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Ether
Ethers (/ˈiːθər/) are a class of organic compounds that contain an ether group—an
oxy gen atom connected to two alky l or ary l groups. They hav e the general formula R–
O–R′, where R and R′ represent the alky l or ary l groups. Ethers can again be classified
into two v arieties: if the alky l groups are the same on both sides of the oxy gen atom,
then it is a simple or sy mmetrical ether, whereas if they are different, the ethers are
The general structure of
called mixed or unsy mmetrical ethers. [1] A ty pical example of the first group is the an ether. R and R'
solv ent and anesthetic diethy l ether, commonly referred to simply as "ether" represent any alkyl or
(CH3 –CH2 –O–CH2 –CH3 ). Ethers are common in organic chemistry and ev en more aryl substituent.
prev alent in biochemistry , as they are common linkages in carbohy drates and lignin.

Contents
Structure and bonding
Nomenclature
Trivial name
Polyethers
Related compounds
Physical properties
Reactions
Ether cleavage
Peroxide formation
Lewis bases
Alpha-halogenation
Synthesis
Dehydration of alcohols
Williamson ether synthesis
Ullmann condensation
Electrophilic addition of alcohols to alkenes
Preparation of epoxides
Important ethers
References
External links

Structure and bonding

Ethers feature C–O–C linkage defined by a bond angle of about 110° and C–O distances of about 140 pm. The barrier
to rotation about the C–O bonds is low. The bonding of oxy gen in ethers, alcohols, and water is similar. In the
language of v alence bond theory , the hy bridization at oxy gen is sp3 .

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Oxy gen is more electronegativ e than carbon, thus the hy drogens alpha to ethers are more acidic than in simple
hy drocarbons. They are far less acidic than hy drogens alpha to carbony l groups (such as in ketones or aldehy des),
howev er.

Depending on the groups at R and R′, ethers are classified into two types:

1. Simple ethers or symmetrical ethers; e.g., diethyl ether, dimethyl ether, etc.
2. Mixed ethers or unsymmetrical ethers; e.g., methyl ethyl ether, methyl phenyl ether, etc.

Nomenclature
In the IUPAC nomenclature sy stem, ethers are named using the general formula "alkoxyalkane", for example CH3 –
CH2 –O–CH3 is methoxy ethane. 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 simpler alky l radical is written in front, so CH3 –
O–CH2 CH3 would be giv en as methoxy(CH3 O)ethane(CH2 CH3 ).

Trivial name
IUPAC rules are often not followed for simple ethers. The triv ial names for simple ethers (i.e., those with none or few
other functional groups) are a composite of the two substituents followed by "ether". For example, ethy l methy l
ether (CH3 OC2 H5 ), dipheny lether (C6 H5 OC6 H5 ). As for other organic compounds, v ery common ethers acquired
names before rules for nomenclature were formalized. Diethy l ether is simply called "ether", but was once called
sweet oil of vitriol. Methy l pheny l ether is anisole, because it was originally found in aniseed. The aromatic ethers
include furans. Acetals (α-alkoxy ethers R–CH(–OR)–O–R) are another class of ethers with characteristic properties.

Polyethers
Poly ethers are compounds with more than one ether group.

The crown ethers are examples of small poly ethers. Some toxins produced by dinoflagellates such as brev etoxin and
ciguatoxin are extremely large and are known as cyclic or ladder poly ethers.

Poly ether generally refers to poly mers which contain the ether functional group in their main chain. The term gly col
is reserv ed for low to medium range molar mass poly mer when the nature of the end-group, which is usually a
hy droxy l group, still matters. The term "oxide" or other terms are used for high molar mass poly mer when end-
groups no longer affect poly mer properties.

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Aliphatic polyethers

Name of the Examples

Name of the polymers with
polymers with high Preparation Repeating unit of trade
low to medium molar mass
molar mass names

Polyoxymethylene Step-growth
Delrin from
Paraformaldehyde (POM) or polyacetal or polymerisation of –CH2O–
DuPont
polyformaldehyde formaldehyde

Polyethylene oxide Ring-opening

Carbowax
Polyethylene glycol (PEG) (PEO) or polymerization of –CH2CH2O–
from Dow
polyoxyethylene (POE) ethylene oxide

Polypropylene oxide
Anionic ring-opening
(PPOX) or
Polypropylene glycol (PPG) polymerization of –CH2CH(CH3)O–
polyoxypropylene
propylene oxide
(POP)

Terathane
from
Polytetramethylene glycol Acid-catalyzed ring-
Polytetrahydrofuran Invista and
(PTMG) or Polytetramethylene opening polymerization –CH2CH2CH2CH2O–
(PTHF) PolyTHF
ether glycol (PTMEG) of tetrahydrofuran
from
BASF

The pheny l ether poly mers are a class of aromatic poly ethers containing aromatic cy cles in their main chain:
Poly pheny l ether (PPE) and Poly (p-pheny lene oxide) (PPO).

