7.

2 Ethers

7.2.1 Nomenclature

7.2.2 Preparations /Reaction

7.2.3 Commercially Useful Ether

Ethers
What Are Ethers?
Ethers are a class of organic compounds that mostly contain an ether group wherein the oxygen
atom is bonded to two alkyl or aryl groups. The word Ether has been derived from the Latin
word ‘aether’ which means ‘to ignite’. At room temperature and under a high-pressure, ethers are
usually flammable. The general formula of ether is given as R-O-R, R-O-R’, R-O-Ar or Ar-O-Ar
where R represents an alkyl group and Ar represents an aryl group.

We generally come across this topic in organic chemistry, and it is also a widely covered topic in
biochemistry where we find common linkages between carbohydrates and lignin. Meanwhile, if
we look at the structure of ethers they basically feature bent C–O–C linkages.

The above figure represents the general structure of an ether. You can see that ether is mainly
characterised by an oxygen atom that is bonded to two alkyl or aryl groups, represented here by
R and R’. The substituents can be the same or different.

Examples Of Ethers
Below we have given a few ethers examples.
1. CH3 – O – CH3 (Dimethyl ether)

2. (CH3)2CH – O – CH(CH3)2 (Diisopropyl ether)

3. Cyclic ethers such as

C6H5 – O – C6H5 (Diphenyl ether)

Physical Properties of Ethers

Dimethyl ether and ethyl methyl ether are both gases at room temperature. Other lower
homologues are colourless, pleasant smelling, volatile liquids with a typical ether smell.

1) Dipole moment: C-O-C bond angle is not 180°, dipole moments of the two C-O bonds do not
cancel each other, and thus ethers possess a small net dipole moment.

2) Boiling point: The boiling points of ether molecules are comparable to that of alkanes but
they are very low compared to that of alcohols of comparable molecular mass. This is because of
the presence of hydrogen bonding in alcohol.

3) Solubility: The solubility of ethers with water resembles those of alcohols of comparable
molecular mass. Ether molecules are soluble in water. This is because of the fact that like
alcohol, oxygen atoms of ether can also form hydrogen bonds with a water molecule. Also,
solubility decreases with an increase in carbon atoms. This is because the relative increase in
hydrocarbon content of the molecule decreases the tendency of H-bond formation.
4) Polarity: Ether is less polar than esters, alcohols or amines because of the oxygen atom that is
unable to participate in hydrogen bonding due to the presence of bulky alkyl groups on both
sides of the oxygen atom. but ether is more polar than alkenes.

5) Hybridization: In ethers, the oxygen atom is sp3 hybridized with a bond angle of 109.50.

Classification of Ethers
Ethers can be classified into two broad categories based on the substituent group attached to its
oxygen atom: symmetrical ethers and asymmetrical (or unsymmetrical) ethers.

Symmetrical ethers are those ethers where two identical groups are attached to the oxygen atom

Example:

CH3 – CH2 – O – CH2 – CH3 (Diethyl ether)

Asymmetrical ethers are those where two different groups are attached to the oxygen atom.

Example:

CH3 – O – CH2 – CH3 (Ethyl methyl ether)

Their structure is similar to that of the structure of the alcohol. Interestingly, the structures of
both ether and alcohol are similar to the structure of water molecules. This is because, in alcohol,
one hydrogen atom of a water molecule is replaced by an alkyl group, and in the case of ethers
both hydrogen atoms of water molecules are replaced by an alkyl or aryl group.

Note: Ether does not possess a hydroxyl group, unlike alcohols and phenols.

Nomenclature of Ethers
Ethers are named simply by the names of two alkyl/aryl groups bonded to oxygen and add the
word ‘ether’. Those alkyl groups are listed in alphabetical order.

