Ethers

Ethers are represented by general formula R – O – R or R – O – R' where R and R' may be alkyl or
aryl group. Ether is also called the dialkyl derivative of water (H – O – H) or alkyl derivatives of
alcohol (R – O – H). Ether has the functional group (– O –) linked by alkyl or aryl groups in the both
sides of O. Examples:
CH3 – O – CH3
Dimethyl ether CH3 – O-

Methyl phenyl ether

Nomenclature of Ethers
There are two types of naming system of ethers.
1. Common system
The common names of ethers are derived by writing the alkyl or aryl groups in alphabetical
order followed by the word ‘ether’ at the end. When the two alkyl groups are identical or
same, a prefix ‘di’ is added before the name of the group.
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For same types of alkyl group: CH3 – O – CH3
Dimethyl ether

For different type of alkyl group: CH3 – O – C2H5

Ethyl methyl ether

2. IUPAC system
According to IUPAC system, ethers are named as alkoxy alkanes. The smaller among the
two alkyl groups with the ethereal ‘oxygen’ is termed as alkoxy group. The larger of the alkyl
groups is taken as an alkane, a parent hydrocarbon.

Formula Common name IUPAC name

CH3 – O – CH2CH3 Ethyl methyl ether Methoxy ethane

CH3CH2 – O – CH2CH3 Diethyl ether Ethoxy ethane

CH3 Iso methyl propyl ether 2-Methoxypropane

CH3 – O – CH – CH3

O – CH2CH3 Butyl ethyl ether 2-Ethoxybutane

CH3 – CH – CH2 – CH3

Classification of Ethers
Ethers are classified into two types:
1. Symmetrical Ethers or simple ethers
Symmetrical ethers or simple ethers are those in which two alkyl groups attach to – O – O – are
same.
CH3 – O – CH3 C2H5 – O – C2H5
Dimethyl ether Diethyl ether
(methoxy methane) (ethoxy ethane)

2. Unsymmetrical (mixed) ethers

Unsymmetrical ether or simple ethers are those in which two alkyl groups attach to – O – O –
are different.
CH3 – O – C2H5 C2H5 – O –C3H7
Ethyl methyl ether Ethyl n-propyl ether
(methoxy ethane) (1-Ethoxy propane)
Ethers are also classified as aliphatic and aromatic ether. If both R and R' are alkyl groups then
the ethers are known as aliphatic ethers
Example:
CH3CH2 – O – CH2CH3 CH3CH2 – O – CH3
Diethyl ether Ethylmethyl ether
If one or two aryl groups (C6H5 –) are present in ether then the ether is called aromatic.
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Example

O – CH3 -O or C6H5 – O –
C6H5
Methyl phenyl ether (Anisole)

Isomerism of Ethers Diphenyl ether

There are two types of structural isomerism in ethers.

1. Functional isomerism
Ethers and monohydric alcohols are functional isomers because of both having the same
general formula (CnH2n + 2O).

Functional isomers
General formula
Ether Alcohol
C2H6O CH3 – O – CH3 C2H5OH
Methoxy methane Ethanol
C3H8O CH3 – O – C2H5 CH3CH2CH2 – OH
Methoxy ethane Propan-1-ol

2. Metamerism
In the metamerism of ethers, different alkyl groups are attached to the etherial oxygen.
The formula C4H10O exhibits three isomers.
CH3 – O – CH2CH2CH3
1-Methoxy propane

C4H10O
CH3 – O – CH – (CH3)2
Methyl isopropyl ether

C2H5 – O – C2H5
Ethoxy ethane

Preparation of Aliphatic and Aromatic Ethers

Williamson's Etherification Process (Williamson’s Synthesis)
This is the most important method of laboratory preparation. It can be used for the preparation of
symmetrical as well as unsymmetrical aliphatic and aromatic ether. In this method an alkyl halide is
treated with sodium alkoxide or phenoxide. The reaction involves the nucleophilic substitution of the
halogen atom by the alkoxide group.

