Ethers R-O-R or R-O-R´

Nomenclature:
simple ethers are named: “alkyl alkyl ether”
“dialkyl ether” if symmetric

CH3 CH3
CH3CH2-O-CH2CH3 CH3CH-O-CHCH3

diethyl ether 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 CH3CH2-O- = ethoxy, etc.

CH3-O-CH2CH2CH2-O-CH3 1,3-dimethoxypropane

HO-CH2CH2-O-CH2CH3 2-ethoxyethanol
 : :
O
Physical properties: R 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-O-R´ + NaX

R´-X should be CH3 or 1o

SN2 mechanism
Mechanism for the Williamson Synthesis = SN2

RDS
R O + R' X R O R' + X

R´-X should be CH3 or 1o

R-OH + Na  R-O-Na+
 R-O-R´
R´-OH + HX  R´-X

(CH3)2CH-OH + Na  (CH3)2CH-O-Na+
+  CH3CH2CH2-O-CH(CH3)2
CH3CH2CH2-OH + HBr  CH3CH2CH2-Br 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 Cannot be made via the Williamson
CH3 CH3 Synthesis. The alkyl halide would
be 3o.

2. Alkoxymercuration-demercuration

A way to make ethers that cannot be made via the Williamson

Synthesis. (later)
 R-H R-X R-OH R-O-R

Acids NR NR  
Bases NR   some NR
Metals NR   NR
Oxid. NR NR  NR
Reduc. NR  NR NR
Halogens NR NR NR NR
Reactions, ethers:

1. Acid cleavage.

R-O-R´ + (conc) HX, heat  R-X + R´-X

CH3CH2-O-CH2CH3 + HBr, heat  2 CH3CH2-Br

Mechanism
H
1) CH3CH2 O CH2CH3 + HX CH3CH2 O CH2CH3 + X

H SN2
2) X + CH3CH2 O CH2CH3 CH3CH2 X + HO CH2CH3

3) CH3CH2 OH + HX CH3CH2 OH2 + X

SN2
4) CH3CH2 OH2 + 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!