PREVIOUS YEAR

PROBLEM SOLVING
IIT JEE MAIN + ADVANCED
ORGANIC CHEMISTRY

BY
NAVNEET JETHWANI

ALCOHOL, PHENOL
&
ETHER

ETOOSINDIA
INDIA’S NO. 1 ONLINE COACHING

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Kota, Rajasthan – 324005 Mob. : 9214233303
ETOOSINDIA N.J. SIR
INDIA’S NO. 1 ONLINE COACHING

JEE MAIN
1. During dehydration of alcohols to alkenes by heating with concentrated H2SO4 the initiation step is
(1) Protonation of alcohol molecule (2) Formation of carbocation [AIEEE-2003]
(3) Elimination of water (4) Formation of an ester
Ans. (1)
2. When CH2 = CH – COOH is reduced with LiAlH4, the compound obtained will be – [AIEEE-2003]
(1) CH3 – CH2 – CH2OH (2) CH3 – CH2 – CHO (3) CH3 – CH2 – COOH (4) CH2 = CH – CH2OH
Ans. (4)
3. Among the following compound which can be dehydrated very easily is : [AIEEE-2004]

H3C H3C

(1) (2)
OH H3C OH

CH3
OH

(3) (4)
H3C CH3 H3C CH3
OH

Ans. (3)
4. Acid catalized hydration of alkenes except ethene leads to the formation of : [AIEEE-2005]
(1) Secondary or tertiary alcohol (2) Primary alcohol
(3) Mixture of secondary and tertiary alcohols (4) Mixture of primary and secondary alcohols
Ans. (1)
5. The best reagent to convert pent–3–en–2–ol into pent – 3–en – 2 – one is [AIEEE-2005]
(1) Acidic dichromate (2) Acidic permanganate
(3) Pyridinium chloro-chromate (4) Chromic anhydride in glacial acetic acid
Ans. (4)
6. Phenyl magnesium bromide reacts with methanol to give - [AIEEE-2006]
(1) A mixture of anisole and Mg(OH)Br (2) A mixture of benzene and Mg(OMe)Br
(3) A mixture of toluene and Mg(OH)Br (4) A mixture of phenol and Mg(Me)Br
Ans. (2)
7. HBr reacts with CH2 = CH – OCH3 under anhydrous conditions at room temperature to give -
(1) BrCH2CHO and CH3OH (2) BrCH2 – CH2 – OCH3
(3) H3C – CHBr – OCH3 (4) CH3CHO and CH3Br
Ans. (4)
P+ I2 Mg HCHO H2 O
8. In the following sequence of reactions CH 3CH 2 OH   A 
Ether
 B   C   D , then com-
pound ‘D’ is [AIEEE - 2007]
(1) Butanal (2) n–Butyl alcohol (3) n–Propyl alcohol (D) Propanal
Ans. (3)

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INDIA’S NO. 1 ONLINE COACHING

9. A liquid was mixed with ethanol and a drop of concentrated H2SO4 was added. A compound with a fruity smell
was formed. the liquid was : [AIEEE - 2009]
(1) CH3COCH3 (2) CH3COOH (3) CH3OH (D) HCHO
Ans. (2)

10. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous ZnCl2, is :
[AIEEE - 2010]
(1) 1–Butanol (2) 2–Butanol (3) 2–Methylpropan–2–ol (4) 2–Methylpropanol
Ans. (3)
11. The main product of the following reaction is : [AIEEE-2010]
conc. H 2SO 4
C6H5CH2CH(OH)CH(CH3)2   
H5 C6 H C6 H5CH2 CH3
(1) C C (2) C C
H CH(CH3)2 H CH3