Or,

R – O Na + X – R' R – O – R' + Nax

Ether (aliphatic)
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Ar – O
Na + X – R' Ar – O – R' + NaX
Aromatic ether
Example,
CH3CH2 – O Na + Br
– CH2CH3 CH3CH2 – O – CH2CH3 + NaBr
Sod. ethoxide Ethyl bromide Ethoxy ethane (simple or symmertical ether)

CH3 – O Na + Br – CH2CH3 CH3 – O – CH2CH3 + NaBr

Sod. methoxide Methoxy ehtane (mixed or unsymmetrical ether)

ONa + Br – CH3 O – CH3 + NaBr

Sod. phenoxide Methyl bromide

Methyl phenyl ether (Anisole)
(Aromatic ether)
In order to prepare unsymmetrical ether, it is better to take 1º alkyl halide for the reaction as 2º and
3º alky halides undergo elimination reaction in the presence of strong alkoxide and phenoxide bases.
For example, to prepare tert-butyl ethyl ether, we should take ethyl bromide and sodium tert-
butoxide.
CH3 CH3
CH3 – C – ONa + CH3CH2 – Br CH3 – C – O – CH2CH3 + NaBr
CH3 CH3
tert-butyl ethyl ether
But if tert-butyl bromide and sodium ethoxide are used here then elimination reaction takes place to
give alkene as the major product.
CH3 CH3
CH3 – C – Br + CH3CH2 – ONa CH3 – C = CH2 + CH3CH2OH + NaBr
CH3 Sod. ethoxide 2-methyl propene
tert-butyl bromide

Physical Properties

1. They are sparingly soluble in

water but dissolve easily in
organic solvents like ethyl
alcohol, benzene, etc. They
are soluble in water due to
the hydrogen bonding
between ether and water
molecules. For example like
ethyl alcohol, dimethyl ether
is completely miscible with
water
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2. The C – O – C bond in ether is 110º, so ether is polar molecule with small dipole moment.
Diple moment of dimethyl ether = 1.3 D while that of diethyl ether is 1.18 D.
R
110º O
R net dipole moment

3. The boiling points of ethers are much lower than the alcohols having same molecular formula.
The higher boiling points of alcohols are due to intermolecular hydrogen bonding which is not
possible in ethers. For example: diethyl ether has much lower boiling point (35ºC) than its
Add your text here
isomeric n-butyl alcohol (117ºC)

Chemical Properties of Ethoxyethane

1. Action of hydroiodic acid (HI)
Ethers react with concentrated hydroiodic (or hydrobromic) acids in cold to form alcohol and
alkyl halide.
cold
R – O – R + HI R – OH + RI
Alcohol Alkyl iodide
Example:
C2H5 – O – C2H5 + HI cold
C2H5OH + C2H5I
Ethoxy ethane Ethanol Ethyliodide
The cleavage of the C – O bond by halogen acids occurs in two steps as follows.
a. The ether undergoes protonation from the acid to give protonated ether or oxonium ion.
b. Then the oxonium ion is attacked by the halide ion as nucleophile.
• • H 
i. R– O –R+
HX
 |+ –
R–O
 – + X
• 
Oxonium ion (protonated ether)
H
|
ii. R – O+ – R + X – R – OH + RX


Halide ion Alcohol Alkyl halide

However when treated with hot hydroiodic acid in excess, only alkyl halides are formed.
hot
R – O – R + 2HI 2RI + H2O
Example:
hot
CH3CH2OCH2CH3 + 2HI 2CH3CH2I + H2O
Dietlyl ether excess Ethyl iodide

The order of the reactivity of the halogen acids is

HI > HBr > HCl
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2. Action of conc. Hydrochloric acid (HCl)
Ethoxy ethane(diethyl ether) reacts with cold conc. mineral acids to form oxonium salts which
are decomposed on dilution with water to regenerate ether.

O°C  H| +
 –
CH3CH2-O-CH2CH3 + HCl CH3CH2 – O – CH2CH3 Cl
  
Diethyl ether Oxonium salt (diethyl oxonium chloride)

3. Action of conc. H2SO4

When diethyl ether is heated with conc. H2SO4, it gives ethyl alcohol and ethyl hydrogen
sulphate.

CH3CH2 – O – CH2CH3 + HO – SO3H CH3CH2 – O – SO3H + CH3CH2OH
Diethyl ether (conc.) Ethyl hydroghen sulphate Ethyl alcohol
Further, diethyl ether reacts with cold conc. H2SO4 to give oxonium salt.

