optically active alcohol is oxidised by

26. (A). Product (A) is: Jones’ reagent (H2CrO4) to an optically inactive
(achiral) ketone. Which of the following compounds
meets these facts?
OH
(1) (2) Ph–C–Ph
(1) (2)
Ph

(3) (4) (3) (4)

O 31. What is the order of solubility of the following in

water?
O
27. A
OH OH
OH
O
Reagent A used in this change is:
(1) Sn/HCl (2) LiAlH4
(3) NaBH4 (4) HI/P4 (1) I < II < III (2) III < II < I
(3) III < I < II (4) II < I < III
28. 32. What is the major product of the following
reaction?
 Alcohols, Ethers and phenol     2.29 |
34. Consider the following roadmap reaction:

O—CH2
H2SO4 Na Z
Y H2/Heat D

(1) (2) The most probable structure of X is

(1) (2)

(3) (4)
(3) (4)

33. The major organic product formed in the following 35. ?

reaction is

(1) (2)

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

(3) (4)

Exercise 3
One and More Than One Option Correct Type Question (3) Isotopic oxygen is present in the new alcohol
1. C2H5Br can be converted into C2H5–O–C2H5 by: *
(EtOH) formed
(1) Reacting by C2H5ONa (4) Rate of transesterification is dependent on the
(2) Heating with moist Ag2O concentration of ester only.
(3) Heating with dry Ag2O 3. In the following reaction.
(4) Treating with C2H5MgBr
2. Which of the following statements is correct about
the transesterification reaction, catalysed by

H3O≈ (H2SO4 or dry HCl) or ROQ (EtONa)?
The possible substitution product (s) is/are

(1) (2)

(1) Alcohol (PrOH) is taken in excess to shift the

equilibrium to R.H.S. OH
(3) (4)
(2) It involves tetrahedral intermediate in which the
O
hybridisation of C of the (C = O) group changes
from sp2 to sp3 4. In the reaction given below,
 |
2.30    Organic Chemistry Module II

8. Consider the following reaction,

X(C6H12O) Gas evolved

The correct statement regarding the outcome of the

above reaction is/are
(1) A pure enantiomer of alcohol is formed
The correct statement(s) concerning X and Y is / are
(2) Racemic mixture of alcohol is formed
(1) Both form immediate turbidity with HCl in the
(3) Product alcohol has deuterium attached to presence of ZnCl2
oxygen
(2) Both change colour of CrO3 – H2SO4
(4) Product alcohol has deuterium attached to
(3) X gives yellow solid with NaOH/I2
carbonyl-carbon atom
(4) X decolourises Br 2-CCl 4 solution forming
5. Which of the following is true statement regarding
C6H12OBr2
reaction of cis and trans-2-hexene with CH3OH/H+
(1) Both react at same rate 9. Consider the following reaction
(2) Cis isomer reacts faster than trans isomer
(3) Both cis and trans isomers give mixture of
positional isomers as the major product
(4) No reaction is possible The correct statements(s) concerning the above trans-
6. Upon treatment with bromine water, allyl bromide formation is/are
gives chiefly primary alcohol BrCH2CHBrCH2OH. (1) If I is treated with Na followed by addition of CH3I
What are the expected primary alcohols in the gives II with the retention of configuration
following reaction?
(2) If I is treated with TsCl followed by the
80
[Normal bromine is Br ] addition of CH3ONa gives II with inversion of
configuration
(3) If I is first heated with concentrated H2SO4
followed by the addition of CH3OH in dil.
H2SO4 gives racemic mixture of II
(1) (2) (4) If I is heated with concentrated H2SO4­ followed
by the treatment with (CH3COO)2Hg—CH3OH
and finally reducing the mercurinium intermediate
with NaBH4 gives a pure enantiomer of II
10. Consider the reaction given below,
(3) (4)

7. Alcohols given below that behaves like 1°-aliphatic

alcohol in Lucas test is/are
The correct statement regarding the above reaction
(1) is/are

(1) The major product is

(2)

(3) (2) The major product is

(3) The product would be a single enantiomer

(4) (4) The product would consist of a racemic
mixture
 |
Alcohols, Ethers and phenol     2.31

11. In the reaction below, Statement-II: It is the property of all the enolic
compounds.
15. Statement-I: 3-Methyl-2-butanol is more reactive than
2-butanol in acid catalysed dehydration to alkene.
The correct statement concerning the above reaction
Statement-II: 3-methyl-2-butanol forms more stable
is/are
carbocation than 2-butanol during dehydration
(1) Y is a racemic mixture while Z is achiral reaction.
(2) Both Y and Z are racemic mixture
(3) A diastereomer of Y gives racemic Z Comprehension Type Question
(4) X shows diastereomerism but not enantiomerism
Passage based questions (Q. 16–18)
12. In the following rearrangement, possible product(s)
An organic compound X(C10­H12O3) is not soluble in water
is/are
or NaHCO3. A solution of Br2 in CCl4 is decolourised
by X forming C10H12O3Br2. X on controlled ozonolysis
followed by the treatment with (CH3)2S gives Y(C8H8O3)
and C2H4O2. Y can also be obtained by reaction between
ortho methoxy phenol with CHCl3 in KOH solution followed

by acid hydrolysis.
O 16. What is the correct structure of X?

(1) (2)
(1)

(3) (4)

(2)
13. 3-methyl-3-hexanol can be prepared by the reaction
of
(1) CH 3 MgBr and 3-hexanone followed by
hydrolysis
(2) C 2H 5MgBr and 2-pentanone followed by (3)
hydrolysis
(3) propyl-MgBr + 2-butanone followed by
hydrolysis
(4) C 4 H 9 MgBr and propanone followed by
hydrolysis (4)

Statement Type Question

17. If X is treated with cold HBr, the major product
(1) If both Statement-I and Statement-II are correct would be
and Statement-II is the correct explanation for
Statement-I
(2) If both Statement-I and Statement-II are correct
and Statement-II is not the correct explanation for (1)
Statement-I
(3) If Statement-I is correct and Statement-II is
incorrect
(4) If Statement-I is incorrect and Statement-II is
correct
14. Statement-I: Phenolic compounds give characteristic (2)
colours with neutral FeCl3.
 |
2.32    Organic Chemistry Module II

(1) a Æ s; b Æ r; c Æ p; d Æ q

(3) (2) a Æ s; b Æ p; c Æ r; d Æ q
(3) a Æ p; b Æ s; c Æ q; d Æ r
(4) a Æ s; b Æ q; c Æ p; d Æ r