For example, t-butyl methyl ether, ethyl methyl ether

If only one alkyl/aryl group is shown in the name of a particular ether, it implies two identical
groups, as in ethyl ether for diethyl ether. Naming for ethers adopted by IUPAC uses a more
complex group as the root name, with the oxygen atom and the smaller group named as an
alkoxy substituent. Thus, in IUPAC systems, ethers are alkoxy alkanes.

Example: ethoxyethane (diethyl ether), methoxy ethane (methyl ethyl ether), 2-methoxy-2-
methylpropane (methyl tert-butyl ether), phenoxy benzene (diphenyl ether).

This IUPAC nomenclature is very useful for naming compounds with additional functional
groups because these functional groups can be described by the root name.

Rules for Naming the Ether Using IUPAC Name

Rule 1: Select the longest carbon chain as the base chain and give the base name.

Rule 2: Change the name of the other hydrocarbon group ends with ‘yl’ change into ‘oxy’.

Example: Methyl becomes methoxy and ethyl becomes an ethoxy group.

Rule 3: Alkoxy name is placed with a locator number in front of the base chain name.

Example:

1. CH3 – O – CH2 – CH2 – CH2 – CH3 (1 – Methoxybutane)

2. CH3 – CH (CH3) – CH2 – O – CH2 – CH3 ( 1- Ethoxy – 2- methylpropane)

Preparation Of Ethers
Ethers can be prepared or synthesized in a number of ways. The most common industrial
methods for preparing ethers are:

Dehydration of Alcohols
Alcohol undergoes dehydration in the presence of protic acids (sulphuric acid, phosphoric acid)
to produce alkenes and ethers under different conditions. The formation of the reaction product
depends on the reaction conditions.

For example, ethanol is dehydrated to ethene at 443K in the presence of sulphuric acid. On the
other hand, ethanol yields ethoxyethane in the presence of sulphuric acid at 413K.

The formation of ethers by dehydration of an alcohol is a nucleophilic bimolecular reaction. That

is, here the alcohol acts as a nucleophile which means it involves the attack of an alcohol
molecule on a protonated alcohol as shown below.

This method is used for the preparation of ethers having primary alkyl groups. To synthesize
ethers in this way, the alkyl group should be unhindered and must be kept at a low temperature
or else the reaction will give rise to alkenes.

Williamson Synthesis
This is an important method for the preparation of symmetrical and asymmetrical ethers in
laboratories. In Williamson synthesis, an alkyl halide is made to react with sodium alkoxide
which leads to the formation of ether.

Example:

This reaction involves an SN2 attack of an alkoxide ion on an alkyl halide. We know that
alkoxides are very strong bases and they react steadily with alkyl halides, and thus they take part
in elimination reactions.

In the case of primary alkyl halides, Williamson synthesis shows higher productivity.

Alkyl Halide with Dry Silver Oxide

When alkyl halide is treated with dry silver oxide, ether is produced

2C2H5Br + Ag2O → C2H5 – O – C2H5 + 2AgBr

Ether Chemical Reactions

Of all the functional groups, ethers are the least reactive ones. Ether bonds are quite stable
towards bases, oxidizing agents and reducing agents. But on the other hand, ethers undergo
cleavage by reaction with acids. The prominent chemical reactions of ethers are as follows;

Cleavage of C-o Bonds in Ethers

Cleavage of C-O bonds in ether takes place in excess hydrogen halide (which are acidic) under
extreme conditions like in concentrated acids (usually HBr and HI) and high temperatures.

For example, the reaction of dialkyl ether produces, initially, an alkyl halide and alcohol. This
alcohol further reacts with halide to form a second mole of alkyl halide and water.
Reactivity of RX: HI>HBr>HCl

It is known that the oxygen atom of ether is basic, similar to the oxygen atom of alcohol. Thus,
the initial reaction between ether and halide produces a protonated ether. The nucleophilic attack
of halide ion on this protonated ether leads to cleavage of C-O bond.

Formation of Peroxides
When ether is exposed to air in the presence of UV light or sunlight, peroxide linkage will be
formed.

