IIT CHEMISTRY

ORGANIC CHEMISTRY
ALCOHOL AND ETHER

CH3CH2OH
ethanol

Diethyl ether
(CH3CH2OCH2CH3)

The alcohol ethanol is obtained from the fermentation of Start your engines! Diethyl ether is the major
carbohydrates contained in fruits and grains. flammable compound in starting fluid.

 Dettol is an effective antiseptic-disinfectant that kills bacteria. It consists chloroxylenol and

terpineol ingredients.
OH CH3

H3C CH3
OH
Cl H3C
CH3
Chloroxylenol -Terpineol
 EXERCISE # I
1. Major product of following reaction is :

Alc
. KOH


(A) (B)

(C) (D)

2. Major product of following reaction is :


H

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

3. Major product of following reaction is :

RMgX
 
H 2O

R R' R R
| | | |
(A) R 'C  CH 2OH (B) RCH 2  C  OH (C) R ' CH 2  C  OH (D) R ' ' CH 2  C  OH
| | | |
R'' R'' R' ' R'

4. Major product of following sequence is :

Mg  Hg
2Ph – C – CH3 
H 2O

Conc. H 2SO4


O

(A) Ph – C – C – Ph (B) CH3 – C – C – CH3

O O O O

Ph Ph
(C) Ph – C – C – CH3 (D) Ph – C – C – CH3
CH3 O O CH3

1
5. Major product (B) of following reaction is :

(CH3)2C = C(CH3)2 
Cl2
A OH
 B
H2O

(A) (B) (C H 3 )2 C  C (C H 3 )2
| |
OH Cl

(C) (C H 3 ) 2 C  C (C H 3 ) 2 (D) (C H 3 )2 C  C (C H 3 )2
| | | |
OH OH Cl Cl

6. For the given diol, choose the correct option(s) :

(A) OH at C2 is more basic than that of at C5 (B) OH at C2 is more acidic than at C5.
(C) Both have same basicity (D) Both have same acidic strength

7. Which of the following reaction will give the best yield of t-butyl methyl ether?
H SO
(A) (CH3)3C–OH 
2
140 C
4
 (B) (CH3)3C–Br + CH3OH 

O   
O
(C) (CH3)3C–Br + CH 3 O Na (D) (CH 3 )3 C  OK  CH 3Br 

8. Major product of following reaction is :

H H
NaNO
 
2 
HCl

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

9. Select the correct schemes A, B, C respectively out of

I acid catalysed hydration II HBO III oxymercuration-demercuration

(A) I in all cases (B) I, II, III (C) II, III, I (D) III, I, II
10. For dehydration of the given alcohols, correct order will be:

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

2
11. Which one of the following can not be the product during dehydration of following alcohol.

H


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

12. Major product (E) of following reaction is :

H OHBr HCHO
CH3MgBr + 
3
 A  B Mg
 / ether
 C    D 
HI E
H O 3

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

13. Major product of A and B respectively for following reaction is :

LiAlH
Glycerol KHSO
 4  A  
4  B

(A) Acrolein, allyl alcohol (B) Glyceryl sulphate, acrylic acid
(C) Allyl alcohol, acrolein (D) Only acrolein (B is not formed)
14. 3-methyl-3-hexanol can not be prepared by
(A) CH3MgI and 3-hexanone, followed by hydrolysis
(B) C2H5MgI and 2-pentanone, followed by hydrolysis
(C) C3H7MgI and 2-butananone, followed by hydrolysis
(D) C4H9MgI and propanone, followed by hydrolysis
15. Major product of following reaction is :
18
OH /MeOH
NO2 – CH – CH2
O

18 18
OH OH OH OH
| | | |
(A) NO 2  CH  CH 2 (B) NO 2  CH  CH 2 (C) NO 2  CH  CH 2 (D) NO 2  CH  CH 2
| | | |
OH OH OH OH
18 18
16. Major product of following reaction is :



H3O

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

3
17. Which of the following option is correct for given path and product :