(4) 21. Match the pairs of compounds in Column-I with

the appropriate Column-II. Distinguishing test in
Column-II
18. What would be the major product if X is treated with
cold concentrated H2SO4? Column-I Column-II
(a) Methanol and ethane-1, (p) Lucas test
(1) (2) 2-diol
(b) O-cresol and Benzyl (q) Iodoform test
alcohol
(c) n-butyl alcohol and (r) Litmus test
(3) (4) iso-butyl alcohol
(d) 2-Pentanol and (s) Periodic acid test
3-pentanol
Column Matching Type Questions
19. Match the statements given in Column-I and (1) A Æ r, B Æ p, C Æ s; D Æ q
Column-II (2) A Æ s, B Æ r, C Æ q; D Æ p
(3) A Æ s, B Æ r, C Æ p; D Æ q
Column-I Column-II
(4) A Æ r, B Æ s, C Æ p; D Æ q
(p) LiAlH4
(a)
22. Make the correct match of the following from List-I
and List-II.
(b) H–CH = O Æ CH3CH2OH (q) Zn-Hg/conc.
HCl List-I List-II
(r) DIBAL-H (A) (P) Picric Acid
(c)

(s) CH3MgBr
(d)
(B) (Q)
(1) a Æ p; b Æ q; c Æ r; d Æ s
(2) a Æ q; b Æ s; c Æ p; d Æ r
(3) a Æ p; b Æ q; c Æ s; d Æ r
(4) a Æ r; b Æ s; c Æ q; d Æ p (C) (R) CH3OH
20. Match the reagents given in Column-I with the appro-
priate items given in Column-II

Column-I Column-II (S)

(a) Conc. HCl–ZnCl2 (p) Reducing agent

(b) LiAlH4 (q) Grignard reagent
(c) pyridinium (r) Oxidising agent (1) A Æ P, B Æ Q, C Æ R, D Æ S
chlorochromate (2) A Æ S, B Æ P, C Æ Q, D Æ R
(d) Ethyl magnesium (s) Lucas reagent (3) A Æ P, B Æ S, C Æ Q, D Æ R
bromide (4) A Æ S, B Æ P, C Æ R, D Æ Q
 Alcohols, Ethers and phenol     2.33 |
23. Make the correct match of the following from List-I
Column I Column II
and List-II.
i. 1-butanol p. Treatment with H+/H2O
List-I List-II gives racemic mixture
(A) Ethyl alcohol (P) FeCl3 Test
ii. 2-butanol q. Changes the colour of
(B) Picric acid (Q) Iodoform Test
acidic K2Cr2O7
(C) Glycerol (R) Lucas Test
(D) Isopropyl alcohol (S) HIO4 iii. (+)-3-methyl- r. Gives turbid solution with
3-hexanol ZnCl2/Conc. HCl at room
temperature
(1) A Æ Q, B Æ P, C Æ S, D Æ R
(2) A Æ P, B Æ Q, C Æ S, D Æ R iv. (–)-2-ethyl s. With LiAlH 4 . gives
oxirane another compound from
(3) A Æ Q, B Æ P, C Æ R, D Æ S column II.
(4) A Æ R, B Æ S, C Æ P, D Æ Q

Codes:
24. Match the reactant from Column I with the reaction(s)
from Column II and mark the correct option from the i ii iii iv
codes given below. (1) p, q p, q, r p, r s
(2) q r p q
Column I Column II (3) p, s r p q
i. p. (4) p, q r s p
Racemic mixture

Single Digit Integer Type Question

ii. q. Pure, single 26. In the reaction given below,
enantiomer

iii. r.
Meso isomer
How many different products are expected?
27. In the following reaction how many different diols,
iv. s. are formed?
Racemic mixture

Codes: 28. An alcohol X(C4H10O3) is chiral and absorbs two

i ii iii iv moles of HIO4 per mole of X. How many stereoiso-
mers exist for X?
(1) r, s q p, s p, s
(2) p q r s 29. When 2-ethyl-3-metyl-1-pentene is treated with
(3) q r s p CH3OH in H2SO4, how many different methoxy
ethers would be formed in significant amount?
(4) q, p s p r
30. An organic compound A(C10H18O8) on treatment with
25. Match the column I with Column II and mark the excess of CH3COCI gives a fully acetylated product
correct option from the codes given below. whose molar mass is found to be 518 g/mol. How
many hydroxyl functional groups are present in A?
 |
2.34    Organic Chemistry Module II

Exercise 4
1. Maximum dehydration takes place that of (3) Boiling points
[AIEEE-2002] (4) Gaseous densities at the same temperature and
pressure
6. p-cresol reacts with chloroform in alkaline medium
(1) (2) to give the compound A which adds hydrogen cya-
nide to form, the compound B. The latter on acidic
hydrolysis gives chiral carboxylic acid. The structure
of the carboxylic acid is [AIEEE-2005]

(3) (4)

(1) (2)

2. An ether is more volatile than an alcohol having the

same molecular formula. This is due to
[AIEEE-2003]
(1) Dipolar character of ethers
(2) Alcohols having resonance structures (3) (4)
(3) Intermolecular hydrogen bonding in ethers
(4) Intermolecular hydrogen bonding in alcohols
3. During dehydration of alcohols to alkenes by heating
with concentrated H2SO4 the initiation step is 7. HBr reacts with CH2 = CH –OCH3 under anhydrous
[AIEEE-2003] conditions at room temperature to give–
(1) Protonation of alcohol molecule [AIEEE-2005]
(2) Formation of carbocation (1) BrCH2CHO and CH3OH
(3) Elimination of water (2) BrCH2–CH2–OCH3
(4) Formation of an ester (3) H3C–CHBr–OCH3
4. Among the following compounds which can be dehy-
(4) CH3CHO and CH3Br
drated very easily is [AIEEE-2004]
(1) CH3CH2CH2CH2CH2OH
8.

