Nomenclature of Ethers

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Ethers are compounds having two alkyl or aryl groups bonded to an oxygen atom, as in the formula R1OR2. The ether functional group does not have a characteristic
IUPAC nomenclature suffix, so it is necessary to designate it as a substituent. To do so the common alkoxy substituents are given names derived from their alkyl
component (below):

Alkyl Group Name Alkoxy Group Name

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

Ethers can be named by naming each of the two carbon groups as a separate word followed by a space and the word ether. The -OR group can also be named as a
substituent using the group name, alkox

Example

CH3-CH2-O-CH3 is called ethyl methyl ether or methoxyethane.

The smaller, shorter alkyl group becomes the alkoxy substituent. The larger, longer alkyl group side becomes the alkane base name. Each alkyl group on each side of
the oxygen is numbered separately. The numbering priority is given to the carbon closest to the oxgen. The alkoxy side (shorter side) has an "-oxy" ending with its
corresponding alkyl group. For example, CH3CH2CH2CH2CH2-O-CH2CH2CH3 is 1-propoxypentane. If there is cis or trans stereochemistry, the same rule still applies.

Examples

CH3CH2OCH2CH3CH3CH2OCH2CH3, diethyl ether (sometimes referred to as just ether)

CH3OCH2CH2OCH3CH3OCH2CH2OCH3, ethylene glycol dimethyl ether (glyme).
Exercises

Try to name the following compounds using these conventions:

Try to draw structures for the following compounds:

2-pentyl 1-propyl ether J

1-(2-propoxy)cyclopentene J

Common names
Simple ethers are given common names in which the alkyl groups bonded to the oxygen are named in alphabetical order followed by the word "ether". The top left
example shows the common name in blue under the IUPAC name. Many simple ethers are symmetrical, in that the two alkyl substituents are the same. These are
named as "dialkyl ethers".

anisole (try naming anisole by the other two conventions. J )

oxirane
 1,2-epoxyethane, ethylene oxide, dimethylene oxide, oxacyclopropane,

furan (this compound is aromatic)

tetrahydrofuran

oxacyclopentane, 1,4-epoxybutane, tetramethylene oxide,

dioxane

1,4-dioxacyclohexane

Exercise

Try to draw structures for the following compounds-

3-bromoanisole J
2-methyloxirane J
3-ethylfuran J

Heterocycles
In cyclic ethers (heterocycles), one or more carbons are replaced with oxygen. Often, it's called heteroatoms, when carbon is replaced by an oxygen or any atom other
than carbon or hydrogen. In this case, the stem is called the oxacycloalkane, where the prefix "oxa-" is an indicator of the replacement of the carbon by an oxygen in
the ring. These compounds are numbered starting at the oxygen and continues around the ring. For example,

If a substituent is an alcohol, the alcohol has higher priority. However, if a substituent is a halide, ether has higher priority. If there is both an alcohol group and a
halide, alcohol has higher priority. The numbering begins with the end that is closest to the higher priority substituent. There are ethers that are contain multiple ether
groups that are called cyclic polyethers or crown ethers. These are also named using the IUPAC system.
 Sulfides
Sulfur analogs of ethers (RSR') are called sulfides, e.g., (CH3)3CSCH3 is tert-butyl methyl sulfide. Sulfides are chemically more reactive than ethers, reflecting
the greater nucleophilicity of sulfur relative to oxygen.

References
1. Schore, Neil E. and Vollhardt, K. Peter C. Organic Chemistry: Structure and Function.
New York: Bleyer, Brennan, 2007.
2. Winter, Arthur. Organic Chemistry for Dummies. Hoboken, New Jersey: Wiley, 2005.
3. Pellegrini, Frank. Cliffs QuickReview Organic Chemistry II. Foster City, CA: Wiley,
2000

Problems
Name the following ethers:

(Answers to problems above: 1. diethyl ether; 2. 2-ethoxy-2-methyl-1-propane; 3. cis-1-ethoxy-2-methoxycyclopentane; 4. 1-ethoxy-1-

methylcyclohexane; 5. oxacyclopropane; 6. 2,2-Dimethyloxacyclopropane)

Contributors
William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook
of Organic Chemistry
Richard Banks (Boise State University)
1.

Physical Properties of Ether

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Dimethylether and ethyl methyl ether are gases at ordinary temperature. The other lower homologues are colorless, pleasant smelling, volatile liquids with typical
ether smell.

Boiling points
The C - O bonds in ether are polar and thus ethers have a net dipole moment. The weak polarity of ethers do not appreciably affect their boiling points which are
comparable to those of the alkenes of comparable molecular mass. Ethers have much lower boiling points as compared to isomeric alcohols. This is because alcohols
molecules are associated by hydrogen bonds while ether molecules are not.

