ALCOHOLS PHENOLS AND ETHERS

ALIPHATIC ETHERS

Ethers are compounds in which oxygen is bonded to two alkyl substituents. If the alkyl
substituents are identical, the ether is symmetrical or simple ether and if they are different, the
ether is unsymmetrical ether.

R O R R O R
A symmetrical or simple ether An unsymmetrical or mixed ether.

The groups R and R can be alkyl or aryl. When both the R groups are alkyl, they are called
alkyl ether and when at least one of the R group is an aryl, they are called aryl ethers.

10. IUPAC NOMENCLATURE OF ETHERS

The common name of ether is obtained by citing the names of the two alkyl substituents in
alphabetical order, followed by the word “ether”. The smallest ether is almost always named by
their common names.
CH3OCH2CH3 CH3CH2OCH2CH3
ethyl methyl ether diethyl ether

CH3
CH3CHOCHCH2CH3 CH3CH2CH2O
CH3
secbutyl isopropyl ether cyclohexyl npropyl ether

The IUPAC system names ether as an alkane that contains an alkoxy substituent.
The alkyl part with greater number of carbon atoms is named as alkane while the other alkyl part is
named as alkoxy by removing the “yl” from the name of the alkyl substituent and adding “oxy”.
CH3CHO
For example, CH3O is called methoxy, CH3CH2O is called ethoxy, CH3 is called
CH3CH2CHO
isopropoxy, CH3 is called secbutoxy and (CH3)3CO is called tertbutoxy. Thus,
IUPAC name for ether is alkoxyalkane.
CH3CHCH2CH3 CH3CH2CHCH2CH2OCH2CH3
OCH3 CH3
2methoxybutane 1ethoxy3methylpentane

CH3CHOCH2CH2CH2CH2OCHCH3
CH3 CH3
1, 4diisopropoxybutane

ClCH2CH2OCH3 CH2OCH=CH2
1chloro2methoxyethane Benzoxy ethene
 ALCOHOLS PHENOLS AND ETHERS

11. GENERAL METHODS OF PREPARATION OF ETHERS

11.1 INTERMOLECULAR DEHYDRATION OF ALCOHOLS

When alcohols are treated with H2SO4 or H3PO4 at 140°C, a molecule of water is eliminated
from two alcohol molecules to give ether. This reaction is called intermolecular dehydration of
alcohols. Alcohols on dehydration intramolecularly, give alkene. Thus, dehydration of alcohols to
ether can be achieved by controlling the reaction conditions i.e. reaction is carried out at low
temperature (it should not increase beyond 140°C). Alcohol should be taken in excess. When the
dehydration is carried out above 140°C, it leads to elimination forming an alkene.
conc. H2SO4
R O H + H O R R O R + H2O
, 140°C
Dehydration of alcohols to ether is useful for the preparation of symmetrical ethers only.
If we try to prepare unsymmetrical ether using a combination of two alcohols (ROH & ROH),
it leads to the formation of a mixture of three ethers (ROR, ROR and ROR).

Dehydration of alcohols to ether is an example of nucleophilic substitution. A protonated

alcohol molecule acts as substrate and the second alcohol molecule act as nucleophile.
The reaction can proceed by SN1 or SN2 process. Primary alcohols react by SN2 process and
secondary & tertiary alcohols undergo reaction by SN1 process.

H .. H H
.. + ROH +
H ..
R  OH
.. H  .O
.
R H2O R O R R  O R + H2O
 SN2 +
Transition state Protonated ether
protonated
alcohol
H+
SN1 Pathway
H2O ROR
.. Symmetrical ether
H
 ROH
.. H+
R ROR ROR
Symmetrical ether
Protonated
ether

Dehydration of alcohols can also be achieved by passing vapours of ethyl alcohol over
heated Al2O3 at 250°C.
A l2O 3
 

C2H5OH + HOC2H5 250 C C2H5OC2H5 + H2O.
11.2 WILLIAMSON’S ETHERIFICATION METHOD
When an alkoxide is treated with an alkyl halide, ether is produced. The method was
developed by Williamson and is useful for the preparation of symmetrical as well as unsymmetrical
ethers.
 
R O + R X R O R + X

where R can be same as or different from R.