CH 3
 |
CH 3  O  C  CH 3  Me3C–I + Me–OH
| |
H CH 3

(A) Me3C–OMe with anhydrous HI gives this reaction

(B) Me3C–OMe with cold HI gives this reaction
(C) Me3C–OMe with hot HI gives this reaction
(D) Me3C–OMe with hydrolysis gives this reaction

18. The reaction of CH3OC2H5 with cold HI mainly gives

(A) CH3I + C2H5I (B) CH3OH + C2H5OH
(C) CH3I + C2H5OH (D) C2H5I + CH3OH

19. If phenyl magnesium bromide and acetaldehyde are the reactants, the product formed after hydrolysis
would be :
(A) Benzyl alcohol (B) 1-Phenylethanol (C) 2-Phenylethanol (D) Acetone

20. Which of the followingforms di-iodide on reaction with HI (excess)?

I II

(A) I and II both (B) II only (C) I only (D) none

21. Ethanol on reaction with acetic anhydride gives
(A) only Acetic ester (B) only Formic ester
(C) only Ethanoic acid (D) Acetic ester and Ethanoic acid both
22. Phenol with Benzene sulphonyl chloride gives
(A) Sulphone (B) Sulphanilic acid
(C) Sulphonic ester (D) Sulphonal
23. Rate of hydration of following compounds will be in order:

, ,

(A) III < I < II (B) I < III < II (C) II < I < III (D) III < II < I
24. Glycol on heating with PI3 mainly gives–
(A) Ethylene (B) Ethylene iodide (C) Ethyl iodide (D) Ethane

4
25. Major product of A and B respectively for following reaction is :

CH OH CH OH
(A)  
3
 3
 (B)
 H 2SO 4
CH 3O

(A) & (B) &

(C) & (D) &

26. Products of the reaction are :

O COOC2H5
LiAlH4

(A) Racemic (B) Diastereomers (C) Meso (D) Optically pure

27. Major product A and B respectively for following reaction is :

CH OH H O18
B  
3
 2  A
CH 3ONa H

CH 3 CH 3 CH 3 CH 3
| | | |
(A) CH 3  C  CH 2 , CH 3  C  CH 2 (B) CH 3  C — CH 2 , CH 3  C  CH 2
| | | | | | | |
OH OH OH OCH 3 OH18OH OH OCH 3
18

CH 3 CH 3 CH 3 CH 3
| | | |
(C) CH 3  C  CH 2 , CH 3  C — CH 2 (D) CH 3  C — CH 2 , CH  C — CH
3 2
| | | | | | | |
OH OH OH 18OH 18 OCH 3 OH
18 18 18OH OH

28. Which of the following reaction is called as ‘Bouveault–Blanc reduction’

(A) Reduction of acyl halide with H2,Pd/ BaSO4
(B) Reduction of ester with Na/C2H5OH
(C) Reduction of anhydride with LiAlH4
(D) Reduction of carbonyl compounds with Na/Hg,HCl

5
29. In the following reaction, final product and mechanism used is:
14
ClCH 2CH  C H 2 NaOC H
 25 
\ /
O
14 14
(A) ClCH 2CH C H 2OC 2 H 5 , SN2 (B) ClCH 2CH C H 2ONa , SNNGP
| |
OH OC2 H 5
14 14
(C) C H 2  CHCH 2OC 2 H 5 , SNNGP (D) CH 2  CH C H 2OC 2 H 5 , SNNGP
\ / \ /
O O
30. For the following set of reactions major product Q is :

conc . H SO
(I) Oxalic acid + P  ; (II) P  24  Q

O
O
(A) (B) (C) CH 2  O  CH 2 (D)
O
| | O
OH OH
31. Among the following choose the incorrect statement ?
(A) Boiling point increases with increase in carbon due to increase in vander wall forces
(B) Branching in carbon decreases the boiling point
(C) High boiling point of alcohols are mainly due to pressure of intermolecular H-bonding
(D) Methoxymethane has higher boiling point than ethanol & propane
32. Major product of the given reaction is :
O 1. KH
HS 2. H2O
OH OH
S O
S
(A) (B) (C) HS–(CH2)5–O–Et (D) HS–(CH2)4 –CH
OH
33. Which of the following order(s) is/are incorrect ?
(A) CH3–CH2–OH > CH3–CH2–CH2–OH > CH3–CH2–CH2–CH2–OH (Solubility in H2O)
(B) CH3–CH2–OH > CH3–O–CH3 > CH3–CH2–CH3 (Boiling point)
(C) Pentan-1-ol > Pentanal > Ethoxy ethane (Boiling point)
(D) CH3–OH > CH3–CH2–OH > CH3–CH2–CH2–OH (Boiling point)