C6 H5 CH(CH3)2 H5C 6CH2CH2

(3) C C (4) C CH2
H H H3C
Ans. (1)
12. Consider thiol anion (RS) and alkoxy anion (RO). Which of the following statement is correct ? [AIEEE-2011]
(1) RS is less basic but more nucleophilic than RO.
(2) RS is more basic and more nucleophilic than RO.
(3) RS is more basic but less nucleophilic than RO.
(4) RS is less basic and less nucleophilic than RO.
Ans. (1)
13. Consider the following reaction :
C2H5OH + H2SO4  Produce
Among the following, which one cannot be formed as a product under any conditions ? [AIEEE -2011]
(1) Ethyl-hydrogen sulphate (2) Ethylene
(3) Acetylene (4) Diethyl ether
Ans. (3)
14. Iodoform can be prepared from all except : [AIEEE - 2012]
(1) Isobutyl alcohol (2) Ethyl methyl ketone (3) Isopropyl alcohol (4) 3–Methyl–2–butanone
Ans. (1)
15. An unknown alcohol is treated with the “Lucas reagent” to determine whether the alcohol is primary, secondary or
tertiary. Which alcohol reacts fastest and by what mechanism : (JEE (Mains) 2013)
(1) secondary alcohol by SN1 (2) tertiary alcohol by SN1
(3) secondary alcohol by SN2 (4) tertiary alcohol by SN2
Ans. (2)
16. The most suitable reagent for the conversion of R – CH2 – OH  R – CHO is : [JEE-Main 2014]
(1) CrO3 (2) PCC (Pyridinium chlorochromate)
(3) KMNO4 (4) K2Cr2O7
Ans. (2)

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17. Allyl phenyl ether can be prepared by heating : [JEE-Main (Online) 2014]
(1) CH2 = CH–CH2–Br + C6H5ONa (2) C6H5–CH=CH–Br + CH3–ONa
(3) C6H5Br + CH2=CH–CH2–ONa (4) CH2=CH–Br + C6H5 – CH2 – ONa
Ans. (1)
18. In the Victor-Meyer’s test, the colour given by 1°, 2° and 3° alcohols are respectively:- [JEE-Main 2014]
(1) Red, blue, colourless (2) Colourless, red, blue (3) Red, blue, violet (4) Red, colourless, blue
Ans. (1)
19. Williamson synthesis of ether is an example of [JEE-Main (Online) 2014]
(1) Nucleophilic addition (2) Electrophilic substitution
(3) Nucleophilic substitution (4) Electrophilic addition
Ans. (3)
20. In the hydroboration - oxidation reaction of propene with diborane, H2O2 and NaOH, the organic compound
formed is : [JEE-Main (Online) 2014]
(1) CH3CH2CH2OH (2) (CH3)3COH (3) CH3CHOHCH3 (4) CH3CH2OH
Ans. (1)

21. CH2 CH CH2 on mercuration-demercuration produces the major product :-

[JEE-Main (Online) 2014]

CH2 CH CH2 CH2 CH2 CH2 OH

(1) (2)
OH

CH2 COOH CH2 CH CH2

(3) (4)
OH OH

Ans. (1)

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INDIA’S NO. 1 ONLINE COACHING

JEE ADVANCED
Subjective Type Questions
1. When t-butanol and n-butanol are separately treated with a few drops of dilute KMnO4 in one case only, purple
colour disappears and a brown precipitate is formed. Which of the two alcohols gives the above reaction and what
is the brown precipitate ? [IIT-1994]
Ans. n-butanol is oxidised by KMnO4 and not t-butanol as the latter does not contain H atom attached to carbinol carbon atom.
 
CH3CH2CH2CH2OH + KMnO4  CH3CH2CH2COO O K + MnO2 + KOH
n-Butanol Brown

CH3

CH3 – C – CH3 + KMnO4 No reaction

OH
t-butanol

2. 3,3-Dimethylbutan-2-ol losses a molecule of water in the presence of a concentrated sulphuric acid to give tetramethyl
ethylene as a major product. Suggest a suitable mechanism. [IIT-1996]

Ans.

1,2-methyl shift

3. A compound D(C8H10O) upon treatment with alkaline solution of iodine gives a yellow precipitate. The filtrate on
acidification gives a white solid (E) (C7H6O2). Write the structures of (D) and (E) and explain the formation of (E).
[IIT-1996]

Ans. Ph – CH – CH3 C6H5COOH

OH
(D) (E)

4. Which of the following is the correct method for synthesising methyl-t-butyl ether and why?
(i) (CH3)3CBr + NaOMe  (ii) CH3Br + tert-BuONa  [IIT- 1997]
Ans. The ether formation involves nucleophilic substitution of alkoxide ion for halide ion.