 ALCOHOLS PHENOLS AND ETHERS

The alkoxide can be prepared by the action of alcohols with sodium or potassium.
ROH + K  ROK+ + ½ H2
This reaction involves SN2 mechanism, with alkoxide ion acting as nucleophile and alkyl
halide as the substrate. The complete mechanism follows as

 

R O + R X RO R X

R O R + X


Transition state
For ether to be obtained as major product, reaction should follow substitution and minimize
elimination reaction. This can be acheived by taking only methyl halides or 1° halides with lesser
branching near the reaction site.

But if we take 2° and 3° alkyl halides, which have more tendency to undergo elimination,
will give very less yield of ethers.

Suppose, we want to prepare ethyl tertbutyl ether. There are two possible routes to
prepare it.


(CH3)3CO Na
+ Route
+ CH3CH2 Br
(A)

(CH3)3COC2H5 + NaBr
Route

CH3CH2O Na+ + (CH3)3C Br Not feasible
(B)

Route (A) is more suitable to prepare given ether as the alkyl halide involved in this route is
a primary one while in route (B), the halide being a 3°, it will lead to elimination reaction forming an
alkene, 2methyl propene.
CH3 CH3

C2H5O 
CH3  C  Br CH3  C = CH2 + C2H5OH + Br
CH3 2methyl propene

Give six type of ethers that cannot be synthesized by the typical Williamson
synthesis.

11.3 ALKOXYMERCURATIONDEMERCURATION
In overall alkoxymercurationdemercuration reaction, ROH is added to the double bond.
The reaction do not involve any carbocation as intermediate, so it is free from rearrangement and
also involves syn addition, which is in accordance to Markownikoff’s rule.
Alkenes react with mercuric acetate in the presence of alcohol to give alkoxymercurial
compound, which on demercuration by NaBH4 gives ethers.

R H H HgOAc H H
Alkoxymercuration NaBH4
C=C + ROH + Hg(OAc)2 OAc
RCCH RCCH
H Demercuration
H
OR H OR H
 ALCOHOLS PHENOLS AND ETHERS

12. GENERAL PHYSICAL PROPERTIES OF ETHERS

Diethyl ether is a highly volatile liquid, used as a solvent, as an anesthetic and in the
preparation of Grignard reagents.
Boiling point of ethers is less than that of the corresponding alcohols (of similar molar
mass) due to absence of hydrogen bonding. The solubility of ethers in water is comparable to that
of the alcohols as both are able to form hydrogen bond with water. The hybridization of oxygen
atom in ether is sp3, so the shape of an ether molecule is angular or bent with bond angle of 110°.
The bond angle is greater than the normal bond angle in a tetrahedron with lone pairs,
as repulsion between the bulkier alkyl groups is dominant over the lone pair repulsion.

R
110°
O
R . ..
.
Ether molecules are polar and they have a small net dipole moment. The net dipole
moment of diethyl ether is 1.18 D.
Et
O
net dipole moment = 1.18 D

Et

13. GENERAL CHEMICAL REACTIONS OF ETHERS

Ethers are quite unreactive compounds as ether linkage is very stable towards bases,
oxidising agents and reducing agents. Ethers can be easily cleaved in the presence of acids.
Few of the common reactions of ether are as follows:

13.1 SALT FORMATION

When ethers are treated with cold concentrated inorganic acids, these form oxonium salts.
The reaction between ether and acid is a Lewis acidbase type interaction.

R .. R 
O: + HCl O  H Cl
R R
Ether hydrochloride

R .. R 
2 O: + H2SO4 OH SO24 
R R 2
Ether sulphate
13.2 CLEAVAGE BY HEATING WITH ACIDS
Ethers on reaction with acids (HX) in presence of heat undergoes cleavage to form an alkyl
halide and an alcohol. Alcohol on further reaction with HX gives second molecule of alkyl halide.
 ALCOHOLS PHENOLS AND ETHERS

ROR + HX  RX + ROH

ROH + HX  RX + H2O
HI is more reactive towards ether than HBr and HBr is more reactive than HCl.
The cleavage of ethers takes place in vigorous conditions i.e. concentrated acids
(HI and HBr) and at elevated temperatures.

