ETHERS

Di-alkyl or aryl derivatives of water or anhydrides of alcohols are called as ethers.

IUPAC name of the ethers: Alkoxy alkane.
The larger alkyl group forms parent chain alkane; the smaller group along with oxygen atom is called
as alkoxy substituent.
CH3- O- CH3 - Di-methyl ether = Methoxy methane
CH3 – O – CH2-CH3 - Ethyl methyl ether = Methoxy ethane

O CH2 CH3 Ethoxy benzene

O Phenoxy benzene

OC 2H5
H3C CH CH3 2- Ethoxy propane

OC 2H5
H3C C CH3 2,2- diethoxy propane
OC 2H5

CH3
H3C CH2 O C CH3
2-ethoxy-2-methyl - propane
CH3

OC2H5 3-ethoxycyclohexene

OH OC2H5
H3C CH CH CH3 3-ethoxy,butan-2-ol

Ethers and alcohols are functional isomers.

PREPARATION METHODS:
1. From alkyl halides:
A: Williamson’s synthesis:
Williamson’s synthesis is mainly used for preparation of mixed / unsymmetrical ethers.
When alkyl halides are treated with sodium alkoxides, ethers are produced. It is Nucleophilic
substitution reaction on alkyl halides through SN1 or SN2 mechanism.

R X + R O - Na R - OR + Na X
Alkoxide nucleophile

But alkoxide is a stronger base. R-X will take part elimination reaction and alkene is produces as a
byproduct. To minimize the elimination reaction, lower degree of alkyl halides should be taken. For
better yield of ethers the alkyl halide should be primary and alkoxide should be secondary or
tertiary.
H3C CH2 Br + H3C CH2 ONa H3C CH2 O CH2 CH3 + Na Br
H3C CH2 Br + H3C CH ONa H3C CH2 O CH CH3 + Na Br
CH3 CH3
20 and 30 alkyl halides are used in this reaction elimination takes place and alkenes are produced.
CH3
H2C C CH3
H3C C Br + H3C CH2 ONa
CH3
+ Na Br
CH3
CH3
CH3
H3C C ONa + H3C CH2 I H3C C O - CH3 Na Br +
CH3
CH3
Aryl halides cannot be used for preparation of ethers in Williamson’s synthesis, because aryl halides
are less reactive towards Nucleophilic substitution reaction than alkyl halides.
Cl

+ H3C ONa No reaction

O - Na
O - CH 2 - CH 3

+ H3C CH 2 -Br
+ Na Br

B: Reaction with dry Ag2O:

Alkyl halides are heated with dry Ag2O, symmetrical ethers are produced. O-2 is nucleophile.

H3C CH2 Br
+ Ag2O H3C CH2 O CH2 CH3 + 2AgBr
H3C CH2 Br

Mixed ethers can be prepared by taking two different alkyl halides. The yield is very less,
because mixture of ethers are obtained.

CH3- Cl + CH3-CH2-Cl + Ag2O ⎯⎯

→ CH3 –O- CH3 + CH3- O- CH2- CH3 + CH3-CH2-O- CH2-CH3
2. From Alcohols:
A: Reaction with conc. H2SO4 at 1400C or Al2O3 at 2500C:
When alcohols are treated with conc. H2SO4 / H3PO4 at 1400C or Al2O3 at 2500C, intermolecular
dehydration takes place and ether is produced.

R-OH + R-OH ⎯⎯⎯⎯⎯⎯ → R-O-R + H2O

2 Con H SO /1400 C
4
Al O / 2500 C
2 3

CH3- OH + CH3-OH ⎯⎯⎯⎯⎯⎯ → CH3- O- CH3 + H2O

2 4 Con H SO /1400 C
Al O / 2500 C 2 3

CH3- CH2- OH + CH3-CH2 -OH ⎯⎯⎯⎯⎯⎯ → CH3-CH2- O-CH2- CH3 + H2O

2 4 Con H SO /1400 C
Al O / 2500 C 2 3

Mechanism:
 + +
H3C CH2 O - H + H H3C CH2 O - H
H
- H2O
H3C CH2

H
+ +
H3C CH2 + H3C CH2 O - H H3C CH2 O CH2 CH3
- H+

H3C CH2 O CH2 CH3

B: Reaction with diazomethane (CH2N2):
When alcohols and phenols are treated with diazomethane, methyl ethers are obtained.