O°C  H| 
+
–
CH3CH2 – O – CH2 – CH3 + H2SO4 CH3CH2 – O – HSO4
CH2CH3  


Diethyl ether (Diethyl oxonoium hydrogen sulphate)

4. Reaction with air (atmospheric oxygen)

Ethers in contact with air slowly react with atmospheric oxygen in the presence of light to form
peroxides, which are unstable and hazardous.
O – OH
• • (air)
CH CH – O – CH CH + CH CH – O – CH CH
O 2 3 2 3 2 3
3 2
• •
Dietlyl ether Diethyl ether peroxide
(Ethoxyethane)

Peroxides are hazardous because they explode violently on heating. During distillation of
diethyl ether, the residue in the distilling flask becomes rich in peroxides. Hence, diethyl ethers
should not be distilled to dryness and are stored in yellow bottles with no air left inside. For the
precaution, a little ethanol is added to inhibit auto-oxidation.
5. Reaction with chlorine
When ethoxyethane reacts with chlorine in the dark, substitution products are obtained. Usually
the hydrogen at  – carbon is displaced most readily.
   
dark
CH3CH2 – O – CH2CH3 + Cl2 CH3CH2 – O – CH(Cl)CH3
– HCl -chloro diethyl ether

Cl2 dark

Cl Cl
CH3 – CH – O – CH – CH3 + HCl
, ' - Dichlorodiethyl ether
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If reaction is carried out in presence of light all the hydrogen atoms are substituted by chlorine
atoms to give perchloro diethyl ether
light
CH3CH2 – O – CH2CH3 + 10Cl2 CCl3CCl2 – O – CCl2CCl3 + 10 HCl
Perchlorodiethyl ether

Answer Questions
1. a. Convert ethoxyethane into methoxy ethane.
b. How will you distinguish diethyl ether and ethyl alcohol?
🗉 a. Ethoxyethane can be converted into methoxyethane by the following reactions
CH CH CH3ONa
– O – CH CH 2HI (excess) 2CH CH I CH OCH CH
3 2 3
3 2 2 3 3 2
 Methoxyethane
Iodoe tane
b. Ethyl alcohol reacts with sodium metal to produce hydrogen gas. Diethyl ether does not
react with sodium.
CH3CH2OH + Na CH3CH2ONa + H2 
Ethyl alcohol Sod. ethoxide
C2H5 – O – C2H5 + Na No reaction
2. What is Williamson’s etherification reaction?
🗉 This is a general method for the preparation of high molecular weight ethers. Both symmetrical
and unsymmetrical ethers can be prepared by this method. For example
Sodium methoxide reacts with ethyl iodide gives methoxyethane as follows:
dry ether CH3-O-C2H5 + NaI
CH3ONa +
IC2H5 ∆
Methoxyethane
(Ethyl methyl ether)
Sod. methoxide unsymmetrical ether

O Na + Br – CH3 O – CH3 + NaBr

Sodium phenoxide Methyl phenyl ether

(aromatic ether)
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3. What happens when
a. Sodium phenoxide reacts with iodomethane.
b. Ethoxyethane is exposed to light and air
🗉 a. Sodium phenoxide and iodomethane react to give anisole (Methoxybenzene)
– +
O Na + ICH3
O – CH3
Sod.
Iodomethane Methoxybenzene
phenoxide
(Anisole)
b. When exposed to light and air for a long time, ethoxythane is oxidized to form peroxide.
O – OH
light, air
CH3CH2 – O – CH2CH3 + O2 CH3CH – O – CH2CH3

Diethyl ether
Peroxide of diethyl ether

4. What happens when ethoxyethane reacts with

a. HCl (cold and conc.) b. aq. HI (hot)
+
🗉 a. CH3CH2 – O – CH2CH3 + HCl (conc.) Cold CH3CH2 – O – CH2CH3 ClH–
H
Diethyl oxonium chloride
Hot
b. CH3 – CH2 – O – CH2 – CH3 + 2HI 2CH3 – CH2 – I + H2O

5. What are the possible isomeric ethers of formula C5H12O.

🗉 There are five possible isomeric ethers as follows:
a. CH3 – O – CH2CH2CH3CH3 b. CH3CH2 – O – CH2CH2CH3
1–Methoxybutane 1–Ethoxypropane