Mechanism:
In the first step, ether is protonated by HX to give protonated ether. In the second step,
halide ion acts as nucleophile and attacks protonated ether to undergo cleavage. This step is
favoured because the leaving group (alcohol) is weakly basic.
H
.. 
R O: R + H X R O R + X
Step I: protonated ether

H 
H 
 SN2
R O R + X pathway X R O R R X + ROH
 +
SN1
pathway


R + ROH

+X
Step II: R X
Reaction in second step can take the direction of SN1 or SN2 pathway, depending upon the
conditions employed and the structure of ether. When both the alkyl groups are methyl or 1°, it will
follow SN2 reaction and when atleast one of the alkyl group is 3°, the reaction follows SN1 pathway.
For all other cases, it can undergo SN1 or SN2 pathway, depending upon the reaction conditions.

For example,
H
HI 
CH3OC2H5 (One equivalent) C2H5OCH3 + I
SN2
pathway
H 

C2H5 O CH3 I CH3I + C2H5OH
 +

H

CH3OC(CH3)3 + HI CH3OC(CH3)3 + I
(One equivalent)
SN1
pathway

I 
(CH3)3CI (CH3)3C + CH3OH

Illustration 4
 ALCOHOLS PHENOLS AND ETHERS

(a) Give SN2 and SN1 mechanisms for the cleavage of ethers with HI. (b) Why does SN2
cleavage occur at a faster rate with HI than with HCl?
Solution:


R O R + HI R O R + I
H
(a) Step 1 base1 acid2 acid1 base2

H
 slow
Step 2 for SN2
I + R O R RI + HOR(Ris 1°)

H
slow +
Step 2 for SN1
ROR R (R is 3°) + ROH

Step 3 for SN1 R+ + I  RI

(b) The transfer of H+ to ROR in step 1 is greater with HI, which is a stronger acid, than with HCl.
Furthermore, in step 2, I, being a better nucleophile than Cl, reacts at a faster rate.
13.3 ACTION OF PCl5 OR SOCl2
Ethers on heating with PCl5 or SOCl2 undergoes cleavage to form alkyl chlorides.

C2H5  O  C2H5 + Cl  PCl3  Cl 2C2H5Cl + POCl3


CH3  O  CH2CH2CH3 + Cl  SO  Cl CH3Cl + CH3CH2CH2Cl + SO2
The cleavage by PCl5 or SOCl2 is used to distinguish metameric ethers as their cleavage
products would be different.

13.4 OXIDATION OF ETHER BY AIR OR OZONE

When ethers are exposed to atmospheric oxygen for a long time, they are oxidised to ether
hydroperoxides. Ether hydroperoxides are solids, which explodes on slightest heating or on
rubbing. So ether samples, which are exposed to air should not be used for solvent extraction, as
during distillation, explosion may occur. Thus, from such ether samples, hydroperoxides are to be
removed before using it for solvent extraction.
RCH2CH2OCH2CH2R + O2 RCH2CHOCH2CH2R
OOH
Ethers are purified by extraction with excess of FeSO4 solution, which reduces the
OOH group to the nonexplosive, innocuous OH group.

This reaction has a radical mechanism in which oxygen (a diradical) is the radical initiator.

Mechanism:
Initiation step:
 ALCOHOLS PHENOLS AND ETHERS

.. .. . .. ..
RCH2CH2OCH2CH2R + . O
..  O
..
. ..  O
RCH2CHOCH2CH2R + H:O ..
.
. .. ..
RCH2CHOCH2CH2R + .O
..  O..
. RCH2CHOCH2CH2R
..
Propagation step 1: .. O...
:O
Propagation step 2:

RCH2CHOCH2CH2R + RCH2CH2OCH2CH2R
..
:O
.. .. .
O .
RCH2CHOCH2CH2R + RCH2CHOCH2CH2R
OOH
Step 1 and 2 of the propagation step are repeated to continue the chain mechanism.
The chain may finally terminate by the collision between any two free radicals.

Which ether, n–propyl or i–propyl is more prone to hydroperoxide formation?

CYCLIC ETHERS

If oxygen atom is a part of carbon skeleton in the ring, then such ethers are called cyclic
ethers. Their general formula is (CH2)nO where n = 2, 3, 4, 5 and 6.

O O O O
(n = 2) (n = 3) (n = 4) (n = 5) (n = 6)
Oxirane Oxetane Oxolane Oxane Oxepane
Three membered cyclic ethers can also be considered as oxides of the parent alkene.
Thus, they are named as alkene oxides or epoxides.

