109.

5
0
Ethers
Definition
Nomenclature
Physical Properties
Reactions
Synthesis
Definition
What are ethers ?
A class of organic compounds in which oxygen
is bonded to 2 carbon groups
General formula: R-O-R
Examples:
CH
3
CH
2
O CH
2
CH
3
Diethyl ether
are like water, with alkyl groups replacing
both of the -Hs:
H-O-H water
R-O-H alcohol
R-O-R ether
relatively unreactive
commonly used as solvents

Structure- functional group
is a Oxygen bonded to 2
carbons

O
CH
3
H
3
C
O O
O
O
Nomenclature
IUPAC: 3-(t-butoxy)-pentane
IUPAC: Methoxyethane
IUPAC: Methoxybenzene
The R-O-R group is strongly polar.
Ethers have two C-O bonds.
Ethers cannot form internal H bonds.
Their boiling points are lower than those of
their alcohol counterparts.


Ethers are better solvents than alcohols for
nonpolar compounds.
Ethers can H bond with water and alcohols

CH
3
CH
2
OH
bp= 78
o
C
CH
3
OCH
3
bp= 36
o
C
Physical Properties
R
:O:
H
H O
R

Hydrogen bonding between

molecules of an alcohols
R
O
R
R
O
R
No hydrogen bonding
Chemical Properties of Ethers
CH
2
CH
3
O CH
3
CH
O CH
3
CH H
I CH
3
CH
2
CH3
HI, H
2
O
CH3
+
Ethyl isopropyl ether Isopropyl alcohol Iodoethane
1. Cleavage of ethers by acids
R-O-R + HX R-OH + RX
O
CH
2
CH
3
HBr, H
2
O
Reflux
OH
CH
3
CH
2
Br
+
CH
3
CHCOOH
OCH
2
CH
3
HI +
100
O
C
H
2
O
CH
3
CH
2
I CH
3
CHCOOH
O
H
+
Phenol
Bromoethane
Iodoethane Lactic acid
Ethyl phenyl ether
2-Ethoxypropanoic acid
Examples:
Examples:
If an excess of acid is used, the
alcohol initially produced is also
converted to an alkyl halide
R-O-R + HX R-OH + RX
R-O-H + HX R-X + H
2
O
2. Reaction with PCl
5
CH
3
CH
2
OCH
2
CH
3
+ PCl
5
2CH
3
CH
2
Cl + POCl
3
CH
3
CH
2
OCH
2
CH
3
+ 2HI

2CH
3
CH
2
l + H
2
O

PREPARATION OF ETHERS
1. Intermolecular dehydration of alcohols
ROH + HOR
H
+
ROR + H
2
O
CH
3
CH
2
OH
CH
2
=CH
2
+ H
2
O
CH
3
CH
2
OCH
2
CH
3
+ H
2
O
Ethene
Diethyl ether
H
2
SO
4
180
o
C
H
2
SO
4
140
o
C
The starting alcohol in the above reaction must be primary and the reaction
temperature must be kept at 140
o
C
2. The Williamson synthesis of ethers
RONa + R' X
X = Br, I
ROR' + NaX
Sodiumalkoxide
Ethers
How to synthesis of ethyl propyl ether (CH
3
CH
2
CH
2
OCH
2
CH
3
)
CH
3
CH
2
CH
2
OH + Na
Propyl alcohol
CH
3
CH
2
CH
2
ONa
Sodium propoxide
+ 1/2 H
2
CH
3
CH
2
CH
2
ONa
+ CH
3
CH
2
I
S
N
2 reaction
CH
3
CH
2
CH
2
OCH
2
CH
3
+ NaI
The Williamson synthesis
2-Methoxypropane
(Isopropyl methyl ether)
Iodomethane
(Methyl iodide)
Sodium
isopropoxide
+ +
CH
3
CH
3
CH
3
I
CH
3
CHO
-
Na
+
CH
3
CHOCH
3
Na
+
I
-
S
N
2
CH
3
CH
3
CH
3
CO
-
K
+
CH
3
Br
S
N
2
CH
3
CH
3
CH
3
COCH
3
K
+
Br
-
+
+
Potassium
tert-butoxide
Bromomethane
(Methyl bromide)
2-Methoxy-2-methylpropane
(tert-Butyl methyl ether)
Williamson ether synthesis
Important ethers
Diethyl Ether
Diethyl ether is a very low-boiling
Highly flammable liquid
Care should always be taken when diethyl ether
is used in the laboratory, because open flames or sparks
from light switches can cause explosive combustion of mixtures
of diethyl ether and air.
CH
3
CH
2
OCH
2
CH
3
O
2
CH
3
CH
2
OCHCH
3
O OH
explosive
a hydroperoxide
autoxidation