CHM 121

ETHERS
 DR. A. F. ADEYEMI
DEPARTMENT OF CHEMISRY,
UNIVERSITY OF MEDICAL
SCIENCES,
ONDO-CITY, NIGERIA
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 OUTLINE

• Structure
• Nomenclature
• Physical Properties
• Chemical Properties
• Preparations
• Applications

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 Structure
• Ethers are compounds having two alkyl or aryl groups bonded
to an oxygen atom.
• Their general formula is R–O–R’.
• Ethers are similar in structure to alcohols, and both ethers
and alcohols are similar in structure to water.
In an alcohol one hydrogen atom of a water molecule is replaced by
an alkyl group, whereas in an ether both hydrogen atoms are
replaced by alkyl or aryl groups.
Ethers do have nonbonding electron pairs on their oxygen atoms

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 Nomenclature
A. Common names
• Common names of ethers simply give the names of the two alkyl
groups bonded to oxygen and add the word ether.
• Name each of the two carbon groups as a separate word followed by a
space and the word ether.
• Name the alkyl groups in alphabetical order e.g. t-butyl methyl
ether
• If just one alkyl group is described in the name, it implies two
identical groups, as in ethyl ether for diethyl ether.
• Examples: CH3-CH2-O-CH3 ethyl methyl ether
CH3CH2OCH2CH3 diethyl ether
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 Nomenclature (cont’d)
B. IUPAC names
• The ether functional group does not have a characteristic IUPAC
nomenclature suffix, so it is necessary to designate it as a
substituent.
• The smaller, shorter alkyl group becomes the alkoxy substituent,
while the larger, longer alkyl group side becomes the alkane base
(parent) name.
• Each alkyl group on each side of the oxygen is numbered
separately. The numbering priority is given to the carbon closest
to the oxygen.
• The alkoxy side (shorter side) has an "-oxy" ending with its
corresponding alkyl group.
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 Nomenclature (cont’d)

Alkyl
Name   Alkoxy Group Name
Group
CH3– Methyl   CH3O– Methoxy
CH3CH2– Ethyl   CH3CH2O– Ethoxy
(CH3)2CH– Isopropyl   (CH3)2CHO– Isopropoxy
(CH3)3C– tert-Butyl   (CH3)3CO– tert-Butoxy
C6H5– Phenyl   C6H5O– Phenoxy
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 Nomenclature (cont’d)
Examples
CH3-CH2-O-CH3 methoxyethane

CH3CH2CH2CH2CH2-O-CH2CH2CH3 1-propoxypentane.

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 Exercise 
Give the structure of each of the following compounds:
1. ethoxyethane
2. methoxyethane
3. 2-methoxy-2-methylpropane
4. Phenoxybenzene
5. 2-pentyl 1-propyl ether

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 Physical Properties
• At room temperature, ethers are pleasant-smelling
colourless liquids.
• Relative to alcohols, ethers are generally less dense, are
less soluble in water, and have lower boiling points.
Because ether molecules cannot engage in hydrogen bonding with each other,
they have much lower boiling points than do alcohols with similar molecular
weights.
For example, the boiling point of diethyl ether (C4H10O,  [M.Wt = 74]) is 35°C
(95°F), but the boiling point of 1-butanol (or n-butyl alcohol; C4H10O, M.Wt = 74)
is 118°C (244°F).
In fact, the boiling points of ethers are much closer to those of alkanes with
similar molecular weights; the boiling point of pentane (C5H12, M.Wt = 72) is
36°C (97°F), close to the boiling point of diethyl ether.
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 Physical Properties (cont’d)
• Ethers do have nonbonding electron pairs on their oxygen
atoms and they can, therefore, form hydrogen bonds with
other molecules (alcohols, amines, etc.) that have O―H or
N―H bonds.

The ability to form hydrogen bonds with other compounds makes

ethers particularly good solvents for a wide variety of organic
compounds and a surprisingly large number of inorganic
compounds.

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 Chemical Properties
• Ethers have relatively low chemical reactivity, but they are still
more reactive than alkanes
• They do not react with bases, active metals, dilute acids,
oxidising agents, and reducing agents
1. Ether cleavage
• Although ethers resist hydrolysis, their polar bonds are cloven
by mineral acids such as hydrobromic acid (HBr) and hydroiodic
acid (HI). Hydrogen chloride (HCl) cleaves ethers only slowly.
Methyl ethers typically afford methyl halides:
ROCH3 + HBr → CH3Br + ROH
• Some ethers undergo rapid cleavage with boron tribromide
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 Chemical Properties (cont’d)
2. Peroxide formation
• When stored in the presence of air or oxygen, ethers tend to
form explosive peroxides, such as diethyl ether peroxide. The
reaction is accelerated by light, metal catalysts, and aldehydes.
3. Lewis bases (and Bronsted bases)
• Ethers serve as Lewis bases and Bronsted bases. Strong acids
protonate the oxygen to give "oxonium ions". For instance,
diethyl ether forms a complex with boron trifluoride, i.e.
diethyl etherate (BF3·OEt2). Ethers also coordinate to the
Mg(II) center in Grignard reagents.
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 Preparations
• Ethers can be prepared by numerous routes. In general alkyl
ethers form more readily than aryl ethers, with the later
species often requiring metal catalysts
1. Dehydration of alcohols
2 R–OH → R–O–R + H2O at temperature of about 140oC

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 Preparations (cont’d)
2. Williamson ether synthesis
• Nucleophilic displacement of alkyl halides by alkoxides
R–ONa + R′–X → R–O–R′ + NaX
• It involves treatment of a parent alcohol with a strong
base to form the alkoxide, followed by addition of an
appropriate aliphatic compound bearing a suitable leaving
group (R–X).
Suitable leaving groups (X) include iodide, bromide, or
sulfonates. This method usually does not work well for aryl
halides (e.g. bromobenzene)
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 Applications
• Ethers are also important in medicine and pharmacology, especially for use
as anesthetics. For example, diethyl ether (CH CH ―O―CH CH ), was first used
3 2 2 3

as a surgical anesthetic in 1842. Codeine, a potent pain-relieving drug, is

the methyl ether of morphine. Because ether is highly flammable, it has
largely been replaced by less-flammable anesthetics, including nitrous
oxide (N O) and halothane (CF ―CHClBr).
2 3

• Diethyl ether is an excellent solvent for extractions and for a wide variety of

chemical reactions. It is also used as a volatile starting fluid for diesel
engines and gasoline engines in cold weather. 
• Dimethyl ether is used as a spray propellant and refrigerant.
• Methyl t-butyl ether (MTBE) is a gasoline additive that boosts the octane
number and reduces the amount of nitrogen-oxide pollutants in the exhaust.
• The ethers of ethylene glycol are used as solvents and plasticizers.

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