CH2 CH2 CH2 CHCH2CH3

O O
ethylene oxide 1, 2butene oxide/2–ethyloxirane
(epoxy ethane) (1,2epoxy butane)

CH2 CHCH3 CH3–CH CHCH3

O O
propylene oxide/ 2methyl oxirane 2, 3butene oxide/
(1, 2epoxy propane) 2, 3dimethyloxirane
(2, 3epoxy butane)

There are two IUPAC approved ways to name epoxides. According to one method, the
threemembered oxygen containing ring is called “oxirane”, with oxygen atom occupying
1position. Thus, propylene oxide is called 2methyl oxirane. Alternatively, an epoxide can also be
 ALCOHOLS PHENOLS AND ETHERS

named as an alkane, with “epoxy” substituent and the numbers of the carbons to which the oxygen
is attached immediately preceding the alkane name.

14. PREPARATION OF EPOXIDES

Epoxide can be prepared by the oxidation of alkene using peroxy acids.
RCH=CH2 + RCO3H RCH  CH2 + RCO2H
O
The reaction is referred as epoxidation and we have already discussed its mechanism in
the lesson alkenes. Three membered cyclic ethers can also be prepared by internal SN2 reaction
of a chlorohydrin.

Cl 
Cl
OH Cl
CH2CH2 CH2CH2 CH2CH2

OH O O

15. REACTIONS OF EPOXIDES

As three membered epoxide ring is highly strained, so they are highly susceptible to ring
cleavage in order to get relieve from the strain. Thus, epoxides can be cleaved by acids as well as
by bases.

15.1 ACIDCATALYSED CLEAVAGE OF EPOXIDES


.. OH2
+
H H2O:
CH2  CH2 CH2  CH2 CH2  CH2
O O OH
Symmetrical H+
epoxide H
Protonated
epoxide OH
CH2  CH2
OH
ethylene glycol
In the first step, protonation takes place to give protonated epoxide. This is then attacked
by H2O ( a poor nucleophile) to undergo ring opening at room temperature, which finally loses H+ to
give ethylene glycol.

15.2 BASECATALYSED CLEAVAGE OF EPOXIDES

OH OH
OH H2O
CH2  CH2 CH2  CH2 CH2  CH2
(Solvent)
O O
 OH OH
ethylene glycol
 ALCOHOLS PHENOLS AND ETHERS

Here, the nucleophile attacks epoxide ring and cleave it, which then abstracts a proton
from the solvent (or from the acid added after the reaction is over) to give ethylene glycol. When a
nucleophile attacks an unprotonated epoxide, the reaction is a pure SN2 and thus nucleophile
attacks the less hindered carbon.
In case of unsymmetrical epoxides, for instance, propylene oxide, the acidcatalysed
cleavage proceeds as follows:
+

OH2
+ .. +
H H2O:
CH3CH  CH2 CH3CH  CH2 CH3  CH CH2
O O O +
H H
Transition state
(Bond breaking exceeds
bond making)


OH OH2
H+
CH3  CH  CH2 CH3  CH  CH2
OH OH
In this case, after the protonation step, nucleophile attacks at the more substituted carbon
because the leaving group (alcohol) is better one and the nucleophile (H2O) is poor one. Thus,
leaving group starts leaving before the nucleophile attacks or in other words, bond breaking is
more than bond making in the transition state. As the carbonoxygen bond breaks faster, a partial
positive charge develops on the carbon that is losing its share of the oxygen’s electrons and
protonated epoxide breaks preferentially in the direction that puts the partial positive charge on the
more substituted carbon because the positive charge is more stable here due to +I effect of methyl
group. Thus, we can say that the reaction proceeds by SN2 pathway with considerable SN1
characteristics in it. The reaction is neither pure SN1 (because a carbocation is not fully formed)
nor pure SN2 (because leaving group begins to depart before the compound is attacked by the
nucleophile).

In propylene oxide, basecatalysed cleavage proceed as follows:

OH OH
OH H2O
CH3  CH  CH2  
CH3 CH CH2 CH3  CH  CH2
(Solvent)

O O OH
Since, this reaction is a pure SN2 reaction, so nucleophile attacks at the less substituted
carbon to undergo ring opening. The alcoholalkoxide ion then takes up a proton from the solvent
to give find product.

The product of acidcatalysed cleavage and basecatalysed cleavage of propylene oxide

are different because they are enantiomers having similar values of optical rotation but with
different sign.