34. Which of the following ethers is the most unreactive to cleavage with conc. HBr?

(A) Ph–CH2–O–CH3 (B) Ph–O–Ph (C) O (D) O

35. Ethoxyethane & butan-1-ol are miscible to almost same extent (7.5 & 9 gm per 100 ml water respec-
tively), because of :
(A) Same molecular mass (B) They are isomers
(C) Both can form hydrogen bond with water (D) Water is universal solvent

6
 EXERCISE # II
1. Compounds which gives alcohol on reduction with Diborane in THF is/are
O O
|| ||
(A) Me  C  Cl (B) Me  C  NH 2 (C) Me  CH  CH 2 (D) Me  C  O  C  Me
|| || \O/
O O
2. For the reaction sequence, choose the correct option(s) :
dil. H SO H
CaC2 H
2O
 P  
2
4  Q 
2
R
2 Ni
Hg

(A) P and R can be differentiate by lucas and bromine water test

(B) R on reaction with sulphuric acid at 453K produces diethyl ether
(C) P is more reactive than Q for catalytic hydrogenation reaction
(D) Both P and R are soluble in aq. NaOH due to acid base interaction

3. HBO, oxymercuration-demercuration and acid catalysed hydration will not give same product in

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

4. Diethyl ether reacts with PCl5 to form

(A) Ethyl chloride (B) Phosphorous oxy trichloride
(C) 1,2-dichloro ethane (D) Ethene

5. For the following sequence, which of the following products are correctly matched :

BH ·THF H O , OH 
(A) 3 2 
2
 NaOH
 

Hg ( OAc) NaBH
(B)    4  NaOH
2    
H 2O

(C) mCPBA
 
CH 2Cl 2

(D)

6. Lucas test is used to make distinction between 1°, 2° and 3° alcohols, for the following choose the
coorect option(s) :
anhydrous ZnCl
ROH + HCl    2  RCl+ H2O
conc.
(A) ROH behaves as a base
(B) Greater the value of pKa (alcohol), greater the reactivity with conc. HCl
(C) RCl is immiscible in lucas reagent and produce white turbidity in solution.
(D) Primary alcohols do not produce turbidity at room temperature and follows SN2 mechanism

7
7. Which method(s) is/are useful for the synthesis of ether?

(A) (excess) aq

. NaOH

(B) C2H5ONa + (CH3)2SO4 

(C) CH3ONa + CH3CH2OSO2 

(D) (CH3)3CBr + CH3CH2ONa 

8. Which of the following(s) will give immediate turbidity with lucas reagent ?

(A) CH3–CH2–OH (B) CH  CH 3 (C) CH2OH (D)

|
OH
9. For the following sequence, choose the correct option(s)
Tilden NH 3 NaNO2
C2H5NH2  (P)  (Q)   (R)
reagent HCl
(A) R will give white turbidity of P with lucas reagent on heating
(B) Both P and R formation involves release of nitrogen gas
(C) Formation of Q involves bimolecular nucleophilic substitution
(D) R on reaction with thionyl chloride produces P with best yield
10. Consider the Squaric acid and select the correct statement(s):

(A) It is aromatic in nature (B) It is more acidic than Acetic acid

(C) It reacts very fast with Lucas reagent (D) It's dianion has four equivalent resonating structure
11. Major product Q and R (respectively) in following conversion is :

conc
 .H 2SO 4
 P OsO
4  Q H
 R
  
H 3O

OH OH
OH
(A) & (B) &
OH
O OH OH O
OH
(C) & (D) &
OH
12. Major product of which of following reactions can give turbidity with lucas reagent within 10 minutes :
O O
|| (i ) CH MgBr ( excess ) || (i ) CH MgBr ( excess )
(A) H  C  Cl  3   
  (B) Ph  C  O  Et  3   
 
