ALCOHOLS, PHENOLS AND ETHERS

Introduction
Alcohols
(a) These are the organic compounds in which –OH group is directly attached with carbon.
(b) These are hydroxyl derivatives of alkanes, mono alkyl derivatives of water.
(c) Their general formula is Cn Hn+1OH or CnH2n+2O.

Applications
The ordinary spirit used for polishing wooden furniture is chiefly a compound containing hydroxyl
group, ethanol.
The sugar we eat, the cotton used for fabrics, the paper we use for writing, are all made up of
compounds containing –OH groups.

Phenols
Phenol contains –OH group(s) directly attached to the carbon atom(s) of an aromatic system
(C6H5OH).

Ethers
The substitution of a hydrogen atom in a hydrocarbon by an alkoxy or aryloxy group (R–O/Ar–O)
yields another class of compounds known as ‘ethers’, for example, CH3OCH3 (dimethyl ether).

Classification of Alcohols
Mono, Di, Tri or Polyhydric- Compounds Alcohols and phenols may be classified as mono-, di-, tri-
or polyhydric compounds depending on whether they contain one, two, three or many hydroxyl groups
respectively in their structures as given below:

Compounds Containing Csp3 – OH Bond

In this class of alcohols, the –OH group is attached to an sp3 hybridised carbon atom of an alkyl
group. They are further classified
(a) Primary, secondary and tertiary alcohols: In these types of alcohols, the –OH group is
attached to the primary secondary and tertiary carbon atom, respectively as depicted below.

(b) Allylic alcohols: In these alcohols, the –OH group is attached to an sp3 hybridised carbon next to
the carbon-carbon double bond, i.e. to an allylic carbon. For example
(c) Benzylic alcohols: In these alcohols, the –OH group is attached to an sp3 –hybridised carbon
atom next to an aromatic ring. For example Allylic and benzylic alcohols may be primary, secondary
or tertiary

(d)Vinylic alcohols: These alcohols contain –OH group bonded to a carbon- carbon double i.e., to a
vinylic carbon or to an aryl carbon. These alcohols are also known as vinylic alcohols
Vinylic alcohol : CH2 =CH-OH

Classification of Phenols
Phenols can be classified into monohydric, dihydric and trihydric based on the number of hydroxyl
groups attached to the benzene ring.
a. Monohydric phenols
b. Dihydric and trihydric phenols

Classification of Ethers

Ethers are classified as simple or symmetrical, if the alkyl or aryl groups attached to the oxygen
atom are the same, and mixed or unsymmetrical, if the two groups are different. Diethyl ether,
C2H5OC2H5 , is a symmetrical ether whereas C2H5OCH3 and C2H5OC6H5 are unsymmetrical ethers.

IUPAC Nomenclature of Alcohols

●​ The name of an alcohol is derived from

the name of the alkane from which the
alcohol is derived, by substituting ‘e’ of
alkane with the suffix ‘ol’.
●​ The position of substituents are
indicated by numerals.
●​ For this, the longest carbon chain
(parent chain) is numbered starting at the
end nearest to the hydroxyl group.
●​ The positions of the –OH group and
other substituents are indicated by using the
numbers of carbon atoms to which these are
attached.
●​ For naming polyhydric alcohols, the ‘e’
of alkane is retained and the ending ‘ol’ is
added.
●​ The number of –OH groups is
indicated by adding the multiplicative prefix, di, tri, etc., before ‘ol’.
●​ The positions of –OH groups are indicated by appropriate locants, e.g., HO–CH2–CH2–OH is
named as ethane–1, 2-diol.
Cyclic alcohols are named using the prefix cyclo and considering the —OH group attached to C–1

Some examples are shared below.

Nomenclature of Phenols
The simplest hydroxy derivative of benzene is phenol. The substituted phenols are named as
derivatives of phenol.

Methyl phenols are known as cresols.

