Page 1 of 15 CPP - SANKALP_AEP-02&3-PH-V

CPP - SHEET – 2, 3
PREPARATION OF ALCOHOL
SUBJECTIVE (LEVEL – 1)
1. Complete the reaction

H2O / H
(a) Et — O — Et  

O
(b) 
H2O / H
R C OR  

H2 / Pt
(c) R — CHO 

H2Ni
(d) R2 CO  

(e) H2 / Pt
CHO 

CN O
(f)
H2 / Pt


H2 / Ni
(g) CHO 
(1 eq)

(h) LiAlH4
CHO 
H2O

O
LiAlH4

H2O
(i)

H2 / Pt


NaBH4
COOH  
(j) H2O

LiAlH4

H2O

O
(k) LiAlH4

H2O

HCl
(l) CH3CHO + LiAlH4 
H2O


HCl
(m) CH3 CHO  LiAlD4 
H2O


DCl
(n) CH3 CHO  LiAlH4 
D 2O


LiAllH4
HCl


(o) CH3 COCH2CH2COOCH3
NaBH4

HCl

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2. Show how you would synthesize the following alcohols by adding appropriate grignard reagent to
formaldehyde (Write complete reaction)

CH2OH
(a) (b)
OH

CH2OH
(c)

3. Show how would you synthesize the following alcohols by adding an appropriate Grignard reagent to an
appropriate carbonyl compound?

OH

(a) (b)
OH

H OH

(c)

4. Synthesize following alcohols starting from a Grignard reagent and acid chloride
(a) Ph3COH (b) 3-ethyl-2-methyl-3-pentanol
(c) Dicyclohexylphenylenethanol
5. Show how would you synthesize the following alcohols by adding Grignard reagent to ethyleneoxide?
(a) 2-phenylethanol (b) 4-methyl-1-pentanol

OH
(c)

6. Complete the following reactions—

i) CH3

H3C CH CH CH2 

(CH3COO)2 Hg
 NaBH4
 ?  
H2O

ii) CH3 CH  CH2  B2H6  ? H2O2

 
OH
iii) Cu Zn
CH3 CH  CH2  CO  H2  
H2

iv) H2O
H3 C  H2C  CH2NH2  HNO 2  

7. Synthesize the following:

(a) Butene to butanol and butan-2-ol
(b) 1-chlorobutane to pentanol and pentan-2-ol
(c) Benzene to 3-(4-chlorophenyl) propanol
(d) Ethyne to butanol
(e) Propane to allyl alcohol

dil H2SO4
8. CH CH CH3   ? (with mechanism)

SUBJECTIVE (LEVEL – 2)
1. Predict major product in the following reaction
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dil H2SO 4
H3C C CHCH3  

(a) dil H2SO4
(b)
 
 F

CHCH3

(c)
dil H2SO4
 


2. Complete the following reactions:

Ac 2O (i) Me MgBr Conc. (i) BH3 / THF

(a) Benzene 
 AlCl3
 B 
 (ii) H O
 C 
H2SO4
 D 
 (ii) H O / OH
E

(A ) 3 2 2

alc. Br2 2NaNH2 RMgBr (1) Acetone

(b) MeCH2Br 
KOH
 B   C   D 
1 mol
 RH  E 
(2) H O
F
3
A

Br alc. NBS Mg / ether (1) Acetone conc. H2SO4


KOH
 B   C   D 
(2) H O
 E  
F
(c) 3
(A)

3. Show how would you synethesize following alcohol adding Grignard reagent to ethylene oxide?
(a) 2-phenylethanol (b) 4-methyl-1-pentanol

OH
(c)

4. An optically active organic compound (A) (C7H11Br) is treated with Mg in ether to give B(C7H11MgBr), which
react violently with D2O to give methylcyclohexene with deuterium atom on the methyl group (C). Reaction of
B with acetone followed by hydrolysis gives D (C10H18O). Heating D with concentrated sulphuric acid gives E
(C10H16). Determine structure of A to E.
5. Determine the structure of compound A through H
O

(1) CH3Mg1 H2SO4 H2 /Pt


(2) H O 
 A   B  C
3

H2SO4 / 
KMnO 4 / 
C10H16 (H) C6H12O(E)
H2SO4 / 

CH3MgBr H3O
C10H18O(G)
O
(ii) (i) Mg / Ether
(iii) H3O
PhCO3H
BrH
C5H9Br(F)     C5H8O (D)

6. Synthesize following alcohol from compound containing no more than five carbons

OH

7. Treatment of the following epoxide with aqueous acid produces a carbocation intermediate that reacts with
water to give a diol. Show the structure of the carbocation, and propose mechanism for the second step

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
H
 [carbocation]  OH
HO
H
O CH
3

8. Reaction of pure (+)-3-methyl-2-pentanone with methyl magnesium bromide followed by acidification yields 2,
3-dimethyl-2-pentanol. What is the stereochemistry of product. Is product optically active?

