ETHERS

• Ethers have two alkyl groups bonded to an oxygen atom.

R – O – R’
 Epoxides
• Epoxides are ethers having the oxygen atom in a three-
membered ring.
• Epoxides are also called oxiranes.

• The C–O–C bond angle for an epoxide must be 60°, a

considerable deviation from the tetrahedral bond angle of
109.5°.
• Thus, epoxides have angle strain, making them more
reactive than other ethers.
 Oxygen Hybridization and Geometry
• The oxygen atom in alcohols, ethers, and epoxides is sp3
hybridized.
• Alcohols and ethers have a bent shape like that in H2O.
• The bond angle around the O atom in an alcohol or ether is
similar to the tetrahedral bond angle of 109.5°.
• Because the O atom is much more electronegative than
carbon or hydrogen, the C–O and O–H bonds are both polar.
 Naming Ethers
• Simple ethers are usually assigned common names. To do so:
• Name both alkyl groups bonded to the oxygen, arrange
these names alphabetically, and add the word ether.
• For symmetrical ethers, name the alkyl group and add
the prefix “di-”.
 Naming Complex Ethers
• More complex ethers are named using the IUPAC system.
• One alkyl group is named as a hydrocarbon chain, and the other is
named as part of a substituent bonded to that chain:
• Name the simpler alkyl group as an alkoxy substituent by
changing the -yl ending of the alkyl group to -oxy.
• Name the remaining alkyl group as an alkane, with the
alkoxy group as a substituent bonded to this chain.

• Cyclic ethers have an O atom in

the ring. A common example is
tetrahydrofuran (THF).
 Naming Epoxides
• Epoxides can be named in three different ways—
epoxyalkanes, oxiranes, or alkene oxides.
• To name an epoxide as an epoxyalkane, first name the alkane
chain or ring to which the O atom is attached, and use the
prefix “epoxy” to name the epoxide as a substituent.
• Use two numbers to designate the location of the atoms to
which the O is bonded.
 Naming Epoxides as Oxiranes

• Epoxides bonded to a chain of carbon atoms can also be

named as derivatives of oxirane, the simplest epoxide having
two carbons and one oxygen atom in a ring.
• The oxirane ring is numbered to put the O atom at position
one, and the first substituent at position two.
• No number is used for a substituent in a monosubstituted
oxirane.
 Naming Epoxides as Alkene Oxides
• Epoxides are also named as alkene oxides, since they are
often prepared by adding an O atom to an alkene. To name
an epoxide in this way:
• Mentally replace the epoxide oxygen with a double
bond.
• Name the alkene.
• Add the word oxide.
Diethyl ether
Enflurane

Divinyl ether
Kyoto Pharmaceutical University
Brevetoxin
Dimethyl ether
MTBE is being used as an O-containing additive
in gasoline to reduce engine knock.
Crown Ethers
 Use of Crown Ethers
• The ability of crown ethers to complex cations can be exploited in
nucleophilic substitution reactions.
• As the complexed cation goes into solution it carries the anion
with it to maintain neutrality.
• The relatively unsolvated anion is extremely nucleophilic.
Polyethylene Glycol
Classification :
•Ethers – may be either:

symmetrical – groups on either side of O are

identical; may be dialkyl or diaryl ethers; named
as di+(alkyl)+ ether or di+(aryl)+ether.
unsymmetrical – groups on either side of O are not
identical; may be named by specifying the groups
ending in (__yl) in alphabetical order + ether

HO
O O
OCH3
tert-butyl methyl ether 3-methoxyhexane 2-ethoxyethanol
(MTBE)
a gasoline additive
Epoxides – the parent ring is called the oxirane ring
and is numbered as follows:

- epoxides may also be named as oxide

derivatives of the alkenes from which they are
derived.
Physical Properties:
• properties are due to a weak residual
dipole moment. Ethers and epoxides are
weakly polar compounds.
• Solubility in water – similar to alcohols due to
H-bonding

example: CH3CH2OCH2CH3 soluble to about

CH3CH2CH2CH2OH 8 g/100g H2O
 Preparation of Alcohols and Ethers

• Alcohols and ethers are both common products of nucleophilic

substitution.

• The preparation of ethers by the method shown in the last two

equations is called the Williamson ether synthesis.
 Williamson Ether Synthesis
• In theory, unsymmetrical ethers can be synthesized in two
different ways.
• In practice, one path is usually preferred.
• The path involving alkoxide attack on a less hindered alkyl halide
is preferred.
 Preparation of Alkoxides
• An alkoxide salt is needed to make an ether.
• Alkoxides can be prepared from alcohols by a Brønsted–Lowry
acid–base reaction. 0
• For example, sodium ethoxide (NaOCH2CH3) is prepared by
treating ethanol with NaH.

• NaH is an especially good base for forming alkoxide because the

by-product of the reaction, H2, is a gas that just bubbles out of the
reaction mixture.
 Forming Epoxides from Halohydrins
• Organic compounds that contain both a hydroxy group and a
halogen atom on adjacent carbons are called halohydrins.
• In halohydrins, an intramolecular version of the Williamson ether
synthesis can occur to form epoxides.
Preparation of Ethers:
- the major preparation reaction is called the
Williamson Ether Synthesis  an SN2 reaction
between an alkyl halide and an alkoxide or
phenoxide

CAUTION: The Williamson Reaction does

not work for 3° alkyl halides and aryl halides
IMPORTANT: In choosing reactants for the
preparation of unsymmetrical ethers, always
choose the less substituted alkyl halide as one of
the substrates:
In the following examples, indicate which
will be the more productive reaction:
Preparation of Epoxides:
Epoxides may be generated from
halohydrins as shown below:

- the reaction is reversible; HO- generates a small

amount of alkoxide which then functions as an
internal nucleophile.
Reactions of Ethers:
Ethers are relatively unreactive compounds.
- They are stable toward bases, oxidizing
agents and reducing agents  they undergo
cleavage reactions only in the presence of strong
acids at high temperature.
General equation:

Mechanism:
Reactions of Epoxides:
A. acid – catalyzed cleavage – the reaction
proceeds with anti-addition; the nucleophile
attacks on the more substituted carbon of the
oxirane ring (SN1-like). A difunctional product
is formed.
B. base – catalyzed cleavage – a special reaction of
epoxides that is not undergone by ethers; the
nucleophile attacks on the less substituted
carbon of the oxirane ring (SN2). A difunctional
product is formed.
ANALYSIS OF ETHERS:
1. solubility in cold concentrated sulfuric
acid
2. (-) results with warm KMnO4 and
chromic acid tests
3. (-) results with Na test
4. Spectroscopic analysis:
IR: 1200 – 1250 cm-1 due to C-O stretch
1H NMR: 3.3 – 4.0 ppm due to H-C-O
13C NMR: 60 - 75 ppm for sp3 C-O