Some dihydric and trihydric phenols are given below:

Nomenclature of Ethers

Common names of ethers are derived

from the names of alkyl/ aryl groups
written as separate words in
alphabetical order and adding the
word ‘ether’ at the end.
For example, CH3OC2H5 is ethyl
methyl ether.
If both the alkyl groups are the same,
the prefix ‘di’ is added before the alkyl
group.
For example, C2H5OC2H5 is diethyl
ether.
According to the IUPAC system of
nomenclature, ethers are regarded as
hydrocarbon derivatives in which a
hydrogen atom is replaced by an –OR or –OAr group, where R and Ar represent alkyl and aryl
groups, respectively. The larger (R) group is chosen as the parent hydrocarbon.

Isomerism in Alcohols
Alcohols exhibits the following isomerism
a. Chain isomerism
Alcohols containing four or more carbons exhibit chain isomerism in which chains attached to the -OH
group differ.
Eg. Butan-1-ol and 2-methyl-propan-1-ol
b. Position isomerism
Alcohols containing three or more carbons exhibit chain isomerism in which the isomers differ in the
position of the -OH group.
Eg. Butan-1-ol and Butan-2-ol
c. Functional isomerism
Monohydric alcohols containing two or more carbons exhibit functional isomerism with ethers
Eg. Ethanol and methoxymethane

Structures of Functional Functional

In alcohols, the oxygen of the –OH group is attached to carbon by a sigma (σ ) bond formed by the
overlap of a sp 3 hybridised orbital of carbon with a sp 3 hybridised orbital of oxygen.

Points to note
1.​ The C-O-H bond angle in alcohols is slightly less than the tetrahedral angle (109°-28′). It is
due to the repulsion between the unshared electron pairs of oxygen.
2.​ In phenols, the –OH group is attached to sp2 hybridised carbon of an aromatic ring. The
carbon– oxygen bond length (136 pm) in phenol is slightly less than that in methanol. This is
due to (i) partial double bond character on account of the conjugation of an unshared electron
pair of oxygen with the aromatic ring (ii) sp2 hybridised state of carbon to which oxygen is
attached.
3.​ In ethers, the four electron pairs, i.e., the two bond pairs and two lone pairs of electrons on
oxygen are arranged approximately in a tetrahedral arrangement. The bond angle is slightly
greater than the tetrahedral angle due to the repulsive interaction between the two bulky (–R)
groups. The C–O bond length (141 pm) is almost the same as in alcohols.

Think Tank 🤔
1.​ Assertion:Dipole moment of phenol is less than ethanol
Reason : Lone pair of electrons on methanol are localised on oxygen
(Hint- Think of resonance effect in phenol)

Preparation of Alcohols
1. From alkenes
(i) By acid catalysed hydration: Alkenes react with water in the presence of acid as a catalyst to
form alcohols. In case of unsymmetrical alkenes, the addition reaction takes place in accordance with
Markovnikov’s rule.

Mechanism
The mechanism of the reaction involves the following three steps:
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O +
H2O + H+ → H3O +

Step 2: Nucleophilic attack of water on carbocation.

Step 3: Deprotonation to form an alcohol.

(ii) By hydroboration–oxidation: Diborane (BH3)2 reacts with alkenes to give trialkyl boranes as an
addition product.
This is oxidised to alcohol by hydrogen peroxide in the presence of aqueous sodium hydroxide.
The addition of borane to the double bond takes place in such a manner that the boron atom gets
attached to the sp2 carbon carrying a greater number of hydrogen atoms.
The alcohol so formed looks as if it has been formed by the addition of water to the alkene in a way
opposite to Markovnikov's rule. In this reaction, alcohol is obtained in excellent yield.

2. From carbonyl compounds

(i) By reduction of aldehydes and ketones: Aldehydes and ketones are reduced to the
corresponding alcohols by addition of hydrogen in the presence of catalysts (catalytic hydrogenation).
The usual catalyst is a finely divided metal such as platinum, palladium or nickel.
It is also prepared by treating aldehydes and ketones with sodium borohydride (NaBH4 ) or lithium
aluminium hydride (LiAlH4 ). Aldehydes yield primary alcohols whereas ketones give secondary
alcohols.

(ii) By reduction of carboxylic acids and esters: Carboxylic acids are reduced to primary alcohols
in excellent yields by lithium aluminium hydride, a strong reducing agent.