Illustration 5
Account for the 14Clabeled product from the following reaction,
 ALCOHOLS PHENOLS AND ETHERS
 14 14 14
MeO + H2 C CHCH2Cl  MeO CH2CH CH2 not H2 C CHCH2OMe
O O O
Solution:
This is not a direct Williamson reaction. Instead the reaction is initiated by an SN2 displacement by
CH3O on the less substituted 14C of the epoxide, giving an intermediate alkoxide ion. The O then acts as a
nucleophile (neighboring group participation) to displace Cl by a second SN2 reaction, forming the product.

14 14 14 

MeO + H2 C CHCH2Cl CH3OCH2CHCH2Cl MeOCH2CH CH2 + Cl

O O O

16. ARYL ETHERS

Phenols are converted into alkyl aryl ethers by reaction in alkaline solution with alkyl
halides. For the preparation of aryl methyl ethers, dimethyl sulfate, (CH3)2SO4 is frequently used
instead of more expensive methyl halides. For example,


OH O Na+ OCH3

NaOH
+ CH3  Br + NaBr
H2O

Anisole


OH O Na+ OCH3

NaOH
+ CH3  OSO2OCH3 + CH3OSO2ONa
H2O

Anisole
The second method is a better method to prepare anisole because methyl sulphonates
(mesylates) are better leaving group than Br, which causes faster substitutions. Secondly, with
respect to CH3Br, dimethyl sulphate is less expensive, so economically, (CH3)2SO4 is better to
cause methylation of phenol.


OH O Na+ CH2Br

NaOH O  CH2
H2O + + NaBr
Benzyl phenyl ether
 ALCOHOLS PHENOLS AND ETHERS

 +
OH O Na OC2H5

NaOH
H2O
C2H5  OSO2OC2H5 + C2H5OSO2ONa

Phenetole

The mechanism of the above reaction can be outlined as follows. In alkaline solutions,
phenol exist as phenoxide ion which acts as nucleophile and attacks the alkyl halide
(or the dialkyl sulfate) and displaces halide ion (or sulfate ion).

ArO + R  X  ArO  R + X
ArO + CH3  OSO3CH3  ArO  CH3 + OSO3CH3
The above reaction is familiar Williamson’s synthesis, which can even be used for the
preparation of unsymmetrical ethers like alkyl aryl ethers.
Since phenoxides are prepared from phenols and since alkyl halides are conveniently
prepared from alcohols, alkyl aryl ethers (like dialkyl ethers) are ultimately synthesized from two
hydroxy compounds.
Aryl halides cannot be used in the Williamson’s synthesis because of their low reactivity
towards nucleophilic substitution. For the preparation of any alkyl aryl ether, there can be two
combinations of reactants, but one combination can usually be ruled out. For example,
Route (A)
+ 
CH3CH2CH2Br + Na O Feasible

CH3CH2CH2O
Route (B)
 +
CH3CH2O Na + Br Not Feasible
Phenyl npropyl ether
ALCOHOLS PHENOLS AND ETHERS
 ALCOHOLS PHENOLS AND ETHERS

PROFICIENCY TEST III

The following 10 questions deal with the basic concepts of this section. Answer the
following briefly. Go to the next section only if your score is greater than or equal to 8.
Do not consult the study material while attempting the questions.

1. ipropyl ether forms hydroperoxide more/less readily than npropyl ether.

2. PhOC2H5 on cleavage with HI gives  and .

3. Williamson’s method is suitable for preparing  ethers.

4. Acidcatalysed dehydration of alcohols is suited for preparing  ethers.

5. ClCH2CH=CH2 is  reactive than BrCH2CH2CH3 for preparing ether using

Williamson’s synthesis.

6. True/False. Ethers are nonpolar molecules.

7. True/False. Ethyl methyl ether on cleavage with PCl5 give equimolar mixture of ethyl
chloride and methyl chloride.

8. True/False. Anisole can be prepared by the reaction of sodium methoxide on

chlorobenzene.

9. True/False. In unsymmetrical epoxides, the nucleophile attacks at more substituted

carbon in acidcatalysed cleavage.

10. True/False. The basecatalysed cleavage of unsymmetrical epoxides proceeds by pure

SN2 mechanism.
 ALCOHOLS PHENOLS AND ETHERS

ANSWERS TO PROFICIENCY TEST III

1. More

2. PhOH and C2H5I

3. Symmetrical and unsymmetrical

4. Symmetrical

5. More

6. False (They have net dipole moment)

7. True

8. False

9. True

10. True