(2) The electrophile involved in the above reaction is

[AIEEE-2006]
(1) dichlorocarbene (:CCl2)
(3) Q
(2) trichloromethyl anion C Cl3
≈
(3) formyl cation (C HO)
≈
(4) (4) dichloromethyl cation (C HCH2)
9. The structure of the compound that gives a tribromo
derivative on treatment with bromine water :is:
5. For which of the following parameters the structural
[AIEEE-2006]
isomer C2H5OH and CH3OCH3 would be expected
to have the same values? [AIEEE-2004] CH3
(1) Heat of vaporisation OH
(2) Vapour pressure at the same temperature (1) (2)
 Alcohols, Ethers and phenol     2.35|
(1) 1-Butanol (2) 2-Butanol
(3) 2-Methylpropan-2-ol (4) 2-Methylpropanol
(3) (4) 17. Consider the following reaction [AIEEE-2011]
C2H5OH + H2SO4 Æ Product
Among the following, which one cannot be formed
10. Among the following the one that gives positive as a product under any conditions?
iodoform test upon reaction with I2 NaOH is (1) Ethylene (2) Acetylene
[AIEEE-2006] (3) Diethyl ether (4) Ethyl-hydrogen sulphate
(1) CH3CH2CH(OH)CH2CH3 18. Thermosetting polymer, Bakelite is formed by the
(2) C6H5CH2CH2OH reaction of phenol with [AIEEE-2011]
(1) CH3CHO (2) HCHO
(3) (3) HCOOH (4) CH3CH2CHO
19. Reagent used to convert allyl alcohol to acrolein is:
(4) PhCHOHCH3 [JEE Main Online-2012]
11. Acid catalysed hydration of alkenes except ethene (1) MnO2 (2) KMnO4
leads to the formation of [AIEEE-2006] (3) OsO4 (4) H2O2
(1) mixture of secondary and tertiary alcohols
20. An unknown alcohol is treated with the “Lucas
(2) mixture of primary and secondary alcohols reagent” to determine whether the alcohol is primary,
(3) secondary or tertiary alcohol secondary or tertiary. Which alcohol reacts fastest
(4) primary alcohol and by what mechanism- [JEE Main-2013]
12. In the following sequence of reactions, (1) secondary alcohol by SN2
[AIEEE-2007] (2) Tertiary alcohol by SN2
(3) Secondary alcohol by SN1
(4) Tertiary alcohol by SN1
the compound D is
21. Rate of dehydration of alcohols follows the order-
(1) butanol (2) n-butyl alcohol
[JEE Main Online-2013]
(3) n-propyl alcohol (4) propanol
(1) 2° > 1° > CH3OH > 3°
13. Phenol, when it first reacts with concentrated sulphuric
acid and then with concentrated nitric acid, gives (2) 3° > 2° > 1° > CH3OH
[AIEEE-2008] (3) 2° > 3° > 1° > CH3OH
(1) o-nitrophenol (2) p-nitrophenol (4) CH3OH > 12° > 2° > 3°
(3) nitrobenzene (4) 2, 4, 6-trinitrophenol 22. An ether (A), C5H12O, when heated with excess of
14. A liquid was mixed with ethanol and a drop of con- hot concentrated HI produced two alkyl halides which
centrated H2SO4 was added. A compound with a when treated with NaOH yielded compounds (B) and
fruity smell was formed. The liquid was (C). Oxidation of (B) and (C) gave a propanone and
an ethanoic acid respectively. The IUPAC name of
[AIEEE-2009]
the ether (A) is- [JEE Main Online-2013]
(1) HCHO (2) CH3COCH3
(1) 2-ethoxypropane (2) ethoxypropane
(3) CH3COOH (4) CH3OH
(3) methoxybutane (4) 2-methoxybutane
15. The major product obtained on interaction of phenol
23. What is the structure of the major product when
with sodium hydroxide and carbon dioxide is–
phenol is treated with bromine water:
[AIEEE-2009]
[JEE Main Online-2013]
(1) Salicyladehyde (2) Salicyclic acid
(3) Phthalic acid (4) Benzoic acid
16. From amongst the following alcohols the one that (1) (2)
would react fastest with conc. HCl and anhydrous
ZnCl2, is– [AIEEE-2010]
 |
2.36    Organic Chemistry Module II

(1) KMnO4
(2) K2Cr2O7
(3) (4) (3) CrO3
(4) PCC (Pyridinium chlorochromate)
29. The major product of reaction
24. Amongst the following alcohols which would react
fastest with conc. HCl and ZnCl2? [JEE main Online-2014]
[JEE Main Online-2013]
(1) Pentanol (2) 2-Methylbutanol

(3) 2-Pentanol (4) 2-Methyl butan-2-ol

(1) (2)
25. The reaction of phenol with benzoyl chloride to give
phenyl benzoate is known as:
[JEE Main Online-2013] (3) (4)
(1) Claisen reaction
(2) Schotten–Baumann reaction 30. Allyl phenyl ether can be prepared by heating:
(3) Reimer–Tiemann reaction [JEE main Online-2014]
(4) Gatterman–Koch reaction (1) C6H5Br + CH2=CH–CH2–ONa
26. The major product in the following reaction (2) CH2=CH–CH2–Br + C6H5ONa
[JEE Main Online-2013] (3) C6H5–CH=CH–Br + CH3–ONa
(4) CH2=CH–Br + C6H5–CH2–ONa
– 31. The following reaction [JEE main Online-2014]
OH
OH
Anhyd
+ HCl + HCN ZnCl2
CHO
Is known as:
(1) (2) (1) Perkin reaction
(2) Gattermann–Koch formylation
(3) Kolbe’s reaction
(4) Gattermann reaction
32. Which one of the following statements is not cor-
(3) (4) rect? [JEE main Online-2014]
(1) Alcohols are weaker acids than water
(2) Acid strength of alcohols decrease in the follow-
27. Phenol on heating with CHCl3 and NaOH gives sali- ing order
cylaldehyde. The reaction is called RCH2OH > R2CHOH > R3COH
[JEE main Online-2013] (3) Carbon–oxygen bond length in methanol,
(1) Reimer–Tiemann reaction CH3OH is shorter than that of C–O bond length
(2) Claisen reaction in phenol
(3) Cannizzaro reaction (4) The bond angle in methanol is 108.9°
(4) Hell-Volhard-Zelinsky reaction
28. The most suitable reagent of the conversion of 33. In the Victor–Meyer’s test, the colour given by 1°,
R—CH2—OH R—CHO is 2° and 3° alcohols are respectively:
[JEE main Online-2014]
 Alcohols, Ethers and phenol     2.37 |
(1) Red, colourless, blue (2) Red, blue, colourless (1) I < II < III < IV (2) I < II < IV < III
(3) Colourless, red, blue (4) Red, blue, violet (3) IV < I < II < III (4) IV < II < I < III
34. Phthalic acid reacts with resorcinol in the presence
of concentrated H2SO4 to give: 41. In the reaction the products are-
[JEE main Online-2014] [IIT-2010]
(1) Phenolphthalein (2) Alizarin
(1)
(3) Coumarin (4) Fluorescein
35. Williamson synthesis of ether is an example of:
[JEE main Online-2014] (2)
(1) Nucleophilic addition
(2) Electrophilic addition (3) Br and CH3OH
(3) Electrophilic substitution
(4) Nucleophilic substitution (4)