(ii ) H (ii ) H

O O
|| || (i ) CH MgBr ( excess )
(C) H  C  O  Et (
i ) CH 3MgBr ( excess )
     (D) H  C  H  3   
 
( ii ) H  ( ii ) H

8
13. Predict major organic product from the following reaction:

(A) (B)

(C) (D)

14. Compond Z in given sequence can be :

PCl5 Al. KOH 1. Conc. H2SO4
Z X Y Z
 2. H2O, boil
(A) CH3–CH2–CH2–OH (B) H 3C  CH  CH 3
|
OH
(C) Diethyl ether (D) Cyclopentanol

15. Which of the following are possible products in the given reaction?
HO

HI

I
I

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

I

16. In which of the following reaction(s) labelled atom will react rapidly with nucleophile :

* *
(A) (B) NaOH

* *
DIBAL
NaBH
(C)  
4  (D) hexane,195K
CH3OH

9
17. Gaseous product C is :
Br Mg 14
(i) CO2 NaHCO3
(A) +
(B) (C)
(ii) H /H2O
(A) CO (B) 14 CO2
(C) CO2 (D) A mixture 14CO2 and CO2

18. Dehydration of alcohols take place more rapidly with POCl3, pyridine than with H2SO4. Select the
correct statement(s) about the following dehydration reaction.

POCl
3 
pyridine

(A) It does not involve carbocation.

(B) It involves R–OPOCl2 with – OPOCl2 as a better leaving group.
(C) It involves E1CB mechanism as pyridine base abstracts proton from the adjacent carbon
(D) It is E1 reaction without formation of carbocation.
19. Functional group present in major product B is :
RMgX
RMgX 
(i) CH3CN
(ii) HClH2O
(A) 
(ii) NH Cl
(B)
4

(A) 1° Amine (B) 3° Alcohol (C) 3° Amine (D) Alkene

20. Major product of given reaction is:

SOCl2 Mg,  O
OH Pyridine
O
Et2O 
H3O
O CH3
OH
(A) (B) CH–C
O
O CH3

CH3
OH
(C) O CH2 – C – CH2 – OH
(D)
O CH2 – CH2 – C – CH3
CH3
CH3
21. Structure of ‘P’ can be :
1. O
Br2/h Mg, Conc. H2SO4
P Q R S
Et2O 2. H2O +


CH3

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

10
22. Major product of given reaction is:
MgBr THF
+ BrMg H3O+
O O

(A) OH (B) OH
HO O

OH
(C) (D)
HO O
OH
23. When 2-chloroethanol is warmed slightly with dilute NaOH, the major product formed is :
(A) CH3–CH2–CH2–O–CH2–CH2–Cl (B) HO–CH2–CH2–CH2–CH2–OH
(C) HO–CH2–CH2–OH (D)
O
24. How many total alcohols are form by acidic hydrolysis of following ether.
OCH3

(A) 5 (B) 6 (C) 7 (D) 8

25. Compound P for following reaction can be :
(i) Hg(OAc) , HOH
P 
A 2

(ii) NaBH ,OH

 1-Methylcyclohexanol.
4

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

26. Products of the following reaction is/are :

CH3MgX
O Product
NH4Cl

(A) Enantiomer (B) Diastereisomer (C) Meso (D) Racemate

27. Major product of given reaction is:

H2O/H
‘X’
O O
CH3

(A) (B) O
HO O CH3 OH HO CH3 CH3 OH

(C) O (D) All of these

HO OH

11
28. Which combinations of reagents can bring about the following conversion?
O

Br
(A) (i) MeMgBr/H (ii) H2SO4/ (iii) HBr/H2O2
(B) (i) MeMgBr/H (ii) Al2O3 (iii) B2H6 (iv) H2O2,NaOH (v) SOBr2
(C) (i) MeMgBr/H (ii) H2SO4/ (iii) HBr/CCl4
(D) (i) MeMgBr/H (ii) POCl3 (iii) B2H6 (iv) Br2