  —
Slow Fast
R'O + R – X   R' O .........R......... X   R' – O – R + X

3° alkyl halide can also involve elimination of HX to give alkene in the presence of a base. So, it is better to start with
3° alkoxide and 1° alkyl halide, i.e., equation (ii) is correct..
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O C OH HOCH2 Conc.H2SO4
5. + (A) [IIT-1997]
O C OH HOCH2

O O

Ans.
O O

6. Write the intermediate steps for the following reaction: [IIT-1998]

H
(i)  

OH O CH3

7. Discuss why o-hydroxy benzaldehyde is a liquid at room temperature while p-hydroxy benzaldehyde is a high
melting solid? [IIT-1999]
Ans. Due to intermolecular H-bonding

8. Write the structures of the product A & B

CH3 C O18C2H5 A+B [IIT-2000]

Ans. A = CH3 – C – OH, B=C2H5O18H

O
9. Cyclobutyl bromide on treatment with magnesium in dry ether forms an organometallic A. The organometallic reacts
with ethanal to give an alcohol B after mild acidification. Prolonged treatment of alcohol B with an equivalent
amount of HBr gives 1- bromo-1-methylcyclopentane (C). Write the structures of A, B and explain how C is obtained
from B. [IIT-2001]

Ans.

Meachnism

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10. Identify X, Y and Z in the following synthetic scheme and write their structure. Explain the formation of labelled
formaldehyde (H2C*O) as one of the products when compound Z is treated with HBr and subsequently ozonolysed.
Mark the C* carbon in the entire scheme.
BaC*O3 + H2SO4 X (gas) [C* denotes C14]
(i) Mg/ether LiAlH 4
CH2 = CH – Br 
(ii) X, (iii)H O+
 Y 
 3
Z [IIT-2001]

• •
•
CO 2 CH=COOH
2 CH2=CH.CH2OH 
Ans. ; ; ; C H 2 O R'O + R – X
(X) (Y) (Z)

11. Mention two esters produced when a racemic mixture of 2- phehyl propanoic acid is treated with
(+) 2- butanol. What is the stereochemical relationship between these esters? [IIT-2003]

Ph H

Ans. CH3 – C – COOH + CH3 – C – COOH

H Ph

(racemic mixture)

Ph H H H

CH3 – C – C – O – C – CH2CH3 + CH3 – C – C – O – C – CH2CH3

H O CH3 Ph O CH3

During esterification reaction only –COOH and –OH participates. There is no effect on structure or configuration of
carbon adjacent to these groups. So when (± acid reacts with pure (+ alcohol two esters are produced which are
diastereoisomers of each other.
12. Carry out following conversion in 3 or less steps.
OH

Asprine (Acetyl salicylic acid) [IIT-2003]

Ans.

13. Carry out following conversion in four or less steps. Also mention all the reagents used and reaction conditions.

NO2 NO2

[IIT-2004]
OH

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14. An organic compound P(C5H10O) reacts 1015 times faster then ethylene with dilute H2SO4 to give two products Q and
R. Both Q and R give positive iodoform test. Identify P, Q and R and also give reason for very high reactivity of P.
[IIT-2004]

Ans.

O
OH
1. O3 NaOH
15. (X) (Y)
2. Zn/CH3COOH

Identify (X) and (Y). [IIT-2004]

O C

C CH2 CH2 H
Ans.
CH3 CH2 CH2
(X) (Y)

NaNO2 ,HCl
16. (X) C5 H13 N 
-N 2
(Y) (Tertiary alcohol + other products) [JEE 2005]
(Optically active)
Find X and Y. Is Y optically active ? Write the intermediate steps.

OH
Ans. X: C C C C C C C C Y: C C C C
NH2 C C NH2 C

Y is optically inactive.

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17. Amongst the following, the total number of compounds soluble in aqueous NaOH is : [JEE 2010]

OH
H3C CH3 COOH OCH2CH3
N
CH2OH

OH
CH2CH3 COOH
NO2
CH2CH3

N
H 3C CH3

Ans. (4)
Objective Type Questions
18. The products of combustion of an aliphatic thiol (RSH) at 298 K are - [IIT-1992]
(A) CO2 (), H2O (g) and SO2 (g) (B) CO2 (g), H2O (g) and SO2 (g)
(C) CO2 (), H2O () and SO2 (g) (D) CO2 (g), H2O () and SO2 ()
Ans. (B)

19. An organic compound C3H6O does not give a precipitate with 2, 4-dinitrophenyl hydrazine reagent and does not
react with sodium metal. It could be - [IIT-1993]
(A) CH3 – CH2 – CHO (B) CH3 – CO – CH3
(C) CH2 = CH – CH2OH (D) CH2 = CH – OCH3
Ans. (D)

20. 
The reaction products of C6H5OCH3 + HI  are : [IIT-1995]

(A) C6H5OH + CH3I (B) C6H5I + CH3OH (C) C6H5CH3 + HOI (D) C6H6 + CH3 OI
Ans. (A)

