Page 1 of 9 CPP - SANKALP_AEP-4 & 5-PH-V

CPP - SHEET – 4 & 5

PROPERITIES OF ALCOHOL
SUBJECTIVE (LEVEL – 1)

1. Complete the reaction:—

– +
i) C2H5OH + NaNH2  ii) C2H5OH + RC  C Na 
iii) C2H5MgBr + C2H5OH  iv) C2H5OH + NaOH 
v) CH3OH + NaOH  vi) CH3COOH + NaOH 
vii) C6HOH + NaOH 
viii) C—C—C—OH + Na 
SOCl2

PCl5
 
ix) C2H5OH
PCl3
 
HCl
 
523 K
 
x) Al2O3
C2H5OH  
623 K
 

2. Write down the mechanism of following reaction

443 K
H H  

conc. 413 K
H C C OH 
H2SO4
 

383 K
H H  

3. Predict major product in the following reactions, give mechanism

CH3

a) H3C C CH CH3  HBr 

H OH
CH3

b) H3C C CH2OH  HCl 

CH3
c) CH2OH  HBr 
4. Starting with a suitable alcohol, outline a synthesis of each of the following.
a) Benzyl bromide
b) Cyclohexyl chloride
(c) Butyl bromide

5. Identify A to E in the following sequence of reaction.

SOCl2
A(C4H10O)  B(C4H9 Cl)

O3 HCl
F  D(C3H6 O2 ) 
H2O2
 C(C4H8 )   E(C4H9 Cl)

6. Give structure of the principle product (s) when each of the following alcohol reacts with
i) Na2Cr2O7/H2SO4 ii) PCC
(a) 1-octanol (b) 3-octanol
(c) 2-cyclohexen-1-ol (d) 1-methyl cyclohexanol

7. Suggest the method that would work best for each of the following laboratory synthesis.
(a) 1 – butanol  butanal (b) 1 – butanol  butanoic acid
(c) 2 – butanol  2- butanone (d) 2-buten-1-ol 2-butanoic acid
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8. Predict major products of sulphuric acid catalysed dehydration of following alcohols
(a) 1-methylcyclohexanol (b) Neopentyl alcohol
(c) 2-methyl-2-butanol (d) 1-pentanol
(e) 3-methylcyclohexanol (f) 1-isopropylcyclohexanol
HO
CH
(g) CH3 (h)
OH

(i)
OH

9. Write equations for the reaction of 1-butanol with each reagent. Where you predict no reaction, write NR.
(a) Na metal (b) HBr, heat
(c) HI heat (d) PBr3
(e) SOCl2, pyridine (f) K2Cr2O7, H2SO4, H2O, heat

10. Complete these equations. Show structural formulas for the major products.

(a) H2CrO4
(b) SOCl2
OH   OH 

HCl
  OH HBr
(c) (d)  
HO Excess

OH

SUBJECTIVE (LEVEL – 2)
1. When the compound (1) is heated with 50% H2SO4, the product of the reaction is the compound (2) and not
(3). Write a step-by-step mechanism showing how II is formed?

HO

H3O
  not
Heat

(1) (2) (3)

2. When the following seven-membered ring alcohol is dehydrated, three alkenes are formed

H2SO4
 
 
Heat 

OH
Propose a mechanism for their formation.

3. A compound X (C14H14O) on mild oxidation yields C14H12O(Y). If X is treated with a dehydrating agent, it loses
a molecule of water and resulting product on vigorous oxidation yields two molecule of benzoic acid. Give
structure of X and Y.

4. Give the products of the pinacol rearrangement of the following glycols in acids.
Me Me H H

(a) Ph Ph (b) Ph Me

OH OH OH OH

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Me H Me

(c) Me H (d) Me

OH OH OH OH

(e)
OH OH

OBJECTIVE (LEVEL – 1)
1. What is the product of the following reaction?
OH
SOCl2

P yridine


Cl Cl
(a) (b) Cl

Cl
(c) (d)

2. Which of the following will not convert 1-butanol into 1-chlorobutane in one step?
(a) SOCl2 (b) PCl3 (c) HCl (d) CCl4

3. Which reagent would be best for the conversion of tert-butanol into teri-butyl bromide?
(a) PBr3 (b) HBr (c) NaBr (d) Br2, NaOH

4. Which of the following alcohols would be the most difficult to oxidize?

(a) CH3C(OH)(CH3)2 (b) CH2CH(OH)CH2(CH3)2
(c) CH3OH (d) HOCH2CH2OH

5. A synthesis of 2, 5-dimethyl-2-hexanol from 2-methypropene requires the formation of X and Y. X and Y

combine to give the desired product after the usual hydrolysis work-up. Select appropriate methods of
preparing X and Y from 2-methylpropene.
(a) For X add HBr, then react with Mg in ether to 2-methylpropene, for Y add water, acid-catalysis 2-
methylpropene
(b) For X add HBr (peroxides), then react with Mg in ether to 2-methylpropene, for Y react with C6H5CO3H in
CH2Cl2 to 2-methylpropene
(c) For X add HOBr to 2-methylpropene, for Y add B2H6 in ether, then NaOH to 2-methylpropene
(d) For X add HOBr to 2-methylpropene, for Y add HBr (peroxides), then react with Mg in ether to 2-
methylpropene