Related compounds
Many classes of compounds with C–O–C linkages are not considered ethers: Esters (R–C(=O)–O–R′), hemiacetals (R–
CH(–OH)–O–R′), carboxy lic acid anhy drides (RC(=O)–O–C(=O)R′).

Physical properties
Ether molecules cannot form hy drogen bonds with each other, resulting in relativ ely low boiling points compared to
those of the analogous alcohols. The difference in the boiling points of the ethers and their isomeric alcohols
becomes lower as the carbon chains become longer, as the v an der Waals interactions of the extended carbon chain
dominates ov er the presence of hy drogen bonding.

Ethers are slightly polar. The C–O–C bond angle in the functional group is about 110°, and the C–O dipoles do not
cancel out. Ethers are more polar than alkenes but not as polar as alcohols, esters, or amides of comparable
structure. The presence of two lone pairs of electrons on the oxy gen atoms makes hy drogen bonding with water
molecules possible.

Cy clic ethers such as tetrahy drofuran and 1,4-dioxane are miscible in water because of the more exposed oxy gen
atom for hy drogen bonding as compared to linear aliphatic ethers.

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Selected data about some alkyl ethers

Ether Structure m.p. (°C) b.p. (°C) Solubility in 1 liter of H2O Dipole moment (D)

Dimethyl ether CH3–O–CH3 −138.5 −23.0 70 g 1.30

Diethyl ether CH3CH2–O–CH2CH3 −116.3 34.4 69 g 1.14

Tetrahydrofuran O(CH2)4 −108.4 66.0 Miscible 1.74

Dioxane O(C2H4)2O 11.8 101.3 Miscible 0.45

Other properties are:

The lower ethers are highly volatile and flammable.

Lower ethers also act as anaesthetics.
Ethers are good organic solvents.
Simple ethers (such as diethyl ether) are tasteless.

Reactions
Ethers are quite stable chemical compounds which do not react with bases,
activ e metals, dilute acids, oxidising agents, and reducing agents. Generally ,
they are of low chemical reactiv ity , but they are more reactiv e than alkanes.
Epoxides, ketals, and acetals are unrepresentativ e classes of ethers and are
discussed in separate articles. Important reactions are listed below. [2]
Structure of the polymeric diethyl
ether peroxide
Ether cleavage
Although ethers resist hy droly sis, their polar bonds are clov en by mineral acids such as hy drobromic acid and
hy droiodic acid. Hy drogen chloride cleav es ethers only slowly . Methy l ethers ty pically afford methy l halides:

ROCH3 + HBr → CH3Br + ROH

These reactions proceed v ia onium intermediates, i.e. [RO(H)CH3 ]+ Br − .

Some ethers undergo rapid cleav age with boron tribromide (ev en aluminium chloride is used in some cases) to giv e
the alky l bromide. [3] Depending on the substituents, some ethers can be clov en with a v ariety of reagents, e.g. strong
base.

Peroxide formation
When stored in the presence of air or oxy gen, ethers tend to form explosiv e peroxides, such as diethy l ether
peroxide. The reaction is accelerated by light, metal cataly sts, and aldehy des. In addition to av oiding storage
conditions likely to form peroxides, it is recommended, when an ether is used as a solv ent, not to distill it to dry ness,
as any peroxides that may hav e formed, being less v olatile than the original ether, will become concentrated in the
last few drops of liquid. The presence of peroxide in old samples of ethers may be detected by shaking them with
freshly prepared solution of a FeSO4 followed by addition of KCN. Appearance of blood red color indicates presence
of peroxides.

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Lewis bases
Ethers serv e as Lewis bases and Bronsted bases. Strong acids protonate the oxy gen to giv e "oxonium ions". For
instance, diethy l ether forms a complex with boron trifluoride, i.e. diethy l etherate (BF3 ·OEt2 ). Ethers also
coordinate to the Mg(II) center in Grignard reagents.

Alpha-halogenation
This reactiv ity is similar to the tendency of ethers with alpha hy drogen atoms to form peroxides. Reaction with
chlorine produces alpha-chloroethers.

Synthesis
Ethers can be prepared in the laboratory in sev eral different way s.

Dehydration of alcohols
The dehy dration of alcohols affords ethers:

2 R–OH → R–O–R + H2O at high temperature

[4] This direct nucleophilic substitution reaction requires elev ated temperatures (about 125 °C). The reaction is
cataly zed by acids, usually sulfuric acid. The method is effectiv e for generating sy mmetrical ethers, but not
unsy mmetrical ethers, since either OH can be protonated, which would giv e a mixture of products. Diethy l ether is
produced from ethanol by this method. Cy clic ethers are readily generated by this approach. Elimination reactions
compete with dehy dration of the alcohol:

R–CH2–CH2(OH) → R–CH=CH2 + H2O

The dehy dration route often requires conditions incompatible with delicate molecules. Sev eral milder methods exist
to produce ethers.