21. The order of reactivity of the following alcohols - [IIT-1997]

CH3 CH3 CH 3
CH3
F
F OH OH OH Ph OH

(I) (II) (III) (IV)

towards conc. HCl is -
(A) I > II > III > IV (B) I > III > II > IV (C) IV > III > II > I (D) IV > III > I > II
Ans. (C)

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22. Among the following compounds, the strongest acid is - [IIT-1998]

(A) HC  CH (B) C6H6 (C) C2H6 (D) CH3OH
Ans. (D)

23. The ether O – CH2 when treated with HI produces [IIT-1999]

(A) CH2 I (B) CH2OH (C) I (D) OH

Ans. (D)

24. Which one of the following will most readily be dehydrated in acidic condition - [IIT-2000]

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

Ans. (A)

25. Identify the correct order of boiling point of the following compounds - [IIT-2002]
(A) CH3CH2CH2CH2OH ; (B) CH3CH2CH2CHO ; (C) CH3CH2CH2COOH
(A) A > B > C (B) C > A > B (C) A > C > B (D) C > B > A
Ans. (B)

C H O¯Na + (excess)
OH + C 2H 5I      

2 5
26. C 2 H 5 OH (anhydrous)
[IIT-2003]

(A) OC 2H5 (B) I (C) C6H5OC6H5 (D) C2H5OC2H5

Ans. (D)
27. Reaction of entainomerically pure acid with 1 chiral carbon and racemic alcohol with 1 chiral carbon gives an ester
which is : [IIT-2003]
(A) Meso (B) Optically active mixture
(C) Racemic mixture (D) Enantiomerically pure
Ans. (B)
28. CH3MgBr + Ethyl ester  which can be formed as product (excess) : [IIT-2003]

CH2CH3 CH3
(A) HO CH2CH3 (B) HO CH2 CH2CH3

CH2CH3 CH2CH3

CH2CH3 CH3
(C) HO CH2CH3 (D) HO CH3
CH3 CH3
Ans. (D)

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29. On acid catalysed hydration, 2-phenyl propene gives : [IIT-2004]

(A) 3-phenyl-2-propanol (B) 2-phenyl-1-propanol
(C) 1-phenyl-3-propanol (D) 2-phenyl-2-propanol
Ans. (D)

30. Conversion of cyclohexanol into cyclohexene is most effective in : [IIT-2005]

(A) concentrated H3PO4 (B) concentrated HCl
(C) concentrated HCl / ZnCl2 (D) concentrated HBr
Ans. (A)

31. Phenyl magnesium bromide reacting with t-Butyl alcohol gives [JEE - 2005]

(A) Ph – OH (B) Ph – H (C) (D)

Ans. (B)

HBr
32. In the reaction OCH3 the products are [JEE -2010]

(A) Br OCH3 and H2 (B) Br and CH3Br

(C) Br and CH3OH (D) OH and CH3Br

Ans. (D)
33. The major product in the following reaction is [JEE -2012]

O
Cl 1. CH3MgBr, dry ether, 0°C
CH3 2. aq. acid

OH
O
(A) H 3C (B) H2C CH3
CH3 CH3

(C) (D) CH3

CH2 CH3
O O
Ans. (D)

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34. The acidic hydrolysis of ether (X) shown below is fastest when [JEE - 2014]

acid
OR OH + ROH

[X]
(A) One phenyl group is replaced by a methyl group
(B) One phenyl group is replaced by a para-methoxyphenyl group
(C) Two phenyl groups are replaced by two para-methoxyphenyl group
(D) No structural change is made to X
Ans. (C)
Multiple Choice Questions
35. When phenol is reacted with CHCl3 and NaOH followed by acidification, salicylaldehyde is obtained which of the
following species are involved in the above mentioned reaction as intermediates ? [IIT-1995]

O OH O O
H CHCl2 H CHCl2
(A) CCl2 (B) (C) CHCl2 (D)
OH

Ans. (A, D)
36. The correct combination of names for isomeric alcohols with molecular formula C4H10O is/are – [JEE - 2014]
(A) tert-butanol and 2-methylpropan-2-ol (B) tert-butanol and 1, 1–dimethylethan-1-ol
(C) n-butanol and butan-1-ol (D) isobutyl alcohol and 2-methylpropan-1-ol
Ans. (A, C, D)
Assertion & Reason
37. Statement-1: p-Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid. [JEE - 2007]
Statement-2 : o-Hydroxybenzoic acid has intramolecular hydrogen bonding.
(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.
Ans. (D)

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