Page 1 of 9 CPP - SANKALP_AEP-7-PH-V

CPP - SHEET – 7
PROPERTIES OF ETHERS
SUBJECTIVE (LEVEL – 1)

1. Draw structural formulas for the major products of each reaction.

CH3

(a) H3C O CH3 

HBr (Excess)


CH3

HBr (Excess)
(b)  
O

2. Draw structural formulas for the products formed when each compound is heated or reflux in concentrated HI.
CH3 O HI
(a) O
HI

1 eq.
 (b) 
1 eq.


O
HI HI
(c) O 
1 eq.
 (d) 
excess

O

3. When C2H5ONa reacts with 1-(chloromethyl)oxirane, labelled with *C as shown by asterisk in I, the major
product is an epoxide bearing the labelled carbon as shown in II. Provide mechanism to explain this fact.
Cl
EtONa OEt
 
O O
I II
4. Which of the following is the product from ethanol addition to dihydropyran (shown below)?

C2H5OH

H


O
5. Predict products of the following reaction.
a) CH3OCH2CH2CH2CH3 + HI 
Cold
b) (CH3)3COCH2CH3 + HI  
O
c)  IH 

6. Show how you might use the Williamson ether synthesis to prepare each ether?
a) b) O
O

7. Suggest reagent for the following transformation.

OH
NH2
O
H3C C CH CH2CH3
(a)
CH3 N

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OH
O
(b) H3C C CH CH3

NH2

OH
O
(c) H3C C CH2 OH

CH3

CH3
O
(d) H3C C  (CH3 )3 C CH(OH) CH2SCH2 CH2CH3

CH3

O
(e)  (CH3 )2 CHCH2OH

SUBJECTIVE (LEVEL – 2)
1. Chysanthemic acid occurs as a mixture of esters in flowers of the chrysanthemum (pyrethrum) family.
Reduction of chrysanthemic acid to its alcohol followed by conversion of the alcohol to its tosylate gives
chrysanthemyl tosylate.Solvolysis of the tosylate gives a mixture of artemesia and yomogi alcohols.

HO  HO  TsO

chrysanthemyl alcohol

O Chrysanthemyl acid OH
OH H2O

DMSO



Atremisia alcohol Yomogi alcohol

Propose a mechanism for the formation of these alcohols from chrysanthemyl tosylate.

2. Predict the product

O O
excess MeMgI
 H O
 Product
3

3. Two isomeric compounds (A) and (B) have molecular formula C2H6O. (A) on heating with HI gives alkyl iodide
and H2O. Whereas (B) gives alkyl iodide and alcohol with dil. HI. What are (A) and (B)?
4. A compound (A), molecular formula C6H14O does not react with Na. When heated with hot HI, it is converted
into a mixture of two isomeric compounds of formula C3H7I. What is the original compound (A) ?
5. An organic compound (A), C8H10O, does not react with sodium. On treatment with HI it yields two compounds
(B) and (C). (B) reacts with sodium to liberate hydrogen and also forms a salt with sodium hydroxide. (B) can
also be brominated and the product contains two bromine atoms. The compound (C) contains iodine. On
treatment of (C) with magnesium in ether, followed by addition of dry ice and finally acidification with dilute
acid, it forms acetic acid. Give the structures of (A), (B) and (C).
–
6. Ethylene oxide reacts readily with HO because of the strain in the three-membered ring. Cyclopropane has
approximately the same amount of strain, but does not react with HO–. Explain.
7. Give the product of each of the following reactions

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O
a) CH3ONa / CH3OH
 

O
b) CH3OH
 
H

O CH3OH
c) 
H


O CH3OH
d) 
CH3ONa


OBJECTIVE (LEVEL – 1)
1. Ethers may be used as solvents they react only with
(a) acids (b) bases (c) oxidizing agents (d) reducing agents

2. What are the products when ethyl isopropyl ether is cleaved with concentrated HI?
(a) Ethanoland 2-iodo-2-methylpropane (b) Ethanol and 2-methylpropane
(c) Iodoethane and isopropyl alcohol (d) Iodoethane and 2-methylpropane