36. CH3MgBr (excess) + Ethyl ester Æ which can be

42. In the reaction intermediate (s) is (are) [IIT-2010]
formed as product [IIT-2003]

CH3
(1) (2) HO CH2CH2CH3  ?
CH2CH3

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

37. The best method to prepare cyclohexene from

cyclohexanol is by using [IIT-2005]
(1) Conc. HCl + ZnCl2 (2) Conc. H­3PO4
(3) HBr (4) Conc. HCl
(3) (4)
38. When phenyl magnesium bromide reacts with tert.
butanol, which of the following is formed?
[IIT-2005]
(1) Tert. butyl methyl ether 43. The major product of the following reaction is
(2) Benzene [IIT-2011]
(3) Tert. butyl benzene

(4) Phenol
39. Consider the given reaction, [IIT-2005]
(1) A hemiacetal (2) An acetal
(3) An ether (4) An ester

Passage: (Q.44 to Q.45)

An acyclic hydrocarbon P, having molecular formula C6H10,
Identify X and Y. gave acetone as the only organic product through the fol-
40. The increasing order of boiling points of the follow- lowing sequence of reactions, in which Q is an intermediate
ing mentioned alcohols is [IIT-2006] organic compound, [IIT-2011]
I. 1, 2-dihydroxy benzene (i) conc. H2SO4 O
(catalytic amount)
II. 1, 3-dihydroxy benzene (i) dil. H2SO4/HgSO4 (–H2O) C
P Q 2
III. 1, 4-dihyroxy benzene (C6H10) (ii) NaBH4/ethanol (ii) O3 H3C CH3
(iii) dil. acid (iii) Zn/H2O
IV. Hydroxy benzene
 |
2.38    Organic Chemistry Module II

44. The structure of compound P is–

(1) CH3CH2CH2CH2–C∫C–H
(2) H3CH2C–C∫C–CH2CH3

(3)

(1) P (2) Q
(4) (3) R (4) S
48. In the following reaction, the product(s) formed
45. The structure of compound Q is [JEE Advance-2013]

(1)

(2)

(3)

OH
(4)

46. Identify the binary mixture(s) that can be separated

into individual compounds, by differential extraction,
CH3 CHCl2
as shown in the given scheme. [IIT-2012]
(R)

(1) P (major) (2) Q (minor)

(3) R (minor) (4) S (major)
49. The acidic hydrolysis of ether x shown below is fast-
est when [IIT-2014]
(1) C6H5OH and C6H5COOH
(2) C6H5COOH and C6H5CH2OH
(3) C6H5CH2OH and C6H5OH
(4) C6H5CH2OH and C6H5CH2COOH
47. The major product(s) of the following reaction is
(are) [JEE Advance-2013]

(1) One phenyl group is replaced by a methyl
group
 Alcohols, Ethers and phenol     2.39 |
(2) One phenyl group is replaced by a para-meth-
oxyphenyl group
(3) Two phenyl groups are replaced by two para- (3)
methoxyphenyl groups
(4) No structural change is made of X
Passage for Q. Nos. (50 and 51)
(4)

52. Reagent (s) which can be used to bring about the

following transformation is (are)

[IIT-2015]
(1) LiAIH4 in (C2H5)2O (2) BH3 in C2H5OH
50. Compound X is
(3) NaBH4 in C2H5OH (4) Raney Ni/H2 in THF
53. The correct statement(s) about the following reaction
sequence is (are) Cummene (C9H12)
(1) (2)

(3) (4)
(1) R is steam volatile
51. The major compound Y is (2) Q gives dark violet colouration with 1% aqueous
FeCl3 solution
(1) (3) S gives yellow precipitate with 2, 4-dinitrophe-
nylhydrazine
(4) S gives dark violet colouration with 1% aqueous
FeCl3 solution
(2)

Answer Key

 Exercise # 1   Exercise # 2 
1. (3) 2. (3) 3. (1) 4. (2) 5. (4) 1. (2) 2. (4) 3. (2) 4. (1) 5. (2)
6. (2) 7. (1) 8. (2) 9. (3) 10. (1) 6. (3) 7. (3) 8. (1) 9. (1) 10. (3)
11. (2) 12. (1) 13. (2) 14. (1) 15. (3) 11. (2) 12. (3) 13. (3) 14. (3) 15. (1)
16. (4) 17. (4) 18. (3) 19. (2) 20. (2) 16. (4) 17. (3) 18. (4) 19. (4) 20. (3)
21. (2) 22. (2) 23. (3) 24. (1) 25. (3) 21. (2) 22. (1) 23. (2) 24. (4) 25. (1)
26. (3) 27. (1) 28. (2) 29. (1) 30. (4) 26. (2) 27. (2) 28. (2) 29. (2) 30. (3)
31. (1) 32. (1) 33. (3) 34. (1) 35. (2) 31. (2) 32. (2) 33. (4) 34. (2) 35. (2)
36. (2) 37. (2) 38. (4) 39. (1) 40. (2)
 |
2.40    Organic Chemistry Module II

 Exercise # 3 
1. (1,3) 2. (1,2,3) 3. (2,3) 4. (2,4) 5. (1,3)
6. (3,4) 7. (1,3) 8. (1,4) 9. (1,2,3) 10. (2,3)
11. (1,3,4) 12. (1,2) 13. (1,2,3) 14. (1) 15. (1)

16. (*) 17. (*) 18. (*) 19. (*) 20. (*)
5. [4]
21. (*) 22. (*) 23. (*) 24. (1) 25. (*) Both enol and 1° alcohol gives negative test with
26. (*) 27. (*) 28. (*) 29. (*) 30. (*) Lucas reagent at room temprature.
6. [2]
 Exercise # 4 
With SeO2, oxidation at allylic position takes place
1. (2) 2. (4) 3. (1) 4. (3) 5. (4) 7. [1]
6. (3) 7. (4) 8. (1) 9. (4) 10. (4)
11. (3) 12. (3) 13. (4) 14. (3) 15. (2)
16. (3) 17. (2) 18. (2) 19. (1) 20. (4)

