Introduction to Ethers

James Richard Fromm

Two alcohol molecules will react under the proper conditions to

produce compounds with the general formula R-O-R'. These
compounds are called ETHERS. The other product of the reaction
is water which is taken up by a dehydration agent.

Simple ethers are prepared commercially by dehydration of the

corresponding alcohols by sulfuric acid:
• A typical reaction is:

• 2CH3-CH2-OH --H2SO4 --> CH3-CH2-O-CH2-CH3 + H2O

• also written:

• 2C2H5OH --H2SO4--> C2H5OC2H5 + H2O

• The ethers are named by naming the radical on either side of the oxygen atom, and
adding the word ether. The two side chains can be the same, of course, in which
case the name is mentioned just once, but preceded by the prefix di-. Thus, in the
preceding reaction, 2 moles of ethanol will react to form 1 mole of diethyl ether.
• Ethers may also be named as OXY DERIVATIVES of the hydrocarbons. In the
IUPAC nomenclature system, ethers are named using the general formula
"alkoxyalkane", for example
• CH3-CH2-O-CH3

• is methoxyethane.

• If the ether is part of a more complex molecule, it is described as an alkoxy

substituent, so -OCH3 would be considered a "methoxy-" group. The nomenclature
of describing the two alkyl groups and appending "ether", e.g. "ethylmethyl ether" is
a trivial usage.
• If the ether is part of a more complex
molecule, it is described as an alkoxy
substituent, so -OCH3 would be considered a
"methoxy-" group. The nomenclature of
describing the two alkyl groups and
appending "ether", e.g. "ethylmethyl ether" is
a trivial usage.
• The ether radicals for the first four alkanes are:

• CH3-O- Methoxy-
• CH3-CH2-O- Ethoxy-
• CH3-CH2-CH2-O- Propoxy-
• CH3-CH2-CH2-CH2-O- Butoxy-
• Another name for diethyl ether is ethoxyethane. Dimethyl ether is methoxymethane,
and methylheptyl ether is 1-methoxyheptane.

• CH3-O-CH3 CH3-O-CH2-CH2-CH2-CH2-CH2-CH2-CH3
• dimethyl ether methylheptyl ether
• The structural formula for 1,4-dimethoxy-2-pentene is
• Ch3-O-CH2-CH=CH-CH(CH3-O)-CH3
• Many ethers are used in industry as solvents. Diethyl ether has found
widespread use as an anesthetic since 1846, in which application it is
referred to simply as ether. It and other ethers are valuable solvents for
gums, fats, waxes, and resins.
• Ethers are highly flammable and have relatively high vapor pressures, so
they constitute a significant fire hazard. Moreover, on standing in air
many simple ethers react slowly with atmospheric oxygen to form
unstable and highly explosive organic peroxides, a significant hazard in
distillations which use ethers.
More complex ether structures are
prepared in multistep synthesis.
• Physical Properties
• Ether molecules cannot form hydrogen bonds among each other, resulting in a
relatively low boiling point comparable to that of the analogous
alcohols. However, the differences in the boiling points of the ethers and their
isometric alcohols become smaller as the carbon chains become longer, as the
hydrophobic nature of the carbon chain becomes more predominant over the
presence of hydrogen bonding.
• Ethers are slightly polar as the C - O - C bond angle in the functional group is
about 110 degrees, and the C - O dipole does not cancel out. Ethers are more
polar than alkenes but not as polar as alcohols, esters or amides of comparable
structure. However, the presence of two lone pairs of electrons on the oxygen
atoms makes hydrogen bonding with water molecules possible, causing the
solubility of alcohols (for instance, 1-butanol) and ethers (ethoxyethane) to be
quite dissimilar.
 Tetrahydrofuran
1,4 Dioxane

Ethers can act as Lewis bases. For instance,

diethyl ether forms a complex with boron
compounds, such as boron trifluoride diethyl
etherate (BF3.OEt2). Ethers also coordinate to
magnesium in Grignard reagents (RMgBr).
Similar Structures
• Organic Reactions
• Ethers can be prepared in the laboratory in several different ways.
• Intermolecular Dehydration of alchohols:
• R-OH + R'-OH rarrow.gif (63 bytes) R-O-R' + H2O
• This direct reaction requires drastic conditions (heating to 140oCelsius and an acid catalyst, usually
concentrated sulphuric acid). Effective for making symmetrical ethers, but not as useful for synthesising
asymmetrical ethers because the reaction will yield a mixture of ethers, making it usually not applicable:
• 3R-OH + 3R'-OH rarrow.gif (63 bytes) R-O-R + R'-O-R + R'-O-R' + 3H2O
• Conditions must also be controlled to avoid overheating to 170 degrees which will cause intramolecular
dehydration, a reaction that yields alkenes. In addition, the alcohol must be in excess.
• R-CH2-CH2(OH) rarrow.gif (63 bytes) R-CH=CH2 + H2O

• Such conditions can destroy the delicate structures of some functional groups. There exist several milder
methods to produce ethers.
• Nucleophilic Displacement of Alkyl halides by alkoxides
• R-O- + R-X rarrow.gif (63 bytes) R-O-R + X-