Solubility
Ethers containing upto 3 carbon atoms are soluble in water, due to their hydrogen bond formation with water molecules.

The solubility decreases with increase in the number of carbon atoms. The relative increase in the hydrocarbon portion of the molecule decreases the tendency of H-
bond formation. Ethers are appreciably soluble in organic solvents like alcohol, benzene, acetone etc.

Reactivity of Ethers
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Ethers are widely used as solvents for a variety of organic compounds and reactions, suggesting that they are relatively unreactive themselves. Indeed, with the
exception of the alkanes, cycloalkanes and fluorocarbons, ethers are probably the least reactive, common class of organic compounds. The inert nature of the ethers
relative to the alcohols is undoubtedly due to the absence of the reactive OH bond.

Cleaving Ethers
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The most common reaction of ethers is cleavage of the CO bond by strong acids. This may occur by SN1 or E1 mechanisms for 3-alkyl groups or by an SN2
mechanism for 1-alkyl groups. Some examples are shown in the following diagram. The conjugate acid of the ether is an intermediate in all these reactions, just as
conjugate acids were intermediates in certain alcohol reactions.
 The first two reactions proceed by a sequence of SN2 steps in which the iodide or bromide anion displaces an alcohol in the first step, and then converts the conjugate
acid of that alcohol to an alkyl halide in the second. Since SN2 reactions are favored at least hindered sites, the methyl group in example #1 is cleaved first. The 2-
alkyl group in example #3 is probably cleaved by an SN2 mechanism, but the SN1 alternative cannot be ruled out. The phenol formed in this reaction does not react
further, since SN2, SN1 and E1 reactions do not take place on aromatic rings. The last example shows the cleavage of a 3-alkyl group by a strong acid. Acids having
poorly nucleophilic conjugate bases are often chosen for this purpose so that E1 products are favored. The reaction shown here (#4) is the reverse of the tert-butyl
ether preparation described earlier.

Ethers in which oxygen is bonded to 1- and 2-alkyl groups are subject to peroxide formation in the presence of air (gaseous oxygen). This reaction presents an
additional hazard to the use of these flammable solvents, since peroxides decompose explosively when heated or struck. The mechanism of peroxide formation is
believed to be free radical in nature (note that molecular oxygen has two unpaired electrons).

ROCH(CH3)2+O2ROC(CH3)2OOHa peroxideROCH(CH3)2+O2ROC(CH3)2OOHa peroxide

Ethers as Protective Groups

Because of their chemical stability, ethers may be used to protect hydroxyl functions from undergoing unwanted reactions.

Reactions of Epoxides
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Epoxides (oxiranes) are three-membered cyclic ethers that are easily prepared from alkenes by reaction with peracids. Because of the large angle strain in this small
ring, epoxides undergo acid and base-catalyzed CO bond cleavage more easily than do larger ring ethers. Among the following examples, the first is unexceptional
except for the fact that it occurs under milder conditions and more rapidly than other ether cleavages. The second and third examples clearly show the exceptional
reactivity of epoxides, since unstrained ethers present in the same reactant or as solvent do not react. The aqueous acid used to work up the third reaction, following
the Grignard reagent cleavage of the ethylene oxide, simply neutralizes the magnesium salt of the alcohol product.
 Sulfur Analogs of Alcohols and Ethers
Sulfur is below oxygen in the periodic table. To see examples of organosulfur compounds and their chemistry Click Here

Alkoxy- mercuration of an Alkene

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The alkoxymercuration reaction is similar to oxymercuration reaction, except alcohol is used instead of water.

Reactions #3 and #4 are examples of this two-step procedure. Note that the alcohol reactant is used as the solvent, and a trifluoroacetate mercury (II) salt is used in
preference to the acetate (trifluoroacetate anion is a poorer nucleophile than acetate). The mechanism of alkoxymercuration is similar to that of oxymercuration, with
an initial anti-addition of the mercuric species and alcohol being followed by reductive demercuration.

Dehydration of Alcohols to Make Ethers

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Acid-catalyzed dehydration of small 1-alcohols constitutes a specialized method of preparing symmetrical ethers.

Introduction
As shown in the following two equations, the success of this procedure depends on the temperature. At 110 to 130 C an S N2 reaction of the alcohol conjugate acid
leads to an ether product. At higher temperatures (over 150 C) an E2 elimination takes place.