21. (2) 22. (1) 23. (1) 24. (4) 25. (2)
Intramolecular esterification
26. (4) 27. (1) 28. (4) 29. (2) 30. (2)
8. [2]
31. (4) 32. (3) 33. (2) 34. (4) 35. (4)
36. (4) 37. (2) 38. (2) 39. (*) 40. (3)
41. (4) 42. (1,2,3) 43. (2) 44. (4) 45. (2)
1 OH increase molecular formula Æ C2H2O
46. (2,4) 47. (2) 48. (2,4) 49. (3) 50. (3)
51. (4) 52. (3) 53. (2,3) C8H8O
No of – OH = ______
​   ​ 
=4
C2H2O
Hint and Solution 9. [3]

Exercise # 1
1. [3]

10. [1]
O OH
NaBD4
CCH3 CH3OH CCH3
D
(Nucleophilic addition takes place)

11. [2]

2. [3] O
18
H2O /H ≈
Fact CH3–CH2–C–O–CH3 CH3–CH2–C– O18H+CH3OH
3. [1]
H–O18–H O
C3H8O C3H6O2
Primary alcohol carboxylic acid
12. [1]
(X) (Y)
Since Y will give white ppt immediately with Lucas
4. [2]
reagent, hence it must be 3° alcohol so that (X) is
Victor Mayer test alkyl alkanoate.
 |
Alcohols, Ethers and phenol     2.41

O
CH3–C–O–C2H5 CH3–MgBr CH –C–CH +C H –OH
H2O/HCl 3 3 2 5
(C4H8O2)
O
(X)

CH3–MgBr H2O/HCl

CH3
CH3–C–CH3
OH

C4H10O (Y)
Lucas Test

White ppt
(within in 5 sec.)

18. [3]
13. [2]
(Refer key concept)
Theory based 19. [2]
NaBH4 do not reduce ester. It reduces only > C=O
14. [1]
in > CH – OH.
20. [2]
Na/D
(A) C2H5–OH C2H5–O–Na (B) Formation of CHI3 with NaOI, proves that (B) must
be methyl ketone like
PCl5
C2H5–OH C2H5Cl (C)

– ≈
C2H5–O–Na+C2H5–Cl SN2
C2H5–O–C2H5
Diethylether

15. [3]

21. [2]
–
CH3–C C
CH3–CH–CH2 CH3–CH–CH2–C C–CH3
SN2
(X)
O O
–
16. [4] CH3 I
Lg
CH3–CH–CH2–C C–CH3
(Y)
OCH3

Syn addition H2Pd-BaSO4
17. [4]

CH3–CH–CH2 CH3
C=C
OCH3 H (Z) H
 |
2.42    Organic Chemistry Module II

22. [2] Æ In acidic medium, SN1 reaction is favoured, i.e.,

nucleophile approach towards most sterically hin-
dered site
Æ In alkaline media, SN2 reaction is favoured, i.e.,
Nucleophile approach towards least sterically hindered

site
23. [3]
O 28. [2]
Q ≈
CH3–CH2–CH2–OH
PCC
CH3–CH2–C–H+CH3–CH–Li C4H10O fi CnH2n + 2O (alcohol/ether)
≈
H3O CH The given reaction indicates that
3
(i) no alcohol, i.e., only ether
OH
(ii) type of H = 3
CH3 Na2Cr2O7 CH3
CH3–CH2–C–CH CH3–CH2–CH–CH (iii) no alcohol
CH3 oxidation CH3
O
2-methyl-3-pentanone Thus
24. [1]
H3O≈ 29. [1]
CH3 – CH2 – O – C = CH2
HO–H
CH3
CH3–CH2–OH+CH3–C=CH2
OH
tautomerise

CH3–C–CH3 Acidic strength > CH3–O–H

O
30. [4]
25. [3]
OH
NaHCO3
Insoluble
CH3
C7H8O Dil NaOH soluble
26. [3] FeCl3 Violet colour
≈
(due to phenolic grp)
LiAlH4 Æ Li+ + AlH 4 Æ AlH3 + HQ
OH
In alkaline medium nucleophilic attack from less
steric side takes plance. Br - water Br Br
Ispo effect
CH3
H 3C CH3
LiAlH4/H≈
H 3C CH3–C–CH3
H
–
Br
O OH C7H5OBr3

27. [1] 31. [1]
Substances containing phenolic group give purple
colour with FeCl3
32. [1]
O H
O
N
Intramolecular H-bond boiling point Ø volatile nature
33. [3]

 Alcohols, Ethers and phenol     2.43 |
OH SO3H SO3H
(i) NaOH COOH
(ii) CO2/140° Br2,FeBr3
D
OH Kolbe Reaction Br
NO2 NO2
OH
COOH OH
CCl4/NaOH (i) NaOH
+ 350°C
(ii) H
Reimer Tiermann
Reaction Br NO2
OH
CH=O 37. [1]
CHCl3/NaOH
Rate of Ar–SN2 reaction µ (EWG) De-activating
power
OH OH 38. [4]
CH=O COOH
HCN/HCl [O]
Gattermann
synthesis

34. [1]
39. [1]
OH OH
Elb’s persulphate oxidation reaction
Br2/water
Br Br
40. [2]
Ipso effect

SO3H Br
2, 4, 6-tribromophenol

Ipso substitution means replacement of any func-
tional group (good leaving group) which already exist
in benzene. Exercise # 2
35. [2] 1. [2]
OH

NaNO2 NaOH
Red Blue
+ HCl
Indophenol

O
+
H
OH OH O OH

SEAr Para
+ NO Tautomerism N
≈

NO N—OH

(Indophenol red) Q
O
Æ x = 3(because 3 OH group present)
36. [2]
 |
2.44    Organic Chemistry Module II

2. [4] 6. [3]
≈
OH CH2–NH2 OH CH2 OH
≈
Q
NaNO2 H shift
HCl ring expansion

Q
H2O/OH

HO OH

Unstable
O
7. [3]
CH3
H–Br Ph CH3 Br
Q

3. [2] Ph CD3 +
OH CD3
Planner carbocation

Ph CH3 Ph CH3
+
Br CD3 CD3 Br
Recemic mixture

8. [1]