NOTE- LiAlH4 is an expensive reagent, and therefore, used for preparing special chemicals only.
Commercially, acids are reduced to alcohols by converting them to the esters , followed by their
reduction using hydrogen in the presence of a catalyst (catalytic hydrogenation).

3. From Grignard reagents

Alcohols are produced by the reaction of Grignard reagents with aldehydes and ketones.
The reaction of Grignard’s reagents with formaldehyde produces a primary alcohol, with other
aldehydes it produces secondary alcohols and tertiary alcohols with ketones.

Think Tank 🤔
2.​ Assertion-Grignard reagent should be prepared in anhydrous conditions
Reason- The reagent decomposes to give corresponding alcohols

3.​ Assertion- During esterification the O-H bond of the alcohol is broken
Reason - Esterification is accompanied by loss of water molecule

4.​ Predict A,B,C in the following scheme

a.​ CH3CH2MgI+ A⟶B+H2O⟶n-propyl alcohol+C (Hint- Think about the appropriate
aldehyde which can undergo addition across the C=O bond)

Preparation of Phenols

Phenol, also known as carbolic acid, was first isolated in the early nineteenth century from coal tar.
Nowadays, phenol is commercially produced synthetically.
In the laboratory, phenols are prepared from benzene derivatives by any of the following methods:

1. From haloarenes- Chlorobenzene is fused with NaOH at 623K and 320 atmospheric pressure.
Phenol is obtained by acidification of sodium phenoxide so produced(Dow’s process)

2. From benzene sulphonic acid- Benzene is sulphonated with oleum and benzene sulphonic acid
so formed is converted to sodium phenoxide on heating with molten sodium hydroxide. Acidification of
the sodium salt gives phenol.

3. From diazonium salts- A diazonium salt is formed by treating an aromatic primary amine with
nitrous acid (NaNO2 + HCl) at 273-278 K. Diazonium salts are hydrolysed to phenols by warming with
water or by treating with dilute acids

4. From cumene
Most of the worldwide production of phenol is from cumene.
Phenol is manufactured from the hydrocarbon, cumene. Cumene (isopropylbenzene) is oxidised in
the presence of air to cumene hydroperoxide. It is converted to phenol and acetone by treating it with
dilute acid. Acetone, a by-product of this reaction, is also obtained in large quantities by this method.

Think Tank 🤔
5.​ Effect the following conversions
a.​ Nitrobenzene to phenol
b.​ Phenol from benzene
c.​ o-nitroaniline to o-nitrophenol

Physical Properties of Alcohols

1.​ Physical state- The lower alcohols are liquids while higher having more than 12 carbon atoms
are solids. They are colourless, neutral substances with characteristic sweet, alcoholic odour
and burning taste.
2.​ Boiling Points- Boiling points of alcohols are much
higher than those of alkanes, haloalkanes or ethers of
comparable molecular masses. This is because in alcohols
strong intermolecular hydrogen bonding exists due to which a
large amount of energy is required to break these bonds.
Among isomeric alcohols, the boiling point decreases with
increase in branching in the alkyl group (due to decrease in
van der Waals forces with decrease in surface area). For isomeric alcohols, the boiling points
generally follow the order:
Primary alcohol > Secondary alcohol > Tertiary alcohol.

3.​ Solubility of alcohols: The first three members are

completely miscible with water. The solubility rapidly decreases
with increase in molecular mass. The higher members are almost
insoluble in water but are soluble in organic solvents like ether,
benzene, etc. The solubility of lower alcohols in water is due to
 their ability to form hydrogen bonds with water molecules.

The solubility of alcohols in water decreases with increase in molecular mass because with
increase in molecular mass the non-polar alkyl group becomes predominant and masks the
effect of polar —OH group. In addition, among the isomeric alcohols the solubility increases
with branching of the chain. It is because the surface area of the nonpolar part in the molecule
decreases, thus enhancing the solubility.

Physical properties of Phenols

1.​ Colour and physical state- Phenol is colourless, but develops mild pink colour due to aerial
oxidation. It's a syrupy liquid or crystalline solid and has a strong odour.
2.​ Solubility- Phenol is sparingly soluble in water due to the hydrophobic nature of the benzene
ring. Phenols, however, are soluble in NaOH and
alcohols.
3.​ Boiling points- The boiling point of phenol is
higher than that of the corresponding Haloarenes of
comparable molecular masses. This is due to
intermolecular H-bonding.