29. Which of the following reactions is/are not matched with major product?
(A) C6H5OH + HBr  C6H5Br + H2O
(B) (CH3)3CCl + NaOCH3  (CH3)3COCH3 + NaCl
Cl OMe
(C) CH3OH


Cl + CH3ONa Cl

(D) C6H5MgBr H3O+ C6 H 5CH 2 C(CH 3 ) 2

O |
OH
30. Choose the correct statement(s) :
(A) t-butyl alcohol reacts less rapidly with metallic sodium than the primary alcohol.
(B) Diethyl ether can behaves as base.
(C) Sometimes explosion occurs during distillation of ether sample.
(D) Ethyl alcohol reacts with HI but not with HCN.

31. Reaction of 1-propanol with each of the following reagents, carboxylic acid will obtain as one product is
(A) Potassium dichromate (K2Cr2O7) in aqueous sulfuric acid, heat

(B) CH3 SO2Cl in the presence of pyridine

O O
|| ||
(C) C 6 H 5COCC 6 H 5 in the presence of pyridine

(D) in the presence of pyridine

32. Major organic product of which reactions can show stereoisomerism :

CH OH
(A) 
NH
3  (B) + CH3ONa 3

methanol

(C) HCl
 (D) CH3(CH2)16CH2OTs + CH3CH2CH2CH2SNa 
CHCl3

12
33. Major product Q of following reaction is :

(i ) LiAlH
  4  P (C3H7ClO) KOH

, H 2O
 Q (C3H6O)
H 2O

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

Paragraph for 34 and 35

For the following sequence :
PCl 
C2H5OH 5  (P) KCN
 (Q) H
3O
NH 3
 (R)  (S) heat
 (T)

34. Which of the following reactions will produce same major product :
(A) P with ammonia (B) Q with tin and hydrochloric acid
(C) T with LiAlH4 in Et2O (D) Q with Na in Ethanol

35. T on reaction with PCl5 produces :

(A) P (B) Acetyl chloride (C) R (D) Q

Paragraph for Que. No 36 to 38 (3 questions)

36. Compound 'B' is?

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

37. Compound 'A' can show :

(A) Tautomerism (B) Nucleophilic addition
(C) Reduction (D) Redox reaction

38. Total number of stereoisomers of A,B respectively are?

(A) 1,2 (B) 0,4 (C) 0,2 (D) 2,2

13
39. Match the column:
CH 3  CH  CH  CH 2 Re  Alcohol
agent

|
CH 3
Column-I Column-II
(Alcohol) (Reagent)
(A) CH 3  CH  CH 2  CH 2OH (P) (i) B2H6 (ii) H2O2 / NaOH
|
CH 3

(B) CH 3  CH  CH  CH 3 (Q) (i) HBr (ii) H2O

| |
CH 3 OH
OH
(C) | (R) (i) Hg(OAc)2, H2O (ii) NaBH4/NaOH
CH 3  C  CH 2 CH 3
|
CH 3
(S) Dil. H2SO4

(T) (i) HBr/H2O2 (ii) aq. NaOH

40. Match the major products in column-I with correct statement in column-II for following sequence
 c 2  (i)CH  I1eq.
 a   b   d  e
i Mg Br
CH2= CH –CH2Br 
(ii)HCHO
2
CCl4
Alc.KOH

 (C4 H 7 OCl)
NaNH 3 eq.


3
(ii)CH3 CH 2  I1eq.
(iii)H 2 O

Column-I Column-II
(A) a (P) Can show stereisomerism
(B) b (Q) Formation involves addition reaction
(C) c (R) 5 - ethoxy pent-2- yne
(D) e (S) Can show substitution reaction
(T) 1 - methoxy hex - 3 -yne

14
 EXERCISE # III (JEE MAINS)
1. When CH2 = CH–COOH is reduced with LiAlH4, the compound obtained will be -

(1) CH3–CH2–CH2OH (2) CH3–CH2–CHO

(3) CH3–CH2–COOH (4) CH2=CH–CH2OH

2. Acid catalyzed hydration of alkenes except ethene leads to the formation of

(1) Secondary or tertiary alcohol
(2) Primary alcohol
(3) Mixture of secondary and tertiary alcohols
(4) Mixture of primary and secondary alcohols