OBJECTIVE (Level – 1)

1. 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

2. In general, the reduction of ketone to an alcohol can be accomplished by all of the following except one
(A) H2/Pt (B) HIO4
(C) LiAlH4 (D) NaBH4

3. What is product of following reaction?

O
(i) LiAlH4

(ii) H2O


O OH
(A) (B)

OH
OH
(C) (D)

OH

4. Your task is to synthesize 2-phenyl-2-hexanol through a Grignard’s synthesis. Which pair(s) of compounds
listed below would you choose as starting materials?
O O

(a) CH3 (b) CH3

Br and Br and

O Br
(c) and (d) Both (a) and (c)

5. What product(s) is/are produced in the 1 : 1 reaction of sec-butylmagnesium bromide with

OH
H
H3C
O
OH CH3 OMgBr
CH3
(a) CH3 (b) H H3C
H3C H3C
OMgBr O

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OH OMgBr

(c) CH3 (d) H (CH3)3CH

H3C H3C
OMgBr CH3 O

6. Which of the following pairs of the compounds can be used as starting materials in the synthesis of 2-phenyl-
2-pentanol?
(a) (CH3)3 CBr and PhCOOH (b) (CH3)2CHCH2Br and PhCOCH3
(c) PhBr and CH3CH2CH2COCH3 (d) PhBr and (CH3)2CHCH2COCH3

7. Which of the following alcohols can be synthesized using the reaction sequence?
O

Mg H3O
H3C Br  
 
ether


(a) H3C CH2CH2OH (b) HOH2C CH2CH2OH

(c) Br CH2CH2OH (d) H3CO CH2CH2OH

8. Which of the following pairs of reagents would you use to prepare 4-methyl-2-pentaol?
(a) (CH3)2CHCH2Li + CH3CHO (b) (CH3)2CHLi + CH3CH2CHO
(c) (CH3)2CHLi + CH3COCH3 (d) CH3CHLi + (CH3)2CHCHO

9. Which cannot be made by reduction of ketone and aldehyde with NaBH4 in methanol?
(a) 1-butanol (b) 2-butanol
(c) 2-methyl-1-propanol (d) 2-methyl-2-propanol

10. Choose the reagent and reactant that would produce 2-methyl-2-butanol as the major product.
O O
(I) (i) C2H5MgBr (II) CH3MgBr

(ii) NH4Cl, H2O
 
NH4Cl, H2O

O
(III) CH3MgBr
 
NH4Cl, H2O
OMe
(a) I & II & III (b) I & III only
(c) I only (d) III only

11. Choose the correct structure for the major compound produced by the following reaction sequence
NaNO2

HCl, 0o C


NH2
HO

(a) (b)
OH
HO O

(c) (d)

HO O

12. 3-Phenyl-2-propanol could be prepared from, which of the following reaction?

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OH
3-Phenyl-2-propanol
O

(a) H (b)  (i) BH3


(ii) H2O2 / NaOH
NaBH4



Cl

NaBH4
(c) NaOH (d)  
  O

13. The increasing order of reactivity of the following towards acid catalyzed hydration is

(I) (II) (III)

(a) I  II  III (b) I  III  II

(c) II  I  III (d) III  II  I

OBJECTIVE (LEVEL – 2)

1. AC6H14O chiral alcohol is converted to a bromide by treatment with PBr3. Reaction of this bromide, first with
Mg in ether, followed by quenching in 0.1 N HCl produces an achiral C6H14 hydrocarbon. Which of the
following is the original alcohol?
(a) 2-ethyl-1-butanol (b) 4-methyl-1-pentanol
(c) 3-methyl-3-pentanol (d) 3-methyl-1-pentanol

2. 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

3. 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

4. The major product of the following reaction is

O


H3O

H2O
 [X]