Chemical Properties of Alcohols

Alcohols are versatile compounds. They react both as nucleophiles and electrophiles.
1.​ The bond between O–H is broken when alcohols react as nucleophiles

2.​ The bond between C–O is broken when they react as electrophiles. Protonated alcohols react
in this manner.

Based on the cleavage of O–H and C–O bonds, the reactions of alcohols and phenols may be divided
into two groups:
a.​ Reactions involving cleavage of O–H bond
b.​ Reactions involving cleavage of carbon – oxygen (C–O) bond in alcohols

Reactions involving cleavage of O–H bond

1.​ Reaction with metals: Alcohols and phenols react with active metals such as sodium,
potassium and aluminium to yield corresponding alkoxides/phenoxides and hydrogen.
The above reactions suggest that alcohols are acidic in nature. Infact, they behave as Bronstead
acids as they can donate a proton to a strong base.
2.​ Acidity of alcohols: The acidic character of alcohols is due to the polar nature of the O–H
bond. An electron-releasing group (–CH3 , –C2H5 ) increases electron density on oxygen
tending to decrease the polarity of O-H bond. This decreases the acid strength. For this
reason, the acid strength of alcohols decreases in the following order:

Acidic strength can also be explained based on the stability of the conjugate base.
Higher the stability of the conjugate base, more will be the acidity of the alcohol.

The basic strength of the alkoxide ion is as follows

Comparison of acidic strength of alcohols and water.

Alcohols are, however, weaker acids than water. This can be illustrated by the reaction of water with
an alkoxide. This reaction shows that water is a better proton donor (i.e., stronger acid) than alcohol.
Also, in the above reaction, we note that an alkoxide ion is a better proton acceptor than hydroxide
ion, which suggests that alkoxides are stronger bases (sodium ethoxide is a stronger base than
sodium hydroxide).

Acidity of Phenols
a.​ Phenols are more acidic than alcohols and water.
b.​ Evidence - The reactions of phenol with metals (e.g., sodium, aluminium) and sodium
hydroxide indicate its acidic nature.
c.​ Reasons- The hydroxyl group, in phenol is directly attached to the sp 2 hybridised carbon of
benzene ring which acts as an electron withdrawing group. Due to this, the charge distribution
in phenol molecules, as depicted in its resonance structures, causes the oxygen of –OH group
to be positive.
(i) Resonance effect in phenol- Due to the higher electronegativity of sp 2 hybridised carbon of
phenol to which –OH is attached, electron density decreases on oxygen. This increases the
polarity of O–H bond and results in an increase in ionisation of phenols than that of alcohols
 (ii)Phenoxide ion is more stable than alkoxide ion-In alkoxide ion, the negative charge is
localised on oxygen while in phenoxide ion, the charge is delocalised. The delocalisation of negative
charge makes phenoxide ion more stable and favours the ionisation of phenol.

Note
1.​ Presence of electron withdrawing groups on phenol increases its acidity, eg- p-nitrophenol is
more acidic than phenol itself
2.​ Presence of electron donating groups on phenol decreases its acidity, eg- p-methylphenol is
less acidic than phenol itself
3.​ Acidity can be measured in terms of pKa values (pKa= - log(Ka) Where Ka is the dissociation
constant)
4.​ Higher the Ka more will be the acidity and vice versa
5.​ Higher the pKa less will be the acidity and vice versa
6.​ The pKa values of various alcohols are attached for your reference

Think Tank🤔
6.​ Assertion- Methanol is more acidic than water
Reason - Methoxide is weaker than water's conjugate base, hydroxide.
7.​ Assertion- Phenol is a million times more acidic than ethanol
Reason - Phenoxide ion is more stable than Ethoxide ion
8.​ Arrange the following compounds in increasing order of their acid strength: Propan-1-ol,
2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, phenol, 4-methylphenol.(NCERT)