Electrophilic Substitution Reaction

Aromatic ethers activate their aromatic ring towards electrophilic substitution reaction just like in
phenol because of the presence of alkoxy groups(-OR). This alkoxy group
is ortho and para directing. In the case of aryl ethers, the lone pair of oxygen is involved in
resonance with the benzene ring, and increases electron density in the ring at ortho and para
positions. This, in turn, facilitates the attack of electrophile at ortho and para positions.
Some of the different types of electrophilic substitution reactions include:

1) Halogenation
Alkyl groups undergo a substitution reaction with halides such as chlorine and bromine. This
reaction yields halogenated ether in the absence of sunlight. In the presence of sunlight, it
constitutes all the hydrogen atoms of ethers. In the benzene ring, phenyl alkyl ethers undergo
usual halogenation. Example: anisole undergoes bromination with bromine in ethanoic acid even
in the absence of iron (III) bromide catalyst. This occurs because of the activation of the benzene
ring by the methoxy group. Para isomer is obtained in 90% yield.

2) Nitration
The nitration of anisole is an electrophilic substitution reaction. Whenever anisole is nitrated
with a mixture of concentrated nitric (HNO3) and sulphuric (H2SO4) acids, it yields a mixture of
ortho-Nitroanisole and para-Nitroanisole (major).

3) Friedel-Crafts Reaction
These are a couple of reactions created by Charles Friedel and James Crafts in 1877 to attach
substituents to aromatic rings. These reactions are of two types:

 Friedel-Crafts Alkylation Reaction:

Friedel-Crafts alkylation involves the alkylation of anisole with alkyl chloride and anhydrous
aluminium chloride (a Lewis acid) as a catalyst.

 Friedel-Crafts Acylation:
This reaction involves the acylation of anisole with an acyl chloride in the presence of anhydrous
aluminium chloride as a catalyst.

Both these reactions follow the electrophilic substitution reaction. To be precise, in both these
reactions, the alkyl and acyl groups are introduced at ortho and para positions by reaction with an
alkyl halide and acyl halide in the presence of anhydrous aluminium chloride.

Some of the important ethers are:

  Ethylene oxide
 Dimethyl ether
 Diethyl ether
 Dimethoxyethane (DME)
 Dioxane
 Tetrahydrofuran (THF)
 Anisole (methoxybenzene)
 Crown ethers
 Polyethylene glycol (PEG)
 Polypropylene glycol
 Platelet-activating factor

Uses of Ether
 Dimethyl ether is used as a refrigerant and as a solvent at low temperatures.
 Diethyl ether is a common ingredient in anaesthesia used in surgeries.
 Ether is used along with petrol as a motor fuel.
 Diethyl ether is a common solvent for oils, gums, resins, etc.
 Phenyl ether can be used as a heat transfer medium because of its high boiling point.

Ether Functional Group

What is the Ether Functional Group?

The ether group consists of an oxygen atom with an R group single-bonded to each side. These R
groups can be the same, however, they are not always.
In an ether, the Oxygen must be bonded to carbon on both sides. If one of the R groups is a
Hydrogen atom, then the compound is an alcohol.

Quick Facts on the Ether Group

 Structure: An Oxygen single bonded to two alkyl groups.
 Formula: R-O-R’
 Atomic Weight: ≥46.07 g/mol
 pH: Generally basic. Ethers can act as Lewis Bases because of the lone pairs on Oxygen
 pKa: When protonated, ethers have a pKa of about -3
 Diethyl ether is a common solvent

Naming Conventions
Naming ethers is fairly simple. The two R groups are named alphabetically, and the suffix “-ether”
follows. If both R groups are the same, the prefix “di-” goes before the name of the R group. Below
are some examples of ethers with their names.

Dimethyl ether

Ethyl isobutyl ether

3-chloropropyl ethyl ether

Ether Group Reactions
Ethers participate in numerous reactions, more often as solvents than reactants. Ethers tend not to be
reactive due to the difficulty of breaking the C-O single bonds. The most famous reaction involving
ethers is the Williamson Ether Synthesis, in which an alkoxide reacts with an alkyl halide to form an
ether.

