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!