3. Which pair of products would result from the acid cleavage of phenyl propyl ether with excess concentrated
HBr at an elevated temperature?
(a) Phenol and 1-propanol (b) Bromobenzene and 1-propanol
(c) Bromobenzene and 1-bromopropane (d) Phenol and 1-bromopropane

4. Which of the following ethers is unlikely to be cleaved by hot conc. HBr?

H2

O C
(a) (b) OC2H5
H

(c) O (d) O

5. If the following *C labelled compound undergo the following reaction, which product would be obtained?
O
One mole of KCN
13  EtOH

C Cl

13
C O
(a) HO Cl (b) 13
C CN
CN
13 O
C
(c) CN Cl (d) CN
13
C
OH

6. Which of the following reacts the fastest with NaOH, H2O?

(a) Ethylene oxide (oxirane) (b) Trans 2,3-dimethyl oxirane
(c) cis-2, 3-dimethyl oxirane (d) 2,2,3,3,-tetra methyl oxirane

7. What is the product of the following reaction?

2HBr
 ?
O
(a) 1,3-dibromo butne (b) 1,4-dibromo butane
(c) 1,3-dibromo propane (d) 1,2-dibromo propane
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8. What are the products of the reaction below?
CH3

HI (Excess)
 


CH2OCH3
CH3 CH3

(a) (b)
 CH3 OH  CH3I

CH2I CH2I
CH3 CH3

(c) (d)
 CH3I  CH3I

CH2OH CH2I

OBJECTIVE (LEVEL – 2)

1. Which would you expect to be the major rearrangement product of the following reaction?
OH

H

O

O O
(a) (b)
O O

(c) (d)
O O
O

2. Which of the following reaction would provide the best synthesis of 2-butanol?
O CO2
(a) CH CH MgBr  H
 (b) CH3CH2CH2MgBr +  H

3 2 OH2
 
H H
(c) CH3MgBr + Acetone 
OH2
 (d) CH3CH2MgBr + CH3CHO 
OH2


3. What is the product from the acid catalyzed addition of methanol to 2, 2-diethyloxirane?
(a) 3, 3-dimethoxypentane (b) 2-ethyl-1-methoxyl-1-butanol
(c) 2-ethyl-1-methoxy-2-butanol (d) 2-ethyl-2-methoxy-1-butanol

4. A chiral C5H10O ether reacts with hot HI to give a C5H10I2 product. Treatment of this with hot KOH in ethanol
produces 1, 3-pentadiene. What is the structure of the original ether?
O
(a) (b)
O
O O
(c) (d)

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Page 5 of 9 CPP - SANKALP_AEP-7-PH-V
5. Predict the major product of the reaction
O CH2CH3

PhMgBr

H O
?
3

OH CH 2CH3
HO
CH2 C CH3 C
(a) (b)

OH OH

CH2 C CH2CH3 Mg CH2 C CH2CH3

(c) (d)

6. Which synthetic pathway gives a racemic mixture of the deuterated compound with little isomeric impurities?

H D  enantionmer

OH H
CH3CO3H (i) LiAlD 4 (i) BD3 / THF
(a) Cyclopentene   
(ii) H2O
 (b) Cyclopentene 
(ii) H2O2 . NaOH

D 2 / Pt Br2 / Pt NaOH DCl H2O, H3OH
(c) cyclopentene  
CCl4
 
OH2
(d) cyclopentene   
Heat


7. Select the structure of the major product formed in reaction?


H
H3C CH2 
H O18
2

O
OH H3C CHCHOH
18
(a) OH (b)
H3C OH
18
OH
H3C CHCH3
(c) (d) H3C CH CH2
OH
OH
18

8. What is the final product of the reaction sequence?

O

PBr3 Mg H3 O
(CH3 )2 CHOH   
Ether
 
  
CH3 CH3
(a) (b)
(CH3)2CHOCHCH2OH (CH3)2CHOCH2CH - OH
CH3 CH3
(c) (d)
(CH3)2CHCH2CHOH (CH3)2CHCHCH2OH

9. The major product of the following reaction is

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Page 6 of 9 CPP - SANKALP_AEP-7-PH-V
O