9. [1]
4. [1] Æ Oxidation at allylic position achieved by MnO2
HOH Æ Oxidation of ordinary alcohol achieved by CrO3
I I
HI excess CH2 CH2 –I2 CH2 = CH2 10. [3]
& heat
I H OH I I I HI H I
Vicinal di iodide O CH3 OH
Conc Hl +2CH3–I
(Unstable) CH3–CH2–I 2 mole
O CH3 OH
5. [2] H I
I
Conc Hl +2H2O
2 mole
I
Unstable
–I2
I HI

E.A.R
1
Rate of esterification µ _____________
​      ​ 1 mole
steric hindrance
Total mole HI (consumed) = 5
 |
Alcohols, Ethers and phenol     2.45

11. [2] 15. [1]

OH OH NaBH4 is weak reducing agent so that only carbonyl
group will be reduced.
Br2(1 aq)CCl4
16. [4]
E.A.R
+ Test x y
Br2 fi weak E
Br2 Unsaturated Saturated
CH=CH2 CH–CH2
Na Metal alcohol ether
Br Br Chromic acid oxidation no oxidation
OH
+M Lucas reagent 1°alcohol ether
with the above reactions possible structure of
> CH2=CH2
X fi Unsaturated primary alcohol &
Y fi Saturated ether
CH=CH2 17. [3]
Due of +M and –I effect of –OH, e-density of C = C
increases at para position. POCl3
Reaction I: CH3 H
Hence (x) more reactive than ethene. Hoffman
12. [3] H OH elimination

Reaction II:

18. [4]

(A)

13. [3]
(B)
This is Riemer–Tiemann reaction

(C) , NaBH4 weak reducing agent

14. [3] so only carbonyl group will
be reduced

(D) These bonds

are affected in esterification

Thus, all four statements are correct
 |
2.46    Organic Chemistry Module II

19. [4] 24. [4]

CH2–OH CH2–OH
NaOH I–CH2–I
excess
OH O– Lg

More acidic
CH2–OH

O–CH2–I

NaOH

CH2–O–

O–CH2–I
Lg

O
20. [3] O

O–H – 25. [1]

O
OH SN2
CH3 –H O CH3 O
2
Br Br

21. [2]

26. [2]
O

O O Ph–MgBr Ph–C–Ph+HO OH
+
22. [1] H
(SN2) O
+
NAR Ph MgBr/H

Ph
Ph–C–Ph

OH
23. [2]
27. [2]

 |
Alcohols, Ethers and phenol     2.47

28. [2] 31. [2]

Æ R Br more reactive than R Cl Dihydric alcohols are always more soluble in water
than monohydric alcohol. Between (I) and (II), (I) is
Cl Br
Mg/ether
Cl MgBr more soluble as it forms intermolecular H-bonds with
water while (II) forms intramolecular H-bonds which
≈ decreases its ability to form intermolecular H-bonds
H—CH=O/H
with water.
32. [2]
Cl CH2—OH

29. [2]

O
HO CH3 Br CH3
CH3MgBr KBr-H2SO4

BrMg CH3
Mg/ether

H–CH=O 33. [4]

+
H /H2O

CH3 CH2–OH

Phenolic —OH does not undergo further substitution.
34. [2]
30. [3]

OH * O
jones Re agent
ΩOΩ
Optically active Optically active

jones Re agent *
OH ΩOΩ
O
* No POS
Optically active
Optically active

jones Re agent
OH ΩOΩ
O
No chiral C

Optically active Optically inactive 35. [2]

OH +
OH
* OH H2O/H OH
Jones Re agent

OH ΩOΩ
O O
Optically active Optically active OH
Tautomerise

 |
2.48    Organic Chemistry Module II

Exercise # 3   5. [1,3]
Both cis and trans 2-hexene forms the same
1. [1,3] carbocation, hence react at same rate.
C2H5ONa
C2H5–Br C2H5–O–C2H5

dry Ag2O
C2H5–Br C2H5–O–C2H5–+2AgBr
2 Mole

2. [1,2,3]

6. [3, 4]
CH2 CH=CH2 + Br2 – H2O
*
Br

≈
Br Br
CH2 CH CH2 CH2 CH CH2
* Br*
Br ≈
(I) (II)
Trans Esterification follow Le-chaterlier principle in OH2 OH2
which for forward reaction PrOH is taken in excess
and for backward reaction EtOH is taken in excess. Br Br*
In the slow step formation of tetrahedral intermediate
it means it having vanderwall repulsion. CH2 CH CH2OH CH2 CH CH2OH
3. [2,3] *
Br (3) Br (4)

H
– 7. [1, 3]
≈
+
shift
O Option (1) and (3) have electron withdrawing groups,
Ag
(I) destabilises carbocation, do not form turbidity with
Lucas reagent at room temperature like primary
O O ≈
alcohols. Option (2) and option (4) have electron
Br Ring
donating groups, stabilise benzylic carbocation, form
expansion ≈
O immediate turbidity with Lucas reagent like 2° and
(II) 3° alcohols.
8. [1, 4]
(I) and (II) undergo nucleophilic attack by H2O
giving the desired products.
CH3 CH3
4. [2,4] H2/Ni
CH2=CH C CH2 CH3 CH3 CH2 C CH2 CH3
Deutride (D–) addition at planar carbonyl carbon
occur from both side of plane with equal probability OH OH
giving racemic mixture of alcohols, Also, deuterium X(chiral) Y(Achiral)

is attached to carbonyl carbon atom only. Br2/CCl4

CH3
CH2–CH C CH2 CH3
Br Br OH
Colourless
(C6H12OBr2)

X neither oxidised by chromic acid nor gives

iodoform.
 Alcohols, Ethers and phenol     2.49 |
9. [1, 2, 3] (I) on deprotonation gives (1) while (II) on deproto-
(1) Reaction does not involve breaking of bonds to nation (2)
chiral carbon, hence retention of configuration. 13. [1,2,3]
(2) With TsCl, —OTs is formed with retention of
configuration. Subsequent reaction with CH3O- (1)
Na involves SN2 reaction, hence inversion of O
configuration takes place.
(2) H2O
(3) With conc. H2SO4­, alkene is formed. Alkene in + C2H5MgBr
the next step reacts via carbocation intermediate, OH
hence racemic product is obtained.
(4) Racemic mixture would be obtained. (3)
10. [2,3]
H 14. [1]
+ SCH3 Theory based
O + O
H CH3SH 15. [1]
H3C H3C C2H5 C CH2OH
SN1
Acid catalysed dehydration of alcohols proceeds
C2H5 C2H5 CH3 via carbocation intermediates. Hence, greater the
Major
stability of carbocation, greater is the reactivity of
In acidic medium, SN1 reaction favourable corresponding alcohols.
11. [1,3,4] 16. [4]
H CH3
CH3 C C CH3 Na C=C (i) CHCl3/OH
–
Liq. NH3
H3C H HO (ii) H3O HO CHO
Ag2O D
CH3O CH3O Y
O
Also, Y is an ozonolysis product of X.
H CH3
H3C H
Y
Racemic