Aside from their synthesis, ethers only react under specific circumstances. For example, epoxides are
a type of ether in which the oxygen and the carbon atoms directly attached to it form a three-
membered ring. Because the bond angles are small, the ring is strained and can be broken in either
acidic or basic conditions.

Williamson Ether Synthesis

When a primary or secondary alkyl halide reacts with an alkoxide, the product of the reaction is an
ether. One side of the ether is an alkyl chain from the alkyl halide, and the other side is an alkyl chain
that came from the alkoxide. An alkoxide is any RO– group.

The alkyl halide must be primary or secondary because the synthesis proceeds as an SN2 reaction. For
the nucleophilic alkoxide to perform the back-side attack on the alkyl halide, there must be enough
space. This means that tertiary alkyl halides cannot undergo Williamson Ether syntheses.

Epoxide Formation and Opening

Epoxides are a type of ether. They are heterocyclic compounds that contain an oxygen and two
carbon atoms. One way to form Epoxides is with the addition of a base and heat to a halohydrin. A
halohydrin is a compound containing both an OH group and a halide.

Once the OH has been deprotonated, the O group attacks the other C, kicking off the Br.

Epoxides also form when an alkene reacts with meta-chloroperbenzoic acid, or m-CPBA.
Epoxide rings can open under both acidic and basic conditions. In acidic conditions, the nucleophile
attacks the ring on the more substituted side. The stereochemistry reverses at the electrophilic carbon.

In basic conditions, the nucleophile attacks the ring on the less substituted side.

Ethers as Solvents

Ethers serve as solvents in a variety of organic reactions. They are moderately polar and aprotic. This
means that ethers can only accept hydrogen bonds.

Diethyl Ether
One of the most well-known examples of this functional group is diethyl ether. Diethyl ether is a
useful solvent for a variety of reactions. Historically, it was used as an anesthetic. However, because
of its flammability, alternatives to diethyl ether are more common. In modern industry, the cyclic
ether tetrahydrofuran is more common than diethyl ether due to the latter’s flammability.

Diethyl ether is highly volatile. Even though it has a boiling point of 34.6°C, diethyl ether will
evaporate rapidly when left in an open container.
 Tetrahydrofuran

Ethereal solvents are often involved in the esterification of acid chlorides. This type of reaction is the
replacement of a Chlorine atom next to a carbonyl group with an alkoxy group. An alkoxy group is
any RO group where the oxygen connects the R group to the rest of the compound.

Nomenclature of Ethers
Ethers are compounds having two alkyl or aryl groups bonded to an oxygen atom, as in the
formula R1–O–R2. 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

 Alkyl Group Name Alkoxy Group Name

C6 H5 – 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 11
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 22
 CH3CH2OCH2CH3 diethyl ether (sometimes referred to as just ether)
 CH3OCH2CH2OCH3 ethylene glycol dimethyl ether (glyme).

Exercises 22
Try to name the following compounds using these conventions:
 J

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 22
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 (R–S–R') are called sulfides, e.g., (CH3)3C–S–CH3 is tert-butyl methyl
sulfide. Sulfides are chemically more reactive than ethers, reflecting the greater nucleophilicity
of sulfur relative to oxygen.

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)

Structure of Ethers
Ethers are a class of organic compounds that contain an sp 3 hybridized oxygen between
two alkyl groups and have the formula R-O-R'. These compounds are used in dyes,
perfumes, oils, waxes and other industrial uses. Aliphatic ethers have no aryl groups
directly attached to the ether oxygen.

Examples of Aliphatic Ethers

Aromatic ethers have at least one aryl ring directly attached to the ether oxygen. In aryl
ethers, the lone pair electrons on oxygen are conjugated with the aromatic ring which
significantly changes the properties of the ether.