Williamson ether synthesis

Nucleophilic displacement of alky l halides by alkoxides

R–ONa + R′–X → R–O–R′ + NaX

This reaction is called the Williamson ether sy nthesis. It inv olv es treatment of a parent alcohol with a strong base to
form the alkoxide, followed by addition of an appropriate aliphatic compound bearing a suitable leav ing group (R–
X). Suitable leav ing groups (X) include iodide, bromide, or sulfonates. This method usually does not work well for

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ary l halides (e.g. bromobenzene, see Ullmann condensation below). Likewise, this method only giv es the best y ields
for primary halides. Secondary and tertiary halides are prone to undergo E2 elimination on exposure to the basic
alkoxide anion used in the reaction due to steric hindrance from the large alky l groups.

In a related reaction, alky l halides undergo nucleophilic displacement by phenoxides. The R–X cannot be used to
react with the alcohol. Howev er phenols can be used to replace the alcohol while maintaining the alky l halide. Since
phenols are acidic, they readily react with a strong base like sodium hy droxide to form phenoxide ions. The
phenoxide ion will then substitute the –X group in the alky l halide, forming an ether with an ary l group attached to it
in a reaction with an SN2 mechanism.

C6H5OH + OH− → C6H5–O− + H2O

C6H5–O− + R–X → C6H5OR

Ullmann condensation
The Ullmann condensation is similar to the Williamson method except that the substrate is an ary l halide. Such
reactions generally require a cataly st, such as copper.

Electrophilic addition of alcohols to alkenes

Alcohols add to electrophilically activ ated alkenes.

R2C=CR2 + R–OH → R2CH–C(–O–R)–R2

Acid cataly sis is required for this reaction. Often, mercury trifluoroacetate (Hg(OCOCF3 )2 ) is used as a cataly st for
the reaction generating an ether with Markov nikov regiochemistry . Using similar reactions, tetrahy dropy rany l
ethers are used as protectiv e groups for alcohols.

Preparation of epoxides
Epoxides are ty pically prepared by oxidation of alkenes. The most important epoxide in terms of industrial scale is
ethy lene oxide, which is produced by oxidation of ethy lene with oxy gen. Other epoxides are produced by one of two
routes:

By the oxidation of alkenes with a peroxyacid such as m-CPBA.

By the base intramolecular nucleophilic substitution of a halohydrin.

Important ethers

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Ethylene oxide Also the simplest epoxide.

An aerosol spray propellant. A potential renewable alternative fuel for

Dimethyl ether
diesel engines with a cetane rating as high as 56–57.

A common low boiling solvent (b.p. 34.6 °C) and an early anaesthetic.
Used as starting fluid for diesel engines. Also used as a refrigerant and
Diethyl ether
in the manufacture of smokeless gunpowder, along with use in
perfumery.

Dimethoxyethane
A high-boiling solvent (b.p. 85 °C):
(DME)

Dioxane A cyclic ether and high-boiling solvent (b.p. 101.1 °C).

Tetrahydrofuran A cyclic ether, one of the most polar simple ethers that is used as a
(THF) solvent.

Anisole An aryl ether and a major constituent of the essential oil of anise
(methoxybenzene) seed.

Crown ethers Cyclic polyethers that are used as phase transfer catalysts.

Polyethylene
A linear polyether, e.g. used in cosmetics and pharmaceuticals.
glycol (PEG)

References
1. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–)
"ethers (http://goldbook.iupac.org/E02221.html)".

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2. Wilhelm Heitmann, Günther Strehlke, Dieter Mayer "Ethers, Aliphatic" in Ullmann's Encyclopedia of Industrial
Chemistry Wiley-VCH, Weinheim, 2002. doi:10.1002/14356007.a10_023 (https://doi.org/10.1002%2F14356007.a10_02
3)
3. J. F. W. McOmie and D. E. West (1973). "3,3′-Dihydroxylbiphenyl" (http://www.orgsyn.org/demo.aspx?
prep=CV5P0412). Organic Syntheses.; Collective Volume, 5, p. 412
4. Clayden; Greeves; Warren (2001). Organic chemistry. Oxford University Press. p. 129. ISBN 978-0-19-850346-0.

External links
ILPI (http://www.ilpi.com/msds/ref/ether.html) page about ethers.
An Account of the Extraordinary Medicinal Fluid, called Aether (http://www.gutenberg.org/etext/12522), by M. Turner,
circa 1788, from Project Gutenberg

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