NaOH H2O
OH
CH3
H
H
CH3 17. [3]
OH
Z ≈

Meso (Achiral) X + HBr Æ HO CH=CH–CH2–OH2

12. [1,2] CH3O –H2O

CH3 CH3
HO OH HO ≈

H
+
+ HO CH=CH–CH2
–H2O
CH3O
OH
+ ≈

Methyl shift HO CH CH=CH2

CH3O Br –
(I)
CH3 Br
≈ OH
HO CH–CH=CH2
Ring
contraction CH3O

(II)
 |
2.50    Organic Chemistry Module II

18. [1] 23. [1]

I2/KOH
CH3–CH2–OH + ve iodoform test
OH
NO2 NO2
FeCl3 Violet coloration
due to phenolic group

NO2
Phenol gives a violet-coloured water soluble complex
with ferric chloride. The complex formed is a coor-
dination compound in which iron is hexavalent.

3– +
19. [2] 6C6H5OH + FeCl3 Æ [Fe(OC6H5)6] + 3H + 3HCl
a Æ q (Clemmenson reduction) violet complex
CH2–OH
b Æ s (NAR) 2HIO4
CH–OH 2HCH=O + HCOOH
c Æ p (reduction by LiAlH4)
d Æ r (specific reduction of ester) CH2–OH
20. [2] Lucas test White turbidity
CH3–CH–CH3 Conc.HCl+Anhy.ZnCl2
Theory based within 5 min
21. [3] OH
(A) Vicinal diol cleaved by HIO4
24. [1]
(B) Benzyl alcohol is neutral towards litmus paper
(i)
(C) Lucas test achieved via SN1, OH
–
CH3
reactivity of SN1 µ stability of OH H H
R CH3
O OH
(D) Only type gives positive iodoform H CH3 Meso
CH3 CH3
H3C H CH3MgBr OH H CH3
H2O +H H
test CH3
H CH3
22. [2] CH3 OH
CH3 CH3 OH Racemic
Hg(OAC)2
O – OH
NaBH4 OH
H H2O H
(A) (S) (ii) CH3 CH2OH
H3C
OH OH Pure enantiomer
Pure enantiomer
NO2 NO2
Conc. HNO3
(iii)
OH H
(B) O OH CH3
NO2 –
CH3 +
H H OH H CH3
(P) H OH
(Picric acid) H3C CH3 H CH3
OH
O CH3 OH Racemic
CH3MgBr
+
H3 O OH CH3
CH3MgBr CH(CH3)2 H
(C) (Q) H2O + CH(CH3)2
Cr2O3–ZnO
H CH3 OH
CO+2H2 CH3–OH
(D) (R) Racemic
 Alcohols, Ethers and phenol     2.51 |
(iv) 26. [5]
OH H
O OH CH3
–
CH3 +
H H OH H CH3
H OH
H3C CH3 H CH3
OH
Racemic

25. [1]

(i)

(ii)
≈
OH H OH 27. [3]

2–
OH OH OH H
Cr2O7 3+ O O NaBH4
+ + Cr +
H H2O
(Orange) O Blue-green H H H OH
Meso (d + I)
HCL
ZnCl2
Cl 28. [4]
Turbid X satisfying the given criteria is

Since, X has two chiral carbon so that four optically

(iii) active isomers exist.
29. [4]

O
≈
(iv) H
HO 30. [6]
(–)-2-ethyl oxirane OH O
A pure enantiomers
( OH) + CH3COCl O C CH3 + HCl
17 59
2–
Cr2O7 Mass gain due to incorporation of one acetyl group
≈ No oxidation
H = 59 – 17 = 42
HCL No truurbidity
ZnCl2 Net mass gain due to acetylation = 518 – 266 =
LiAlH4 252
Hence, six hydroxyl groups (6 × 42 = 252) were
OH present.
2-butanol
 |
2.52    Organic Chemistry Module II

7. [4]
Exercise # 4 
1. [2]
In Presence of > C = O group dehydration takes
places according to E1CB reaction
Rate of E1CB µ stability of carbanion

8. [1]
..
CHCl3 + KOH Æ CCl2 + KCl + H2O
Dichlorocarbene

9. [4]

2. [4]
Alcohol has polar H which makes intermolecular
H-bonding possible. Ether is non-polar, hence has
no H-bonding. Lack of H-bonding in ether makes it
more volatile than alcohol.
3. [1]
Protonation of —OH is first step. It involves conver-
sion of poor leaving group (—OH) into good leaving 10. [4]
+
group (—OH2).
For positive iodoform test, alcohol molecule must
4. [3]
have group
Rate of dehydration µ stability of carbocation
5. [4]
Gas equation
PV = nRT Thus, iodoform test is given by only (4)
w
P = ___
​ mv  ​  RT while others will not give this test.
r
P = __
​ m  ​   RT

Pµr

6. [3]
11. [3]
Hydration of ethane gives 1° alcohol (ethanol) while
all other alkenes give either 2° or 3° alcohols.

 Alcohols, Ethers and phenol     2.53|
+
CH3 C=CH2 H2O/H stability of carbocation formed faster sis the reaction
(CH3)3COH
2-methylpropan-2-ol gives 3° carbocation. Hence, it
CH3 reacts rapidly with conc. HCl and anhydrous ZnCl2
≈
[(3° alcohol through 2° carbocation (CH3)3C] (Lucas reagent).
17. [2]
CH3 CH3
+ ≈
H2O/H
CH3 CH CH=CH2 CH3CH CH CH3
2° carbocation
–
H2O 1, 2H shift
2° alcohol
CH3
CH3 C CH2 CH3
≈
3° carbocation
H2O
Option (1), (3) and (4) may be formed but option (2)
3° alcohol
is never formed.
12. [3] 18. [2]

OH
≈
HCH=O/H
Bakelile (Thermosetting polymer)
Phenol

19. [1]
By the use of MnO2 oxidation of only allylic alcohol
13. [4] takes place.