3. The best reagent to convert pent–3–en–2–ol into pent –3–en –2–one is -

(1) Acidic dichromate (2) Acidic permanganate
(3) Pyridinium chloro-chromate (4) Chromic anhydride in glacial acetic acid

4. Phenyl magnesium bromide reacts with methanol to give-

(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

5. 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

P  I2
6. In the following sequence of reactions CH3CH2OH   A 
Mg
Ether
 B 
HCHO
 C 
H2 O
 D,
then compound 'D' is -
(1) Butanal (2) n–Butyl alcohol (3) n–Propyl alcohol (4) Propanal

7. The number of stereoisomers possible for a compound of the molecular formula

CH3–CH = CH–CH(OH) – Me is :-
(1) 4 (2) 6 (3) 3 (4) 2

8. 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 :
(1) CH3COCH3 (2) CH3COOH (3) CH3OH (4) HCHO

9. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous
ZnCl2, is :
(1) 1–Butanol (2) 2–Butanol
(3) 2–Methylpropan–2–ol (4) 2–Methylpropanol

10. Consider the following reaction :

C2H5OH + H2SO4  Produce
Among the following, which one cannot be formed as a product under any conditions ?
(1) Ethyl-hydrogen sulphate (2) Ethylene
(3) Acetylene (4) Diethyl ether

15
11. Iodoform can be prepared from all except :
(1) Isobutyl alcohol (2) Ethyl methyl ketone (3) Isopropyl alcohol (4) 3-Methyl–2–butanone
12. 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 :
(1) secondary alcohol by SN1 (2) tertiary alcohol by SN1
(3) secondary alcohol by SN2 (4) tertiary alcohol by SN2
13. Allyl phenyl ether can be prepared by heating:
(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
14. In the Victor-Meyer's test, the colour given by 1°, 2° and 3° alcohols are respectively :-
(1) Red, blue, colourless (2) Colourless, red, blue
(3) Red, blue, violet (4) Red, colourless, blue
15. Williamson synthesis of ether is an example of
(1) Nucleophilic addition (2) Electrophilic substitution
(3) Nucleophilic substitution (4) Electrophilic addition
16. The major product of the following reaction is:
O


HI(excess)



NC O
OH I OH I

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

NC I NC OH NC OH NC I

17. The major product of the following reaction is :

OCH3

 
Conc HBr(excess)
heat

CH=CH2

Br OH Br OH

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

CH2CH2Br Br–CHCH3 Br–CHCH3 CH2CH2Br

18. The major product the following reaction is :


(i)Br2
(ii)EtOH


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

16
19. The major product of the following reaction is :

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

20. The major product of the following reaction is:

CH3
OH
(i) aq. NaOH
(ii) CH3I

CH3 CH3 CH3 CH3

OCH3 OH OH OH
(1) (2) (3) (4)
CH3 CH3
CH3
21. The major product of the following reaction is :
Cl

(i)HBr
(ii)alc.KOH

O
OH Cl Cl

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

O OH O O

22. Which of the following compounds will produce a precipitate with AgNO3 ?

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

23. The major product obtained in the following conversion is :-

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

17
24. The major product of the following reaction is :

(1) (2)

(3) (4)

25. The major product of the following reaction is:

(1) (2) CH3CH=C=CH2

(3) (4) CH3CH2CCH

26. The major product of the following reaction is:

CH2CH3

H3C C Cl 
NaOEt



COOCH2CH3

OCH2CH3

(1) H3CH2C C CO2CH2CH3 (2)

CH3
CH2CH3
(3) H3C C OCH2CH3 (4)

COOCH2CH3

27. The major product in the following conversion is :

(1) (2)

(3) (4)

18
 EXERCISE # IV (A) (JEE ADVANCED)
1. The products of combustion of an aliphatic thiol (RSH) at 298 K are:
(A) CO2(l), H2O (g) and SO2(g) (B) CO2(g), H2O (g) and SO2(g)
(C) CO2(l), H2O (l) and SO2(g) (D) CO2(g), H2O (l) and SO2(l)