Example of Aromatic Ethers

The sp3 hybridization of oxygen gives ethers roughly the same geometry as alcohols
and water. The R-O-R' bond angle is close to what is expected in a tetrahedral
geometry. The bond angle of dimethyl ether is 112 o which is larger than the H-O-H
bond angle in water (104.5o) due to the steric repulsion of the methyl groups.

The presence of an electronegative oxygen atom gives ethers a small dipole moment
with the electron density primarily on oxygen (red and orange in the electrostatic
potential map).

Comparisons of Physical Properties of Alcohols and

Ethers
Ethers, unlike alcohols, have no hydrogen atom on the oxygen atom (that is, no OH
group). Therefore, there is no intermolecular hydrogen bonding between ether
molecules, which makes their boiling points much lower than an alcohol with similar
mass. Despite the presence of a small dipole moment, ethers have boiling points that
are about the same as alkanes of comparable molar mass. (Table 18.1.2).
 Table 18.1.2: Comparison of Boiling Points of Alkanes, Alcohols, and Ethers

Intermolecular
Condensed
Molar Boiling Hydrogen
Structural Name
Mass Point (°C) Bonding in
Formula
Pure Liquid?

CH3CH2CH3 propane 44 –42 no

dimethyl
CH3OCH3 46 –25 no
ether

ethyl
CH3CH2OH 46 78 yes
alcohol

CH3CH2CH2CH2CH3 pentane 72 36 no

diethyl
CH3CH2OCH2CH3 74 35 no
ether

butyl
CH3CH2CH2CH2OH 74 117 yes
alcohol

Ether molecules do have an oxygen atom, however, and engage in hydrogen bonding
with water molecules. Consequently, an ether has about the same solubility in water as
the alcohol that is isomeric with it. For example, dimethyl ether and ethanol (both
having the molecular formula C2H6O) are completely soluble in water, whereas diethyl
ether and 1-butanol (both C4H10O) are barely soluble in water (8 g/100 mL of water).

Peroxide Formation
Many ethers can react with oxygen to form explosive peroxide compounds n a free
radical process called autoxidation. For this reason ethers should not be stored for long
periods of time and should not be stored in glass bottles. The danger is particularly
acute when ether solutions are distilled to near dryness. The hydroperoxides can
become more concentrated during a distillation because they tend to have a slightly
higher boiling point than the corresponding ether. Before performing an ether
distillation great care should be taken to test for the presence of peroxides.
Naming Ethers
When no other functional group is present, simple ethers are often given common
functional class names. Both alkyl groups attached to the oxygen atom are named as
substituents (in alphabetical order) and then the word ether is added. The common
names for alkyl substituents discussed in Section 3.3 are often used.

Example 18.1.1

IUPAC nomenclature for ethers should be used for complicated ethers, compounds with
more than one ether linkage, and compounds where other functional groups are
present with an ether. In these cases, an RO group of the ether is named as an alkoxy
substituent. Common alkoxy substituents are given names derived from their alkyl
component. The suffix -yl is replaced with -oxy. (Table 18.1.1):

Table 18.1.1: Common Alkyl and Alkoxy Groups

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

Example 18.1.2

Cyclic Ethers
Cyclic ethers are a type of heterocycle with one or more oxygens located in the ring.
Many cyclic ethers have common names and are often used as solvents due to their
inert nature. These ring structures are also found in many biological molecules such as
sugars and DNA. The rings are numbered so that an oxygen gets position 1.

Example 18.1.3
Exercise 18.1.1

Name the following ethers:

a)

b)

c)

d)

e)
f)

g)

Answers

a) 3-Isopropoxypentane

b) 1,3-Dimethoxybenzene

c) 2-Methyltetrahydropyran

d) Cyclopentyl ethyl ether

e) 4-Bromo-1-ethoxybenzene

f) Dicyclohexyl ether

g) 4-Butoxycyclohexene