2 CH3CH2-OH + H2SO4 130 C CH3CH2-O-CH2CH3 + H2O

CH3CH2-OH + H2SO4 150 C CH2=CH2 + H2O

In this reaction alcohol has to be used in excess and the temperature has to be maintained around 413 K. If alcohol is not used in excess or the temperature is higher,
the alcohol will preferably undergo dehydration to yield alkene.

If ethanol is dehydrated to ethene in presence of sulfuric acid at 433 K, but as 410 K, ethoxyethane is the main product. The dehydration of secondary and tertiary
alcohols to get corresponding ethers is unsuccessful as alkenes are formed easily in these reactions.

This reaction cannot be employed to prepare unsymmetrical ethers. It is because a mixture of products is likely to be obtained.

Ether Synthesis
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Ethers are usually prepared from alcohols or their conjugate bases. One important procedure, known as the Williamson Ether Synthesis, proceeds by an SN2 reaction
of an alkoxide nucleophile with an alkyl halide. Reactions #1 and #2 below are two examples of this procedure. When applied to an unsymmetrical ether, as in this
case, there are two different combinations of reactants are possible. Of these one is usually better than the other. Since alkoxide anions are strong bases, the possibility
of a competing E2 elimination must always be considered. Bearing in mind the factors that favor substitution over elimination, a 1-alkyl halide should be selected as a
preferred reactant whenever possible. Thus, reaction #1 gives a better and cleaner yield of benzyl isopropyl ether than does reaction #2, which generates considerable
elimination product.

A second general ether synthesis, alkoxymercuration, is patterned after the oxymercuration reaction. Reactions #3 and #4 are examples of this two-step procedure.
Note that the alcohol reactant is used as the solvent, and a trifluoroacetate mercury (II) salt is used in preference to the acetate (trifluoroacetate anion is a poorer
nucleophile than acetate). The mechanism of alkoxymercuration is similar to that of oxymercuration, with an initial anti-addition of the mercuric species and alcohol
being followed by reductive demercuration.

Acid-catalyzed dehydration of small 1-alcohols constitutes a specialized method of preparing symmetrical ethers. As shown in the following two equations, the
success of this procedure depends on the temperature. At 110 to 130 C an S N2 reaction of the alcohol conjugate acid leads to an ether product. At higher temperatures
(over 150 C) an E2 elimination takes place.

2 CH3CH2-OH + H2SO4 130 C CH3CH2-O-CH2CH3 + H2O

CH3CH2-OH + H2SO4 150 C CH2=CH2 + H2O

Making Epoxyethane from Ethene

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This page looks at the manufacture of epoxyethane from ethene, and then at some of the products that are made from epoxyethane.

The manufacture of epoxyethane

Conditions

Temperature: about 250 - 300C

Pressure: about 15 atmospheres

Catalyst: silver

Problems and hazards during manufacture

The main problem comes in controlling the temperature. The reaction is exothermic and so the temperature will tend to rise unless it is carefully controlled. At higher
temperatures the ethene burns in the oxygen to produce carbon dioxide and water which means that the temperature would increase even more - and the whole thing get
completely out of hand! Two hazards during manufacture come from the nature of epoxyethane. It is

poisonous and carcinogenic (cancer producing);

highly flammable or explosive in contact with air.

The reactivity of epoxyethane

Ring strain
The reason that epoxyethane is so reactive is that bonding pairs in the ring of atoms in the molecule are forced very close together. The bond angles are about 60 rather than
about 109.5 when carbon atoms normally form single bonds.

The overlap between the atomic orbitals in forming the carbon-carbon and carbon-oxygen bonds is less good than it is normally, and there is considerable repulsion between
the bonding pairs. The system becomes more stable if the ring is broken. When epoxyethane reacts a carbon-oxygen bond is always broken and the ring opens up.
IUPAC system and IUPAC rules of naming ethers
Common names of ethers follow after the names of alkyl / aryl groups written as separate words
in alphabetical order. The word ether is added at the end.
In case of simple ethers, the prefix di is attached before the name of the alkyl group.
Examples:
C2H5 - O - C2H5 is Diethyl ether
C6H5 - O - C6H5 is Diphenyl ether
C2H5 - O - C6H5 is Dthyl phenyl ether.
According to the IUPAC nomenclature ethers are regarded as hydrocarbon derivatives in which
a hydrogen atom is replaced by an alkoxy group - OR, the larger group (R) being chosen as the
parent hydrocarbon. Ethers are named as alkoxyalkenes. The larger alkyl group forms the part
of parent chain while lower alkyl group constitutes the alkoxy radical.
Examples:

The numbering of the parent chain is done so that the carbon atom linked to the -O-atom gets
the lowest number.