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Ethers

Ethers have the general structure R-O-R' and can be named as alkyl alkyl ethers or dialkyl ethers if symmetric. They can be synthesized via the Williamson Synthesis using sodium alkoxides and primary or methyl alkyl halides, or via alkoxymercuration-demercuration. Ethers undergo acid-catalyzed cleavage to alkyl halides and undergo nucleophilic substitution.

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183 views17 pages

Ethers

Ethers have the general structure R-O-R' and can be named as alkyl alkyl ethers or dialkyl ethers if symmetric. They can be synthesized via the Williamson Synthesis using sodium alkoxides and primary or methyl alkyl halides, or via alkoxymercuration-demercuration. Ethers undergo acid-catalyzed cleavage to alkyl halides and undergo nucleophilic substitution.

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Jihee Yoon
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Ethers

R-O-R

or

R-O-R

Nomenclature:
simple ethers are named:

alkyl alkyl ether


dialkyl ether if symmetric

CH3CH2-O-CH2CH3
diethyl ether

CH3 CH3
CH3CH-O-CHCH3
diisopropyl ether

CH3-O-C(CH3)3

tert-butyl methyl ether

(MTBE)

If complex, the ether part is named as an alkoxy group:


CH3-O- = methoxy

CH3-O-CH2CH2CH2-O-CH3

HO-CH2CH2-O-CH2CH3

CH3CH2-O- = ethoxy, etc.

1,3-dimethoxypropane

2-ethoxyethanol

Physical properties:

R'

oxygen is sp3 hybridized, bond angle ~ 109.5o


ethers are polar; no hydrogen bonding
mp/bp moderate
water insoluble

Diethyl ether = very important organic solvent, polar, water


insoluble, bp = 35o. Very flammable & forms explosive
peroxides.

Industrial synthesis for diethyl ether:


2 CH3CH2-OH

H2SO4, 140oC

CH3CH2-O-CH2CH3

H2O

Not generally useful for syntheses of ethers in the lab:


a) Only symmetric ethers can be made this way.
b) Conditions are very compound specific
( at 180o ethanol would yield ethylene instead of the ether)

Synthesis of ethers

1. Williamson Synthesis.

R-O-Na+ + R-X

R-X should be CH3 or 1o


SN2 mechanism

R-O-R + NaX

Mechanism for the Williamson Synthesis = SN2

RDS
R O + R'

R-X should be CH3 or 1o

R O R'

R-OH + Na

R-O-Na+
R-O-R

R-OH + HX

R-X

(CH3)2CH-OH + Na (CH3)2CH-O-Na+
+
CH3CH2CH2-OH + HBr CH3CH2CH2-Br

CH3CH2CH2-O-CH(CH3)2
isopropyl n-propyl ether

note: the alkyl halide is primary!

CH3CH2CH2-OH + Na CH3CH2CH2-ONa
+

CH3CH2CH2-O-CH(CH3)2

(CH3)2CH-OH + HBr (CH3)2CH-Br

2o

alkene

The product of this attempted Williamson Synthesis using a


secondary alkyl halide results not in the desired ether but in an
alkene!

The alkyl halide in a Williamson Synthesis must beCH3 or 1o!

Synthesis of di-tert-butyl ether?


CH3 CH3
CH3C-O-CCH3
CH3 CH3

Cannot be made via the Williamson


Synthesis. The alkyl halide would
be 3o.

2. Alkoxymercuration-demercuration
A way to make ethers that cannot be made via the Williamson
Synthesis. (later)

Acids
Bases
Metals
Oxid.
Reduc.
Halogens

R-H

R-X

R-OH

R-O-R

NR
NR
NR
NR

NR

NR

some

NR
NR
NR

NR
NR

NR

NR
NR

NR
NR

Reactions, ethers:

1. Acid cleavage.

R-O-R + (conc) HX, heat

CH3CH2-O-CH2CH3

HBr, heat

R-X +

R-X

2 CH3CH2-Br

Mechanism
1) CH3CH2 O CH2CH3 + HX

SN2
H
O CH2CH3

2)

3)

CH3CH2 OH + HX

4)

+ CH3CH2

CH3CH2

CH3CH2 OH2 + X

CH3CH2 X + HO CH2CH3

CH3CH2 OH2

SN2

H
O CH2CH3 + X

CH3CH2 X

+ H2O

Alkanes
Nomenclature
Syntheses
1.
2. reduction of an alkyl halide
a) hydrolysis of a Grignard reagent
b) with an active metal and acid
3. Corey-House Synthesis
Reactions
1. halogenation
2. combustion (oxidation)
3. pyrolysis (cracking)

Alkyl halides:
nomenclature
syntheses:
1. from alcohols
a) HX

b) PX3

2. halogenation of certain alkanes


3.
4.
5. halide exchange for iodide
reactions:
1. nucleophilic substitution
2.
3. formation of Grignard reagent
4. reduction

Alcohols:
nomenclature
syntheses
later
reactions
1. HX
2. PX3
3.
4. as acids
5. ester formation
6. oxidation

Ethers
nomenclature
syntheses
1. Williamson Synthesis
2.
reactions
1. acid cleavage

Mechanisms:

Free radical substitution

SN2

SN1

Memorize (all steps, curved arrow formalism, RDS) and know which
reactions go by these mechanisms!

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