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OH CH2OH

(a) (b)
CH3 CH3

OH OH
CH2OH CH3

(c) (d)
CH3

CH3 OH

5. Which of the following alcohol will give the compound “A” the fastest upon treatment with H3PO4?
OMe

O
O

O
A
OMe OMe

OH
OH
(a) (b)
O O
O O

O O
OMe OMe

OH
(c) (d)
O O
O O
OH
O O

+
6. Which of the following statement is true regarding the reaction of cis, trans 2-hexenewith CH3OH, H ?
+
(a) Cis and trans-2-hexene react with CH3OH, H at the same rate
(b) Cis-2-hexene reacts at faster rate than trans
+
(c) Reaction of both cis and trans-2-hexene with CH3OH, H gives a mixture of positional isomers as the
major product
(d) both (a) and (c)

7. Which of the following reagent or set of reagents will best bring about the following reaction?
H3C CH3 H3C CH3 H3C CH3
H OH OH
O OH OH
HO CH3 HO CH3 HO CH3
(a) H3O+ (b) (i) POCl3 (ii) H+/CH3OH
(c) NaOH/CH3I (d) (i) H3PO4 (ii) NaBH4

8. Consider the following reaction scheme

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OH

C CH2 A
OH

OH

A, B and C are respectively

–
(a) Hg (OAc)2/H2O/NaBH4; dil H2SO4; B2H6/H2O2/HO
–
(b) dil. H2SO4; Hg(OAc)2/H2O/NaBH4; B2H6/H2O2/HO
–
(c) dil. H2SO4; B2H6/H2O2/HO ; Hg(OAc)2 / H2O/NaBH4
–
(d) B2H6/H2O2/HO ; Hg(OAc)2/H2O/NaBH4; dil. H2SO4

9. There may be something seriously wrong with the following proposed synthesis of the drug terfenadine.
Identify the problem if any, and propose specific steps needed to make this route workable.
N Br
Mg

Ether


OHC
OH

OH
N

OH

(a) There is nothing wrong

(b) In presence of —OH group, Grignard synthesis can’t be carried oout
(c) N will be involved in neighbouring group participation
(d) Both (b) and (c)

10. Which is/are true regarding the following reaction?

O
OH2
 NaBH4  
(a) The product will be a single pure enantiomer
(b) The product will be a racemic mixture
(c) It involves nucleophilic addition reaction
(d) If D2O is used, CH3CH2CD(OH)CH3 is formed

——
ANSWER KEY (SHEET 2 & 3)
SUBJECTIVE LEVEL - 1

1. (a) EtOH
(b) RCOOH + ROH
(c) R—CH2OH

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OH

(d) R C R

(e) CH2OH

H2NH2C HO
(f)

(g) CH2OH

(h) CH2OH

OH OH

(i)

OH OH
(j)
COOH, CH2OH

OH
(k)

(l) CH3CH2OH

(m) CH3CHDOH

(n) CH3CH2OD

(o) CH3CH(OH)CH2CH2CH2OH + CH3OH, CH3CH(OH)CH2CH2COOCH3

H H
O
Br MgBr
H C OMgBr
Mg
 

(C2H5 )2 O

H
2. (a)
H2O / H

CH2OH  Mg(OH)Br

(b) Br Mg MgBr 

(i) HCHO

  (ii) H O /H 
Et 2O 2
OH
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Br
OH
(c) (1)Mg /Et 2 / O

(2) HCHO


(3) H2O / H

Mg/ Et 2O (1) CH3CHO

Br    
(2) H O / H
3. (a) 2

OH

OH CH3
Mg /Et 2O (i) Ph CHO
(b) CH3CH2Br  
 Ph (ii) H2O /H

H OH
CHO
(c) Mg/ Et O (i)
Br   
2
(ii) H O /H

2


OMgBr
O O OMgBr
C  
PhMgBr
  Ph Cl Mg(Cl)Br PhMgBr
  C
Ph Cl Ph Ph Ph Ph
Ph
Ph

4. (a) H / H2 O Mg(OH)Br

OH

C
Ph Ph
Ph

O OMgBr OH

H / H2O
Cl  
(b) 
 2C2H5MgBr

H3C

OH
OMgBr
O
MgBr
C 
H2O / H
  Ph  
(c) Ph Cl Exess

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H
H OH
C
O C
5. (a) H
PhMgBr  H3O 
 H