6. Which one of the following alcohols will be oxidized by Jones’ reagent (CrO3 in 50% sulphuric acid) to a
ketone having the same number of carbon atoms?
(a) 1-methylcyclohexanol (b) 3,3-dimethylcyclopentanol
(c) 3-methyl-1-hexanol (d) 3-ethyl-3-hexanol

7. What reagent would be suitable for distinguishing 1-methoxy-3-methyl-2-butene from its isomer 4-methyl-3-
penten-1-ol?
(a) Bromine in methylene chloride (b) KMnO4 in aqueous base
(c) AgNO3 in dilute NH4OH (d) Sodium metal suspended in hexane

8. Which reaction condition would be best to perform the following transformation?

Cyclohexanol  1-methyl cyclohexene
(a) (i) PCC; ii) MeMgBr, iii) POCl3 (b) TsCl/MeMgBr
(c) HBr/Mg/MeI (d) NaOH/MeI

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9. What is the product of the reaction?
CH3
TsCl NaCN(aq.)
H    
H
OH
CH3 CH3

(A) (B)

CN CN
CH3 CH3

(C) (D)

CN CN
10. What is the major product of the reaction?
CH3

CH3
HBr
 
OH
CH3 CH3

CH3 Br
(A) (B)

Br CH3
CH3 CH3

(C) CH2Br (D)

CH3Br
11. What is the major product of the reaction?
CrO3 , H2SO4
PhCH2OH  
O O
(A) (B)
C C
Ph H Ph OH
+
O OH
(C) PhCH3 (D)
C
Ph H

12. Which of the following will react with per iodic acid to give an aldehyde product?
OH

(A) (B)
OH
OH
O
(C) (D)
OH OH
13. Which of the following alcohols is oxidized to a ketone by chromic acid?
OH OH
(A) (B)

CH2OH CH2OH
(C) (D)

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OBJECTIVE (LEVEL – 2)

1. What is the product formed in the following synthesis?

OH
1. PBr3
2. CH3COONa

CH COOH

3

OCOCH3
(a) O (b)

Br
(c) (d)

2. Treatment of 3-methylpentanol with POCl3 in pyridine will provide

(a) a mono substituted alkene (b) a disubstituted alkene
(c) a tisubstituted alkene (d) a tetrasubstituted alkene

3. A chiral C5H10O alcohol is reduced by catalytic hydrogenation to an achiral C5H12O alcohol. The original
alcohol is oxidized by activated MnO2 to an achiral carbonyl compound (C5H8O). Which of the following might
be the chiral alcohol?
(a) 1-penten-3-ol (b) 4-pentn-2-ol
(c) 3-methyl-2-butene-1-ol (d) 2-methyl-2-butene-1-ol

4. A C5H12O compound is optically active, and is oxidized by PCC in CH2Cl2 to an optically active C5H10O
product, which is racemized in acid or base. Which of the following best fits these facts?
(a) 2-pentanol (b) 2-methoxybutane
(c) 2-methyl-1-butanol (d) 3-methyl-1-butanol

5. What is the major product of the following reaction

H3C CH3
CH3CH2OH
H3C O  

O S CH3

O
OCH2CH 3 OCH2CH3
(a) (b)
OCH2CH3

(c) (d)
OCH2CH3

6. Choose those reactions that would give the following amine.

OH NH2


PBr3 N3 1. LiAlH4 PCC NH3 H2 Pd / C PBr3 :CN 1. LiAlH4
                
 2. H2O
 2
  2. H2O


1 3

(A) 1 + 2 + 3 (B) 1 + 2
(C) 2 + 3 (D) 1 + 3

7. Predict the major organic product of the following reactions.


(1) LiAlH4 PBr3 KCN H2O, H
(CH3)2CHCO2H 
(2) H2O
   
DMSO

 
Heat

(A) (CH3)2CHCH2CH2NH2 (B) (CH3)2CHCHBrCO2H
(C) (CH3)2C = CHCO2H (D) (CH3)2CHCH2CO2H
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Page 6 of 9 CPP - SANKALP_AEP-4 & 5-PH-V
8. Which of the following diol(s) will not undergo a periodate (HIO4) cleavage?
OH
CH3

H3C OH OH OH

HO CH3
HO
CH3
(I) (II) (III)
(A) III (B) II
(C) I, II, III (D) II,III

9. Which of the following is not readily oxidized by K2Cr2O7 in H2SO4/H2O in?

(A) n-butyl alcohol (B) Sec-butyl alcohol
(C) Iso-butyl alcohol (D) Tert-butyl alcohol