CH3 –OH + CH2N2 ⎯⎯

→ CH3 – O – CH3 + N2
CH3 – CH2 –OH + CH2N2 ⎯⎯
→ CH3 –CH2– O – CH3 + N2
CH3 -CH (OH) – CH3 + CH2N2 ⎯⎯
→ CH3 -CH (OCH3) – CH3 + N2

O - CH 3
OH

+ CH 2 - N2 + N2

3. Preparation of aryl ethers:

Phenols are converted in to alkyl phenyl ethers by treating with alkaline solution of alkyl halides.
OH O - Na O - CH 3
NaOH
+ CH 3 -Br
+ Na Br

Aryl methyl ethers can also be prepared by treating with dimethyl sulphate instead of expensive
methyl halides.
OH O - Na
O - CH 3
O
NaOH O
+ CH 3 -O S
O
O - CH 3
+ CH 3 -O S O - Na
O
Anisole

OH O - Na
O - C 2 H5
O
NaOH
O
+ C2H5 -O S O - C 2 H5
+ C2H5 -O S O - Na
O
O
Phenetole

PROPERTIES OF ETHERS:
1. Lower ethers dimethyl ether and diethyl ethers are gases and higher ethers are
colourless pleasant smelling low boiling point liquids.
2. Ethers are neutral compounds and stable compounds.
 3. Ether vapour vapours are highly inflammable.
4. Ether structure is similar to that of water.

O
R R
1100

5. The C-O-C bond angle in ethers is (1100 ) slightly greater than that of
water(104.28”).the larger bond angle in ethers may be greater repulsive interactions
between two alkyl groups as compared to smaller H- atoms in water.
Ethers have bent structure or angular structure and have a net dipole moment
6. Insoluble in water, due to lack of hydrogen bonding.
7. BP of ethers (diethyl ether BP=306.7K) are very less when compare to the corresponding
alcohols, due to lack of hydrogen bonding in ethers.
8. Ether is used as solvent for organic compounds.
REACTIONS ON ETHERIAL OXYGEN:
1. Action of air- Peroxide formation:
When ethers are exposed to air in presence of sunlight, slowly undergoes oxidation and
produces hydroperoxides /peroxides, which are explosive.

air/h
H3C CH2 O CH2 CH3 H3C CH O CH2 CH3
O O H
In the above reaction oxidation takes at the carbon atom next to ethereal oxygen to form
peroxide which is less volatile and explosive. These hydroperoxides are impurity in the
ether.
If ether having hydroperoxide is used as solvent, the peroxide oxidizes organic
compound. Ether which is used as solvent should be free from peroxide.
Peroxide in ether can be detected and removed by KI or mohr,s salt.
KI: The peroxide can be removed by shaking with aqueous solution of KI. The ether
peroxides are reduced to ether and KI is oxidized to Iodine, violet vapours are evolved.
Mohr,s salt: [FeSO4 + (NH4)2SO4]: Ether is first is treated with freshly prepared FeSO4
or Mohr’s salt followed by NH4CNS/ KCNS, blood red colour solution is formed. Fe+2 is
oxidizes into Fe+3 and produces Fe(CNS)3.
2. Formation of Oxonium salts- Reaction with Conc. HCl/ H2SO4:
Ethers act as Lewis bases due to the presence of two lone pairs of electrons on oxygen.
When ethers are treated with cold concHCl/H2SO4forms stable Oxonium salts.
 + -
R O R + H Cl R O R Cl
H