CH3
CH3
c. CH3 – O – C – H CH3CH2 – O – CH
d.
CH2 CH3
CH3 2–Ethoxypropane
2–Methoxybutane

e. CH3
CH3 – O – CH2 – CH – CH3
1–Methoxy–2–methyl propane
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6. Compound (A) C4H10O is found to be soluble in conc. suphuric acid in cold condition. (A)
does not react with sodium metal or KMnO 4. When (A) is heated with excess of HI, it is
converted into single alkyl halide. Identify the compound (A)
🗉 The compound (A) must be diethyl ether which reacts with cold and conc. H 2SO4 to give
oxonium salt. The diethyl ether does not react with sodium metal but reacts with excess HI to
give ethyl iodide.
cold, conc.H2SO4 +
CH CH
3 2– O – CH CH
2 3 [CH CH
3 2 ]3
–2 O – CH CH HSO
Diethyl ether (A)
H
Soluble oxonium salt
CH3CH2 – O – CH2CH3 + Na No reaction
CH3CH2 – O – CH2CH3 + 2HI 2CH3CH2 – I + H2O
(excess) Ethyl iodide

Objective Questions
1. In Williamson synthesis of mixed ether having a primary and a tertiary alkyl group if tertiary
halide is used, then:
a. Rate of reaction will be slow due to slow cleavage of carbon-halogen bond.
b. Alkene will be main product.
c. Simple ether will form instead of mixed ether.
d. Expected mixed ether will be formed.
2. Williamson synthesis of ether is an example of :
a. Nucleophilic addition b. Electrophilic addition
c. Nucleophilic substitution d. Electrophilic substitution
3. In Williamson’s synthesis, ethoxyethane is prepared by
a. passing ethanol over heated alumina b. sodium ethoxide with ethyl bromide
c. ethyl alcohol with sulphuric acid d. ethyl iodide and dry silver oxide
4. Formation of diethylether from ethanol is based on a
a. Dehydration reaction b. Dehydrogenation reaction
c. Hydrogenation reaction d. Heterolytic fission reaction
5. Which of the following compound is soluble in water
a. Oils and fat b. Water
c. NaCl d. PCl5
6. The reaction of sodium ethoxide with ethyl iodide to form diethyl ether is termed
a. Electrophilic substitution b. Nucleophilic substitution
c. Electrophilic addition d. Radial substitution
7. Which of the following product is formed, when ether is exposed to air?
a. Oxide b. Alkanes
c. Alkenes d. Peroxide of diethyl ether
8. Ether which is liquid at room temperature is
a. C2H5OCH3 b. CH3OCH3
c. C2H5OC2H5 d. None
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9. In the following reaction
Red P + HI
C2H5OC2H5 + 4[H] 2X + H2O
a. Ethane b. Ethylene
c. Butane d. Propane
10. The ether that undergo electrophilic substitution reaction
is
a. C2H5OCH3 b. CH3OCH3
c. C2H5OC2H5 d. C6H5OCH3
11. Etherates are
a. Ethers b. Solution in ether
c. Complexes of ethers with Lewis acid d. Complexes of ethers with Lewis base
12. Methyl phenyl ether can be obtained by reacting
a. Phenolate ion and methyl iodide b. Methoxide ion and bromobenzene
c. Meythanol and phenol d. Bromobenzene and methyl bromide
13.13.The cleavage of an aryl alkyl ether with cold HI gives:
a. Alkyl iodide and water b. Aryl iodide and water
c. Alkyl iodide, aryl iodide and water d. Phenol and alkyl iodide
14. Ethers are stored in brown bottles. This is because on exposure to air and light ethers are
converted to
a. Peroxides b. Oxonium ions
c. Ozonides d. Electrophiles
15. Which of the following statements is false?
a. Diethyl ether has been used as a general anesthetic
b. Ethyl alcohol is present in all alcoholic beverages
c. Methyl alcohol is produced by fermentation of sugars
d. Ethylene glycol is a common antifreeze for automobiles

Hints and Solution

1. (b) The tertiary alkyl halide undergo elimination reaction to give alkenes.
2. (d) The nucleophilic substitution of halides with alkoxide leads to desired
product.
3. (b) Straight
4. (a) Straight
5. (a) Straight
6. (b) It is Williamsons synthesis and hence it is nucleophilic substitution
reaction.
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7. (d) Straight
8. (c) First two ethers are gases others are liquid
9. (a) It first gives ethyl iodide under cleavage of ethers and then under reduction
it gives ethane.
10. (b) Only alkyl aryl ethers can undergo electrophilic substitution reaction.
11. (c) Etherate is a complex R2OBF3 (BF3 is a lewis base)
12. (a) Straight
13. (d) R–O–Ar + HI →Ar–OH + RI
14. (a)

15. (c)