CH2 =CH–CH2–OH CH2=CH–CH=O

20. [4]
The reaction of alcohol with Lucas reagent is mostly
SN1 reaction and the rate of reaction is directly pro-
portional to the stability of carbocation formed in the
reaction.
Since, 3° R—OH forms 3° carbocation (most stable)
14. [3] hence, it will react fastest by SN1 reaction.
21. [2]
Rate of dehydration µ stability of carbocation
22. [1]
15. [2]

16. [3]
The reaction of alcohol with conc. HCl and
anhydrous ZnCl2 follows SN1 pathway, so greater the
 |
2.54    Organic Chemistry Module II

23. [1] 28. [4]

Mild oxidising agents like PCC (Pyridinium chloro-
chromate are particularly used for the conversion of
R—CH2OH R—CHO
29. [2]
NaNO /H SO +
2 2 4

NH2 OH OH

Q
1 : 2 CH3 shift +
O–H
+
–H

So that Ar-SE reaction takes places at all o/p O
position.
30. [2]
24. [4]
CH2=CH–CH2–Br + C6H5ONa
The reaction of alcohol with conc. HCl and anhydrous
ZnCl2 follows SN1 pathway, so greater the stability of CH2=CH–CH2– O–C6H5
carbocation formed faster sis the reaction 2-methyl Allyl bromide gives resonating stable allyl carboca-
butan-2-ol gives 3° carbocation. Hence, it reacts tion so it easily gives SN reaction.
rapidly with conc. HCl and anhydrous ZnCl2 (Lucas 31. [4]
reagent). Given reaction is known as Gattermann reaction.
25. [2] 32. [3]
1
Acidic strength µ – I µ ___
​    ​ 
+ I
• So option (1) is correct

• + I Power (R3–C– > R2–CH– > R–CH2–) So

option (2) is correct.
1
26. [4] • Bond length of single bond µ ​ _________
    ​
Resonance
C–O bond of phenol involve in resonance bond
length decreases.
So that C–O (CH3–OH) > C–O(Ph–OH) hence
option (3) is incorrect.
• Bond angle of sp3
33. [2]
34. [4]
35. [4]

R–X

Nucleophilic substitution
27. [1] 36. [4]

 Alcohols, Ethers and phenol     2.55 |
37. [2] 43. [2]
+
H RCH2O
+
+ –H
O O O OCH2R
Acetal
Concentrated H3PO4 solution does not involve any Resonance
substitution product while with others, substitution stablilisation
product are also formed
38. [2] +
O
C6H5MgBr + (CH3)3COH C6H6 + Mg [(CH3)3CO]Br
(Benzene) 44. [4]
39. 45. [2]
(44 to 45)
The final ozonolysis product indicates that the alkene
before ozonolysis is

Also P (C6H16) has two degree of unsaturation and

oxymercuration–demercuration hydration indicates
that it is an alkyne. As alkyne, on hydration, gives a
carbonyl compound which on reduction with NaBH4
gives a 2° alcohol.

40. [3]
All dihydroxy benzene will have higher boiling points
than monohydroxy benzene Also, among dihydroxy
benzenes, 1, 2-di-hydroxy benzene has lowest boiling
point due to intramolecular H-bonding.
The secondary alcohol that can give above shown
alkene on acid catalysed dehydration is

41. [4]

42. [1,2,3]
Since OH group is activating group so that negative
charge is developed at ortho and para position during
resonance.
  Hence (1), (2) and (3) are the intermediate obtained

during mechanism.
 |
2.56    Organic Chemistry Module II

44. 49. [3]

This problem can be solved by using the concept of
stability of carbocation and SN1 reaction.
  When two phenyl groups are replaced by two para
methoxy group, carbocation formed will be more
stable.
45. Explained in the beginning.   As the stability of carbocation formed increases,
46. [2,4] rate of acidic hydrolysis increases.

(1) Both phenol and benzoic acid forms salt with

NaOH, hence this mixture can’t be separated.
(2) Benzoic acid forms salt with NaOH while
benzyl alcohol does not, hence the mixture can
be separated using NaOH. Also, benzoic acid
forms salt with NaHCO3 but benzyl alcohol does
not, hence NaHCO3 can be used for separation.
(3) Neither benzyl alcohol nor phenol forms salt
with NaHCO3, mixture cannot be separated
using NaHCO3.
(4) C6H5CH2COOH forms salt with NaOH, C6H5-
CH2OH does not, hence NaOH. C6H5CH2COOH
50. [3]
forms salt with NaHCO3. C6H5CH2OH does
not, hence mixture can be separated using The reaction condition indicates that starting com-
NaHCO3. pound is phenyl acetylene.
47. [2]

OH OH
Aq. Br2(3 Equivalent) Br Br
lpso effect

SO3H Br

48. [2,4]
Hydroboration oxidation brings about anti-
Q
OH O O O Markownikoff’s hydration of alkene.
51. [4]
CHCl3 CCl2
–
OH
Q
Q
CH3 CCl2
CH3 CH3 CH3
H2O

OH OH CH3 CH–Cl2
CHO
CHCl3
–
OH

CH3 CH3

 |
Alcohols, Ethers and phenol     2.57

52. [3] OH O OH
Only –CHO group is to be reduced to –CH2OH
H
It can be done using NaBH4 in C2H5OH. +

Major
O IV O CHO
C O (Q)
Manor
(R)
O III H
II
COOH
I
(1) LiAlH4/(C2H5)2O reduces I, II and III into O–H O–Na Br CH2–Ph O–CH2Ph
–CH2OH, and IV into diol. CHO
CHO CHO
(2) BH3/THF show same properties as (1). NaOH Williamon’s
Synthesis
(3) NaBH4/C2H5OH reduces III into –CH2OH Major
(4) Raney nickel, same as (1) and (2),
(Q) (S)
Thus (3) is correct reagent.
53. [2, 3] (1) R is not steam volatile, but Q is steam volatile
CH3 thus, incorrect.
CH3 (2) Q has enolic group; thus it gives violet colour
CH–CH3 O–O–CH with 1% aqueous FeCl3 solution thus, correct.
CH3
O2 H3O
+
(3) S has Carbonyl group hence, gives yellow
precipitate with 2,4-DNP thus, correct.

OH (4) S does not give colour with FeCl 3 thus,

O incorrect
CHCl3/NaOH
+ CH3–C–CH3 Remimer- Tiemann
acetone reaction
Phenol
(P)