Ethers

functional isomer of alcohol

ELEMENTARY ORGANIC CHEMISTRY

CH2

CH3

ETHERS

H3C

CH2

H2C

LECTURE

C H
H

weakly polar
Boiling point

weakly polar
Boiling point

Ethanol
Dimethyl ether

OH

H3C

C
H
H
C
3
3
O

increases with increasing MW

Molecular weight BP, C

H2
C

Physical Properties

Propane

CH2

Physical Properties

Lower than to alcohols of similar MW

CH3

>

44

-42

46

78.5

46

-24

>

44

21

1-propoxypropane (MW = 46) 2-(propan-2-yloxy)propane (MW = 46)

BP = 90.5C
BP = 68C

methoxymethane (MW = 46)

BP = -24.9C

ethoxyethane (MW = 74)

BP = 34.6C

for isomeric ethers, decreases with branching

Ethanal
H

Physical Properties

Preparation of Ethers

weakly polar
Solubility in water

Formation of symmetric ethers

comparable to alcohols of similar MW

decreases with increasing MW

Reagent: conc. H2SO4

only for 1 ROH (formation of alkenes if 2 or 3 ROH)
Mechanism: SN2

<
methoxymethane (MW = 46)

ethoxyethane (MW = 74)

for isomeric ethers, increases with branching

<
1-propoxypropane (MW = 46) 2-(propan-2-yloxy)propane (MW = 46)

Preparation of Ethers

Preparation of Ethers

Williamson Ether Synthesis

Williamson Ether Synthesis

can be used to form unsymmetric ether

Reagent: alkoxide
Substrate: best for 1 RX (formation of alkenes if 3 RX,
no reaction if ArX)
Mechanism: SN2
Example:

Mechanism: SN2
Example:

Preparation of Ethers

Exercises

Williamson Ether Synthesis

How to produce alkoxide? (RECAP: acidity of ROH and
ArOH
ROH with a metal
ROH with a metal hydride
ArOH with NaOH

1. Draw a functional isomer

with a higher boiling point.

H 3C
O
H 3C

Exercise

Chemical Reactions

Propose a mechanism for the synthesis of the following

molecules.

Acidic cleavage

O
H
CC
H
2
3
O

Reagent: strong acid at elevated temperature

General:
R-O-R + HX R-X + R-OH
Mechanism:
SN1 if R is benzylic, allylic, or 3
SN2 if R is CH3, 1, 2

R-OH cannot react with another mol of HX if R is Ar

R-OH + HX R-X + H2O

Chemical Reactions

Epoxides (oxiranes)

Acidic cleavage

3-membered cyclic ethers

H
C
2

C
H
2

O
ethylene oxide

How to prepare oxiranes?

Reaction of alkene with mCpBA
Halohydrin formation, followed by intramolecular
nucleophilic substitution

Reactions of Epoxides

Reactions

Acid-Catalyzed Ring Opening

follows SN1 mechanism => formation of the more
stable carbocation

Base-Catalyzed Ring Opening

CH3

CH3
H3C

C H

CH3OH
CH2

follows SN2 mechanism => base attacks the less

substituted C

H+

H3C

CH2OH

H 3C

C H
O

OCH3

C H

C H 3O C H 3O H

H 3C

C
O H

C H 3O C H

OH

1.

Exercises

OH

2.

H2SO4, 140

H 3C

C H 2C H 3

K M nO 4

O
C
H
3
C
H
2
O
(
H
C
)
C
3
3

H
+

C
H
2
O
(
H
C
)
C
3
3

N a

3.
O H

H
B
r

C H 3C H 2C H 2C l

C
H
3
C

3 . v ia w h a t m e c h a n is m ?

C
H
3
O
C

CH3

4.

C
H
3

CH3

H2
C

C
H
3
C
H
2
O
-

C
CH3

HCl(in excess)

C
H
3
C
H
2
O
H

C
H
3

OH

1.

H 2 S O 4 , 1 4 0

N a

2.
O H

C H 3C H 2C H 2C l
3 . v ia w h a t m e c h a n is m ?
4. m ost acidic
OCH3

Cl

OH

L ew is

OH

M ike

H arvey

1 . (2 p ts)

H O

K 2C r2O
H

2 . (2 p ts)

H 3C

OH

C H 2C H 3

K M nO 4

3. (3 pts)

HBr (excess)

CH3

4. (4 points)

CH3

H2
C

C
O

CH3

HCl(in excess)

NaOCH3 / CH3OH

1. (3pts)

OCH2CH3

2. (2pts) ?
HO