H3O

H2O
 [X]

OH CH2OH

(a) (b)
CH3 CH3
OH OH
CH 2OH CH3

(c) (d)
CH3
CH3 OH

10. Treatment of “A” with excess of HBr with provide?

OH
OH H
N

HO
OH OH
Br H OH H
N N
(a) (b)

HO Br
Br Br
OH H Br H
N N
(c) (d)

HO HO

11. Which of the following reagent or set of reagents will best bring about the following reaction?
CH3
H3C H

O 
HO CH3
CH3 CH3
H3C OH H3C OH

(a) (b)

HO CH3 HO CH3
CH3 CH3
H3C OH H3C OH

(c) (d)

HO CH3 HO CH3

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Page 7 of 9 CPP - SANKALP_AEP-7-PH-V
12. The major product of the following reaction is

H2SO4
OH 
Warm



(a) (b)

(c) (d)

——
ANSWER KEY

SUBJECTIVE (LEVEL – 1)
1. i) (CH3)3CBr + CH3Br
ii) Br(CH2)5Br
OH
2. (a) C2H5I + C3H7OH (b) C2H5I 

CH2I
(c) (d) CH2 = CH2
OH
4.

O OC2H5
5. a) CH3I + CH3CH2CH2CH2I
b) (CH3)3Cl + C2H5I
c) 2-(3-iodopropyl) Phenol
6. a) OH
Br
O
Na

 Product
Heat
[Allyl halide is more reactive is SN2 reaction]
b) Na
OH   Cl
Heat
Product

7. (a) (b) NH3

NH2

(c) NaOH/H2O (d) CH3CH2CH2SNa/H2O

(e) CH3MgBr, H2O

SUBJECTIVE (LEVEL – 2)
1. OH

 H



 H2 O
H3C

formed form tosylate H H2O

OH

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2. O O O O–
MeMgI
 
CH3

O
O

CH3

MeMgI

O–
O–

H3+O

OH
OH

3. (A): C2H5OH (B): CH3OCH3

4. C6H14O is an ether as it does not show any reaction with Na. Hot HI cleaves the ether linkage and forms two
isomers of C3H7I. So it must be unsymmetrical ether with similar number of carbon atoms in the alkyl part but
differs in branching. The two isomeric compound of molecular formula C3H7I are
CH3  CH2  CH2I and CH3  CH  I
|
CH3
Hence, the structure of (A) should be
CH3CH2CH2  O  CH(CH3)2
2propoxypropane
O—CH3 OCH3 OH OH
CH3 CH3
5. or ; or , CH3I (C);

CH3 CH3
(A) (B)
6. Polarity of C—O bond in oxirane ring makes carbon electrophilic and nucleophilic attack of HO– takes palce.
Due to lack of polarity in cyclopropane, no such nucleophilic attack occur on the carbon of the cyclopropane
ring.

OH
OCH3
7. a)

OH
b)
OCH3
OCH3
c)
OH
OH

d)
OCH3
OBJECTIVE (LEVEL – 1)
1. A
2. C
3. D
4. C
5. D
6. A
Oxiane, although ether, highly reactive due to large angle strain.
7. C
8. B

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OBJECTIVE (LEVEL – 2)

1. B
2. D
3. D
4. B
5. A
It is not a reactive intermediate.
6. A
7. A
Protonated oxirane will undergo nucleophilic attack at more substituted ring carbon, hence O18 will be
attached to 3° carbon.
8. C
9. B
10. D
Both OH bonded to sp3 carbon will be substituted by Br– but not the phenolic —OH.
11. D
–
Protonation on oxygen of oxirane followed by nucleophilic attack by H at the more substituted carbon will give
the desired products.
12. C
——

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