2. 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:
(A) CH3–CH2–CHO (B) CH3–CO–CH3 (C) CH2=CH–CH2OH (D) CH2= CH–OCH3

3. 
The reaction products of C6H5OCH3 + HI  are:
(A) C6H5OH + CH3I (B) C6H5I + CH3OH
(C) C6H5CH3 + HOI (D) C6H6 + CH3OI
4. The order of reactivity of the following alcohols:

towards conc. HCl is:

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

5. Among the following compounds, the strongest acid is:

(A) HCCH (B) C6H6 (C) C2H6 (D) CH3OH

6. Which one of the following will most readily be dehydrated in acidic condition:

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

7. Identify the correct order of boiling point of the following compounds:

CH3CH2CH2CH2OH CH3CH2CH2CHO CH3CH2CH2COOH
1 2 3
(A) 1 > 2 > 3 (B) 3 > 1 > 2 (C) 1 > 3 > 2 (D) 3 > 2 >1

8. Major product of following reaction is :

C H O  Na  ( excess)
OH + C2H5I      
2 5
C 2H5OH ( anhydrous)

(A) OC2H5 (B) I (C) C6H5OC6H5 (D) C2H5OC2H5

9. Reaction of entainomerically pure acid with 1 chiral carbon and racemic alcohol with 1 chiral carbon
gives an ester which is:
(A) Meso (B) Optically active mixture
(C) Racemic mixture (D) Enantionmerically pure

19
10. On acid catalysed hydration, 2-phenyl propene gives:
(A) 3-phenyl-2-propanol (B) 2-phenyl-1-propanol
(C) 1-phenyl-3-propanol (D) 2-phenyl-2-propanol

11. Phenyl magnesium bromide reacting with t-Butyl alcohol gives

(A) Ph – OH (B) Ph – H (C) (D)

12. Statement-1: p-Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid.
because
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.

13. In the reaction OCH3 HBr

 the products are

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

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

14. Amongst the following, the total number of compounds soluble in aqueous NaOH is
H3C CH3
N COOH OCH2CH3 OH
CH2OH

OH
NO2 CH2CH3 COOH
CH2CH3

N
H 3C CH3
15. The major product in the following reaction is
O
Cl 1. CH3 MgBr, dry ether, 0°C
CH3 2. aq. acid
OH
O
(A) H3C (B) H2C CH3
CH3 CH3

(C) (D) CH3

CH2 O CH3
O

20
16. The acidic hydrolysis of ether (X) shown below is fastest when

acid
OR OH + ROH

(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
17. The correct combination of names for isomeric alcohols with molecular formula C4H10O is/are

(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

18. Total number of isomers, considering both structural and stereoisomers, of cyclic ethers with the molecular
formula C4H8O is ____

21
 EXERCISE # IV (B) (JEE ADVANCED : SUBJECTIVE)
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?

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.

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).

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 

O  C  OH HOCH 2
Conc .H 2SO 4
5. | + |     (A)
O  C  OH HOCH 2

6. Discuss why o-hydroxy benzaldehyde is a liquid at room temperature while p-hydroxy benzaldehyde is
a high melting solid?

7. White the structures of the product A & B


CH 3  C  O18C 2 H 5 H
3O
 A + B
||
O
8. 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.

9. 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    
Y    Z
(ii ) X ,(iii ) H 3O

10. Mention two esters produced when a racemic mixture of 2-phenyl propanoic acid is treated with (+)
2-butanol. What is the stereochemical relationship between these esters?

22
11. An organic compound P(C5H10O) Reacts 1015 times faster then ethylene with dil.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.

12. (X) C5H13N NaNO , HCl

 2 (Y) (Tertiary alcohol + other products)
N2

(Optically active)
Find X and Y. Is Y optically active? Write the intermediate steps.