2. Esterification

a.​ Alcohols and phenols react with carboxylic acids, acid chlorides and acid anhydrides to form

esters.
b.​ The reaction with carboxylic acid and acid anhydride is carried out in the presence of a small
 amount of concentrated sulphuric acid. The reaction is reversible, and therefore, water is
removed as soon as it is formed.
c.​ The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to
neutralise HCl which is formed during the reaction. It shifts the equilibrium to the right hand

side.
d.​ The introduction of acetyl (CH3CO) group in alcohols or phenols is known as acetylation.
Acetylation of salicylic acid produces aspirin

Think Tank 🤔
9.​ Assertion- Esterification involves the cleavage of O-H bond of Alcohols
Reason - Esters are sweet smelling substances

Reactions involving cleavage of carbon – oxygen (C–O) bond in alcohols

The reactions involving cleavage of C–O bonds take place only in alcohols. Phenols show this type of
reaction only with zinc.
1. Reaction with hydrogen halides: Alcohols react with hydrogen halides to form alkyl halides.
Note
a.​ The difference in reactivity of three classes of alcohols with HCl distinguishes them from one
another (Lucas test).
b.​ Alcohols are soluble in Lucas reagent (conc. HCl and ZnCl2 ) while their halides are
immiscible and produce turbidity in solution.
c.​ In case of tertiary alcohols, turbidity is produced immediately as they form the halides easily.
Primary alcohols do not produce turbidity at room temperature.
d.​ 30 alcohols often do not need a lewis acid catalyst for reaction with lewis acid.

Order of reactivity of Halogen acid - HI>HBr>HCl

Order of reactivity of Alcohol- 30>20>10

Think Tank🤔 0
10.​Assertion- 3 alcohols are highly reactive towards halogen acid
Reason - The reaction involves the formation of 30 carbocation which is highly stable.

2. Reaction with phosphorus halides: : Alcohols are converted to alkyl halides by reaction with
phosphorus trihalides or pentahalides.

3. Dehydration: Alcohols undergo dehydration (removal of a molecule of water) to form alkenes on

treating with a protic acid e.g., concentrated H2SO4 or H3PO4 , or catalysts such as anhydrous zinc
chloride or alumina
Ethanol undergoes dehydration by heating it with concentrated H2SO4 at 443 K.

Secondary and tertiary alcohols are dehydrated under milder conditions.

The relative ease of dehydration of alcohols: 30>20>10

Tertiary carbocations are more stable and therefore are easier to form than secondary and primary
carbocations; tertiary alcohols are the easiest to dehydrate.

Points to note about dehydration

1.​ Dehydration of 20and 30 alcohols always takes place in accordance to Saytzeff’s rule (an
alkene with more number of alkyl substitutions on either side of the double bonded carbon,
being the most preferred product)

2.​ As dehydration involves the formation of a carbocation, there exists a scope of rearrangement.
For example,

Mechanism Step 1: Formation of protonated alcohol.

Step 2: Formation of carbocation: It is the slowest step and hence, the rate
determining step of the reaction.

Step 3: Formation of ethene by elimination of a proton.

4. Oxidation:
a.​ Oxidation of alcohols involves the formation of a carbon oxygen double bond with cleavage of
 an O-H and C-H bonds. Such a cleavage and formation of bonds occur in oxidation reactions.
b.​ These are also known as dehydrogenation reactions as these involve loss of dihydrogen from
an alcohol molecule.
c.​ Depending on the oxidising agent used, a primary alcohol is oxidised to an aldehyde which in
turn is oxidised to a carboxylic acid.
d.​ Strong oxidising agents such as acidified potassium permanganate are used for getting
carboxylic acids from alcohols directly.

e.​ CrO3 in anhydrous medium is used as the oxidising agent for the isolation of aldehydes.

f.​ A better reagent for oxidation of primary alcohols to aldehydes in good yield is pyridinium
chlorochromate (PCC), a complex of chromium trioxide with pyridine and HCl.

g.​ Secondary alcohols are oxidised to ketones by chromic anhydride (CrO3 ).

h.​ Tertiary alcohols are generally resistant to oxidation, however under very strong oxidising
conditions (H2SO4+KMnO4 or H2SO4+ K2Cr2O7),cleavage of various C-C bonds takes place
and a mixture of carboxylic acids containing lesser number of carbon atoms is formed.