Dialkyl oxonium hydrogenchloride

+ -
H5 C2 O C 2 H5 + H Cl H 5 C2 O C2H5 Cl
H

Diethyl oxonium hydrogenchloride

+
R O R + H2SO 4 R O R HSO 4
H

Dialkyl oxonium hydrogen sulphate

3. Reaction with Lewis acids- Formation of etherates:

Being Lewis bases, ethers forms complexes compounds etherates with Lewis acids such
as BF3, AlCl3, FeCl3 etc.,

R O R + BF 3 R O R

BF 3

H5C2 O C2H5 + BF3 H5C2 O C2H5

BF3
Boron trifluoride etherate

Similarly diethyl ether is also react with Grignard reagent and forms Grignard reagent
etherate. Due the formation of etherate, RMgX dissolved in ether. Ether is used as solvent of
the preparation of RMgX.
R

H5C2 O Mg O
2 H5C2 O + R Mg X
X
C2 H5

H5C2 H5C2 C2 H5

REACTIONS INVOLVING CLEAVAGE OF - C – O- BOND

4. Reaction with one mole or dilute HI:
In ethers ethereal bond is strong bond. It is difficult to cleave the bond. They show
chemical inertness. The cleavage of ethereal bond can be carried out with HI, H2SO4,
PCl5.
i. When ether is treated with equimolar quantities of HI, lighter alkyl is converted in to
iodide and bulky alkyl group is converted in to alcohols.

H3C O C2H5 +H I H3C I + H3C CH2 OH

Attack of I- on CH3+ is easier (SN)

 H3C CH2 CH2 O C2 H5 +H I H5 C 2 I + H3C CH2 CH2 OH

ii. If a tertiary alkyl group is present in ether, tertiary alkyl group is converted in to alkyl
Iodide and the other group is converted in to alcohol (SN1 route).
CH3 CH3
1 Equiv HI
H3C O CH3 H3C I + CH 3 - OH
CH3 CH3

iii. In case of aryl alkyl ethers, always alkyl group is converted in to alkyl Iodide
irrespective of concentration.
O OH
CH3 1 equiv HI
+ CH 3 - I
O OH
CH3 Excess HI
+ CH 3 - I
O CH OH
CH2 3
1Equiv or Excess HI
+ CH 2 - CH 3 - I
Iv: Benzyl alkyl ethers are treated with HI, C6H5- CH2-I and ROH are formed.
R OH
O 1 Equiv HI
+ R- I

CH3 OH
O 1 Equiv HI
+ CH 3 - I

This can be explained on the basis of steric hindrance. The alkyl halide is formed by
attack of Iodide ion on the protonated ether. Therefore the attack of halide ion occurs at
smaller alkyl group which offers less steric hindrance. So alkyl halide is formed from
smaller alkyl group.
Mechanism:

+ -
H5C2 O C2H5 + H I H 5 C2 O C2H5 + I
H
Protonated ether or Oxonium salt

-
H5 C2 O
+
C2 H 5 + I H3C CH2 OH + C2H5 -I

H
The order of reactivity of halogen acids is HI > HBr > HCl
The above reactions are not possible with HCl and HBr, as the attacking nucleophiles are Cl-
and Br- are weaker nucleophiles than R-OH the leaving group.
5. Reaction with excess or conc HI:
 Ethers are treated with excess of HI or conc HI , both alklyl groups are converted into
corresponding alkyl Iodides.

Excess HI or Conc HI
H3C O C2H5 H3C I + H3C CH2 I + H2O

Excess HI or Conc HI
H5 C2 O C2 H5 2 H3C CH2 I + H2O

Benzyl
6. Cyclic ethers with HI:
Cyclic ethers are treated with HI/HBr, cyclic ethers easily undergoes cleavage to form di
halo alkanes.