10. Which one the following diols would cleave into two fragments with HIO4?
(A) 1, 3-hexanediol (B) 2, 4-hexanediol
(C) 3, 4-hexanediol (D) 1, 6-hexanediol

11. As a reducing agent, NaBH4 donate _____________ to a ketone or aldehyde?

(A) Proton (B) Hydrogen atom
(C) Hydrid ion (D) Hydrogen molecule

12. Which of the reagent below will oxidize a secondary alcohol to a ketone?
(A) LiAlH4 (B) HIO4
(C) K2Cr2O7, H2SO4/H2O (D) HgSO4, H2SO4/H2O

13. When the compound below is oxidized with Cr2O72– in acid, the major product is
OH

CH3
(A) ketone which is meso
(B) an optically active ketone
(C) a racemic mixture of ketone that is optically active
(D) an aldehyde that is meso and optically inactive

——

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ANSWER KEY
SUBJECTIVE (LEVEL – 1)
1. i) C2H5ONa + NH3
ii) RC  CH + C2H5ONa
iii) C2H6 + Mg(OC2H5)Br
iv) No reaction
v) No reaction
vi) CH3COONa + H2O
vii) C6H5ONa + H2O
viii) C—C—C—ONa + H2
ix) C2H5Cl + SO2 + HCl
C2H5Cl + POCl3 + HCl
C2H5Cl + H3PO3
C2H5Cl + H2O
x) (C2H5)2O; C2H2
2. H H
443K
  H2C  CH2

conc. 413K
H3C C C OH 
H2SO4

   C2H5OC2H5
383K
H H   CH3 CH2OSO3H

HOSO2OH  H  HSO4

H
H
 443K
H3C C O H  H  H3C CH2 O  
H
H
At 383 K

CH3 CH2  OSO3H  CH3 CH2OSO3H
At 413 K
H

CH3 CH2  O CH2CH3  H3C C O C2H5 H2SO4
  C2H5OC2H5
H
H H
At 443K
H H H
H C C H 
 HSO 
4
H2SO 4
 C C
H H H
H
3. a) (CH3)2C (Br)CH2—CH3
b) (CH3)2C (Cl)CH3
c) C Br

TsCl NaBr
4. a) C6H5CH2OH   C6H5CH2OTs   C6H5CH2Br
OH Cl
TsCl NaCl
b)    

TsCl
c) C4H9OH  NaBr
 C4H9Br
5. A 1-butanol B 1-chlorobutane
C 1-butene D Propanoic acid
E 2-chlorobutane F Formic acid
6. (a) (i) Octanoic acid (ii) Octanal (b) (i) 3-octanone (ii) 3-octanone

(c) (i) O (ii) O

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(d) No reaction

7. (a) PCC (b) Na2CrO4/H2SO4

(c) Na2CrO4/H2SO4 (d) PCC followed by treatment with Ag2O/H2O
8. (a) Methyl cyclohexene (b) 2-Methyl-2-butene
(c) 2-Methyl-2-butene (d) 2-Pentene
(e) 4-Methyl cyclohexene

(f) (g)

(h) (i)

1
9. a) ROH  Na  RONa  H2
2
Br
b)

OH  HBr 

OH  HI  
c)
I
d) OH  PBr3  Br
e) OH SOCl2  Cl
COOH
f) H
 K 2Cr2 O7 


OH

10. (a) (b)

COOH
Cl
Br
Cl
(c) (d)

Br

SUBJECTIVE (LEVEL – 2)

1. HO 
H
H 
 

 H2O



H Ring 
H

 H2O


contraction
Methyl shift
   

OH

2. H
H

3. X : PhCH(OH)CH2Ph, Y : PhCOCH2Ph

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CH3 CH3 H CH3

4. (a) Ph C C O (b) Ph C C
O
Ph H

(c) (CH3)2CHCHO (d)

(e)

OBJECTIVE (LEVEL – 1)

1. D
2. D
3. B
4. A
5. B
6. B
7. D
8. A
9. A
Tosylate formation followed by SN2.
10. B
11. B
CrO3 is acidic medium oxidises 1° alcohol to acid.
12. B
Vicinal diol undergo periodic acid cleavage to give carbonyls.
13. B
2° alcohol is oxidised to ketone.

OBJECTIVE (LEVEL – 2)
1. B
2. A
3. A
4. C
5. B
6. B
Both 1 and 2 give the desired product, C will increase the chain length by one unit.
7. D
8. D
Only syn, vicinal, diols undergo priodate cleavage.
9. D
3° alcohol cannot be oxidised under normal condition.
10. C
It is a vicinal diol
11. C
NaBH4 is a hydride donor
12. C
K2Cr2O7/H2SO4/H2O oxidises a 2° alcohol to ketone.
13. B
——

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