23
 ANSWER KEY
EXERCISE # I
1. D 2. D 3. B 4. C 5. A
6. A 7. D 8. D 9. C 10. C
11. C 12. D 13. A 14. D 15. A
16. B 17. B 18. C 19. B 20. C
21. D 22. C 23. C 24. A 25. B
26. B 27. A 28. B 29. D 30. A
31. D 32. A 33. D 34. B 35. C
EXERCISE # II
1. CD 2. AC 3. ABD 4. AB 5. ABC
6. ABCD 7. ABC 8. BD 9. ABCD 10. ABCD
11. D 12. ABC 13. B 14. B,D 15. BCD
16. ABC 17. C 18. AB 19. B 20. D
21. C 22. A 23. D 24. D 25. AB
26. AD 27. A 28. ABD 29. ABC 30. ABCD
31. ACD 32. ABC 33. B 34. BCD 35. D
36. C 37. BCD 38. C
39. (A) P,T ; (B) R; (C) S,Q 40. (A) Q,S ; (B) P,Q,S ; (C) P,S ; (D) R,S
EXERCISE # III (JEE MAINS)
1. 4 2. 1 3. 4 4. 2 5. 4
6. 3 7. 1 8. 2 9. 3 10. 3
11. 1 12. 2 13. 1 14. 1 15. 3
16. 1 17. 2 18. 4 19. 3 20. 1
21. 2 22. 4 23. 4 24. 2 25. 4
26. 4 27. 4
EXERCISE # IV (A) (JEE ADVANCED)
1. B 2. D 3. A 4. C 5. D
6. A 7. B 8. D 9. B 10. D
11. B 12. D 13. D 14. 4 15. D
16 C 17. ACD 18. 10.00

EXERCISE # IV (B) (JEE ADVANCED : SUBJECTIVE)

1. 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  CH 3CH 2CH 2COO O K + MnO2 + KOH
n-Butanol Brown
CH 3
|
CH 3  C  CH 3 + KMnO4  No reaction
|
OH
t-Butanol

24
 H Me Me
| | H Me |
| |  H O 
2.

CH 3  C — C  CH 3 H  2
 CH  C H  C  CH
CH 3  C — C  CH 3  3
| 3
| | | |
O H
Me  Me
  OH Me 2

Me Me
|  |
H
CH 3  C  C  CH 3  CH 3  CH  C CH 3
| 
|
Me Me

3. (D) Ph  CH  CH 3 (E) C6H5COOH

|
OH
4. The ether formation involves nucleophilic substitution of alkoxide ion for halide ion.
 Fast
Slow
 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 (b)

5.

6. Due to intermolecular H-Bonding

7. A  CH 3  C  OH , B = C2H5O18H
||
O

H O
8. Mg
 MeCHO
  
3
 HBr

Et 2O

(A) (B) (C)

Mechanism


H 
2 H O
 


 Br


2°carbonium 3° carbonium

* * * *
9. X : C O 2 ; Y : C H 2  CH  C OOH ; Z : CH 2  CH C H 2OH ; C H O
2

25
 H
|
Ph H (  ) CH3CH 2 COH
|
| | CH3
10. CH 3  C  COOH + CH 3  C  COOH     
conc. H 2SO 4 , 
| |
H Ph
(recemic mixture)
Ph H H H
| | | |
CH 3  C  C  O  C  CH 2 CH 3  CH 3  C  C  O  C  CH 2 CH 3
| || | | || |
H O CH 3 Ph O CH 3
during esterification reaction only – COOH and – OH participates. There is no effect on structure of
configuration of carbon adjacent of these groups. So when (±) acid reacts with pure (+) alcohol two
esters are produced whinc are diastereoisomers of each other.

CH 2
||
11. P : CH 3  CH 2  O  C  CH 3
Q : CH3CH2OH
R : CH 3  C  CH 3
||
O
when ethylene reacts with dil. H2SO4CH3CH2 is produced during rate determining step, whereas P
gives resonance stabilized intermediate.
CH 3 CH 3
| |
CH 3  CH 2  O  C  CH 3 CH 3  CH 2  O  C  CH 3
 
due to extra stability of intermediate the rate of reaction is very fast

OH
|
12. X: CCCC Y: CCCC
| | |
C NH 2 C
Y is optically inactive.

26