1 Equiv HI
I CH2 CH2 CH2 OH
O

Excess HI

O
I CH2 CH2 CH2 I + H2O

7. Reaction with dil H2SO4:

i. dil H2SO4: Ethers are treated with dil H2SO4 under pressure, ethers undergoes
hydrolysis produces alcohols.

dil H2SO4
H3C O CH3 / pressure
H3C OH + H3C OH

dil H2SO4
H5C2 O C2H5
/ pressure
H5C2 OH + H5C2 OH

dil H2SO4
H5C2 O CH3
/ pressure
H5C2 OH + H3C OH

ii. Conc. H2SO4: When ethers are heated with conc.H2SO4, alcohol and alkyl hydrogen
sulphate is obtained.

Conc. H2SO4
H3C O CH3 
H3C OH + H3C HSO 4

Conc. H2SO4
H5C2 O C2H5

H5C2 OH + H5C2 HSO4

When 20 and 30 ethers are heated with Conc.H2SO4 alkenes are produced.
CH3 Conc. H2SO4 CH3
H3C O CH3 H2C C + H3C OH
CH3 CH3

8. Reaction with PCl5:

Ethers on reaction with PCl5, ethereal bond cleavage takes place and alkyl halides
produced.
 PCl5
H3C O CH3 H3C Cl + H3C Cl + POCl 3


PCl5
H5C2 O CH3 H5C2 Cl + H3C Cl + POCl 3


9. Reaction with Acid chloride (SNAC reaction):

Ethers are treated with acid chlorides in the presence of anhydrous ZnCl 2, alkyl halide
and ester are produced.

O
CH3 COCl
H3C O CH3 H3C Cl + H3C C O CH3
anhydrous ZnCl2

O
CH3 COCl
H5C2 O C2H5 H5C2 Cl + H3C C O C2H5
anhydrous ZnCl2

10.Reaction with Acetic anhydride(SNAC reaction):

Ethers are treated with acid chlorides in the presence of anhydrous ZnCl2, esters are
produced.

O O
CH3 CO - O - CO - CH3
H5C2 O C2H5
anhydrous ZnCl2
H3C C O C2H5 + H3C C O C2H5

-
H3C CH2 O O O O
O + H3C C O C CH3 H3C C O C CH3
+
H3C CH2 H3C O
CH3
CH2 CH2

-
O O O O
H3C C O CH2 CH3 + H3C C O CH2 CH3 H3C C O C CH3

O
CH3
CH2

11.Reaction of alkyl groups of ethers –Halogenation:

The alkyl groups of ethers behave like alkane. But  -carbon is slightly activated due to
–I effect of ethereal oxygen. When ethers are treated with chlorine or Bromine, hydrogen
atoms of the carbon directly attached to oxygen atoms are more readily substituted.
Diethyl ether on reaction with Cl2/ Br2 in the dark, 1,1-dichloro diethyl ether is produced.
Halogenation preferentially occurs at  -carbon.
 Dioethyl ether is treated with excess of Cl2 or Br2 in the presence of sunlight, all the
hydrogen atoms are alkyl groups are substituted by halogen perchloro diethyl ether is
obtained.

Cl2 (Excess)
H3C CH2 O CH2 CH3 Sunlight / h
Cl 3C CCl 2 O CCl 2 CCl 3

Diethyl ether and chloroform is used as anaesthestic agent.

12.Ring substitution in aromatic ethers:
Alkoxy group is ring activator and ortho, para directing group. Ethers are relatively less
reactive than phenols towards electrophilic substitution reactions. Methyl phenyl ether is
treated with Br2 in the presence of CS2 ( non –polar solvent) ortho and para bromo
methyl phenyl ethers are produced.
Methyl phenyl ether is treated with nitrating mixture ( conc HNO3 + conc H2So4) ortho
and para nitro methyl phenyl ethers are produced.
OCH 3 OCH 3
O Br
CH3 Br2 /CS2
+
Br
Methyl phenyl ether is treated with nitrating mixture ( conc HNO3 + conc H2So4) ortho
and para nitro methyl phenyl ethers are produced.
OCH 3 OCH 3
O NO 2
CH3 Conc HNO3 + H2SO4

Nitrating mixture
+
NO 2

CYCLIC ETHERS / OXIRANES

Three membered cyclic ethers are called as oxiranes or epoxides or ethylene oxides.