(b) O OH

H3O
MgBr   

MgBr O OH
(c) 
 H3O
 


CH3 H H CH3 H H

6. i) H3C CH3 NaBH4

  H C C C H

OH HgOCOCH3 CH3 OH H

H H

ii) H3C C C H2O2 / OH

B 
–
 H3 C — CH2 — CH2OH  H3BO3

H H 3

iii) CH3CH2CH2CH2OH + (CH3)2CHCH2OH

OH
iv) OH  H3C
H3C
CH3

H H H
(1) BH3
C — C — C  C 
(2) H2O2 /H
 H3C C C C OH

H H H
7. a)
H H
(1) Hg (OAc )2 /H2O

(2) Na BH4
 H3C C C CH3

H OH (1) BH3
C — C — C  C  
(2) H O /H
2 2

OH
b) C C (1) Mg /Et 2O C C OH 

(2) HCHO
 (1) H / 
  H3C CH3
C C Cl (3) H2O / H C C C (2) Hg(OAc )2 /H2O
(3) NaBH4

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CH3 CH2Br CH2-CH2-CH2OH

(1) CH3Cl / AlCl3 NBS (1) Mg /Et 2O

c)      
(2) Cl2 / Fe
(2)
O
(3) H2O / H

Cl Cl Cl

(1) NaNH2 (1) HB3 / THF

d) H — C  C — H 
(2) C2H5Br
 C  C — C2H5 
( 2) H O / OH
 1bu tan ol

2 2
(3) H2 / Pd

(1) Br2 / H (1) NBS

e) C — C — C 
(2) Alc. KOH
 C  C — C 
(2) Aq. NaOH
 C  C — C — OH

OH

8. CH CH3  H  C CH2CH3 

H O
 2
C CH2CH3

H H H

SUBJECTIVE LEVEL - 2

CHCH3 CH3
CH3
1. (a) H hydride
  H
  H shifting
H2O
  O H 
  OH
H

H OH H
H3C H

H
(b) C C  H3C C C CH3 
H O
 H3C 2 C C CH3
F CH3
F H F H

CH2CH3 CH2CH3 CH2CH3 HO CH2CH3

2
1
H  H 2
  H2 O:
..

  

1 Ring Expansion

CH3 CH3
(c) hydride
 
shifting

Benzylic carbocation
H2 O H H2 O

OH
CH3 CH3

OH

(Major)

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Page 13 of 15 CPP - SANKALP_AEP-02&3-PH-V

O HO
CH3
C C
CH3 conc. H2 SO4
 
(CH3 CO)2 O
PhH  
(i) MeMgBr
  CH3 C CH2
AlCl3 (ii) H O
3
(A )

(D)
CH3
(B) (C)
2. (a)
H H

(i) BH / THF
C C OH 
(ii) H O / OH2
 3

2


CH3 H
(E)

Br
NaNH RMgBr
Alc. KOH
MeCH2Br  Br2
 C  C   C C   H — C  C — H 
2
 R — H  HC  CMgBr
(B) (D) (E)
(b) Br (C)
H3C CH
C
(i) CH3COCH3

(ii) H O 

H3C 3

OH

Br alc. KOH NBS Br Mg/ Et 2O

MgBr
     
(A) (B)
(C)

H3C CH COCH
(c) CH2 
HO
3

3

CH2 
conc. H SO
 2 4
3

H3C
OH
(E)

H H
O 
3. (a) Ph MgBr  H
 Ph C C OH

H H

(b) O
MgBr  H


OH

MgBr O
OH
(c)  

H

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Page 14 of 15 CPP - SANKALP_AEP-02&3-PH-V

CH3

CH2Br CH2MgBr CH2D  OH

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

(d)

CH3
C C
CH3
(E) H

HO
OH Br
O

(A) (B) (C) (D) (E) (F) H

5.
OH

(G) (H)

Br MgBr O OMgBr

Mg / Et 2O
  
  OH
6.

 

HO

+ HO
O
7. H

H2O

 H

OH
HO
HO

8. Product formed with retention of configuration at chiral carbon

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Page 15 of 15 CPP - SANKALP_AEP-02&3-PH-V

CH3 H3C CH
3
CH3MgBr

H


H H
O OH

OBJECTIVE – LEVEL – 1
1. D
2. B
HIO4 is an oxidising agent
3. B
LiAlH4 resduces carbonyls but not the olefins.
4. A
5. B
6. C
7. A
8. A
9. D
10. A
11. D
12. D
13. A

OBJECTIVE – LEVEL – 2
1. D
2. A
3. C
4. B
5. A
6. B
7. A
8. C
9. D
10. B, C

——

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