Ethylene oxide/ Ethylene epoxide/ oxirane

O

Propylene oxide/ 1,2-epoxy propane/ 2- methyl oxirane

O

Propylene oxide/ 1,2-epoxy propane/ 2,2- dimethyl oxirane

O

H2C O
Oxitane/ Oxo cyclobutane
H2C CH2 O
 THF / Tetra hydro furan
O
O
1,4- dioxane / Diethylene dioxide
O

PREPARATION OF EPOXIDES / OXIRANES ( CYCLIC ETHERS):

A: From ethylene with per acids:
When ethylene is treated with per acids / peroxy acids (Per acetic acid-CH3COOOH (PAA)/ per
benzoic acid C6H5COOOH (PBA)) gives oxiranes.
H2C CH2
CH3COOOH (PAA)/
H2C CH2 C6H5COOOH(PBA)
O
Ethylene epoxide/ oxirane

H3C HC CH2
CH3COOOH (PAA)/
H3C CH CH2 C6H5COOOH(PBA)
O
Methyl oxirane

B. From ethylene glycol:

When ethylene glycol is heated to 5000C, ethylene oxide or oxirane is obtained.

H2C OH 
500 °C O
H2C OH
C: Ethylene and conc. H2O2:

When ethylene is treated with conc. H2O2, epoxides are formed.

H2O2 H2C CH2

H2C CH2
O
Ethylene epoxide/ oxirane

D: Ethylene, Ag /Air:

Ethylene is treated with Silver and air at 200-4000C, oxirane is produced.

1/ 2 O2 H2C CH2
H2C CH2
200- - 400 °C
O
Ethylene epoxide/ oxirane

E: From ethylene cyano hydrin:

Ethylene cyano hydrin is treated with conc. Solution of NaOH, epoxide is obtained.
H2C OH Conc a H2C OH
O
H2C Cl H2C OH

F: Dioxane is prepared by distilling mixture of ethylene glycol and conc. Or fuming H2SO4.
 Fuming H2SO4

2 HO OH
O O + 2 H2O

Dioxane

Dioxane is a useful solvent.

PROPERTIES OF CYCLIC ETHERS/ OXIRANES:

Oxiranes is a 3- membered cyclic compound. Due to angle strain it take part in addition
reactions through ring opening process. It take part in addition reactions with electrophilic as
well as nucleophilic reagents. In presence of electrophilic reagents SN 1 addition takes place, in
presence of nucleophilic reagents SN2 addition takes place.
1. Oxirane / ethylene epoxide on heating undergoes molecular rearrangement and produces
acetaldehyde.

H
H- Shift ( Hydride ion shift) O
H2C CH
H3C C H
O

2. Reaction with HCl:

H2C CH2 H - Cl H2C CH2
+ -
O H Cl O
+

SN1 +
H2C CH2 OH
Cl CH2 CH2 OH

3. Reaction of oxiranes:

H2C CH2 H - CN
MeOH
MeO- H+ O H+ CN- OH CN
OH OMe
H2O/ H+ OH- NH2/ H+ NH2-
RMgBr/R- +MgBr

R OMgBr OH NH2
OH H
4. Reaction of methyl oxiranes:
 H3C CH CH2 CN
OH

HCN
H3C CH CH2 OC 2H5 H3C CH CH2 NH2
C2H5OH NH3
OH OH
O

HCl
C2H5MgI
H2O18 SN1 SN1

18
H3C CH CH2 C2H5 H3C CH CH2 OH
H3C CH CH2 Cl
OMgI OH
OH

5. Reduction with LiAlH4:

LAH
H3C CH2 OH
O H2O

Substituted oxiranes on reduction gives two products.

OH OH
LAH
O
H3C CH CH3
+ H3C C CH3
HO 2
2-propanol -- major product 1-propanol -- minor product

OH
LAH
O
H3C C CH3
+ H3C CH OH
H2O CH3 CH3
2-propanol -- major product 1-propanol -- minor product