5. Dehydrogenation- When the vapours of a primary or a secondary alcohol are passed over heated
copper at 573 K, dehydrogenation takes place and an aldehyde or a ketone is formed while tertiary
alcohols undergo dehydration.

Things to ponder!
Biological oxidation of methanol and
ethanol in the body produces the
corresponding aldehyde followed by the
acid. At times the alcoholics, by mistake,
drink ethanol, mixed with methanol also
A methanol poisoned patient is treated by giving
 intravenous infusions of diluted ethanol. The enzyme called denatured alcohol. In the body,
responsible for oxidation of aldehyde (HCHO) to acid is methanol is oxidised first to methanal
swamped allowing time for kidneys to excrete and then to methanoic acid, which may
methanol. cause blindness and death.

Reactions of phenols
Following reactions are shown by phenols only.

1. Electrophilic aromatic substitution

a.​ In phenols, the reactions that take place on the aromatic ring are electrophilic substitution
reactions
b.​ The –OH group attached to the benzene ring activates it towards electrophilic substitution.
Also, it directs the incoming group to ortho and para positions in the ring as these positions
become electron rich due to the resonance effect caused by –OH group. The resonance
structures are shown under acidity of phenols.
(i) Nitration: With dilute nitric acid at low temperature (298 K), phenol yields a mixture of ortho and
para nitrophenols.

The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam volatile
due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to intermolecular
hydrogen bonding which causes the association of molecules

With concentrated nitric acid, phenol is converted to 2,4,6-trinitrophenol. The product is commonly
known as picric acid. The yield of the reaction product is poor.

Nowadays picric acid is prepared by treating phenol first with concentrated sulphuric acid which
converts it to phenol-2,4-disulphonic acid, and then with concentrated nitric acid to get
2,4,6-trinitrophenol.
(ii) Halogenation: On treating phenol with bromine, different reaction products are formed under
different experimental conditions.
(a) When the reaction is carried out in solvents of low polarity such as CHCl3 or CS2 and at low
temperature, monobromo phenols are formed.

The usual halogenation of benzene takes place in the presence of a Lewis acid, such as FeBr3 , which
polarises the halogen molecule. In case of phenol, the polarisation of bromine molecules takes place
even in the absence of Lewis acid. It is due to the highly activating effect of the –OH group attached
to the benzene ring.
(b)When phenol is treated with bromine water, 2,4,6-tribromophenol is formed as white precipitate.

2. Kolbe’s reaction Phenoxide ion generated by treating phenol with sodium hydroxide is even more
reactive than phenol towards electrophilic aromatic substitution. Hence, it undergoes electrophilic
substitution with carbon dioxide, a weak electrophile. Ortho hydroxybenzoic acid is formed as the
main reaction product.

3. Reimer-Tiemann reaction On treating phenol with chloroform in the presence of sodium hydroxide,
a –CHO group is introduced at the ortho position of the benzene ring. This reaction is known as the
Reimer - Tiemann reaction. The intermediate substituted benzal chloride is hydrolysed in the
presence of alkali to produce salicylaldehyde.

4. Reaction of phenol with zinc dust Phenol is converted to benzene on

heating with zinc dust.

5. Oxidation Oxidation of phenol with chromic acid produces a conjugated diketone known as
benzoquinone. In the presence of air, phenols are slowly oxidised to dark coloured mixtures
containing quinones.

Some Commercially Important Important Alcohols

1. Methanol
a.​ Methanol, CH3OH, also known as ‘wood spirit’, was produced by destructive distillation of
wood.
b.​ Today, most of the methanol is produced by catalytic hydrogenation of carbon monoxide at
high pressure and temperature and in the presence of ZnO – Cr2O3 catalyst.
c.​ Methanol is a colourless liquid and boils at 337 K.
d.​ It is highly poisonous in nature. Ingestion of even small quantities of methanol can cause
blindness and large quantities causes even death.
e.​ Methanol is used as a solvent in paints, varnishes and chiefly for making formaldehyde.

2. Ethanol
a.​ Ethanol, C2H5OH, is obtained commercially by fermentation, the oldest method is from
sugars. The sugar in molasses, sugarcane or fruits such as grapes is converted to glucose
and fructose, (both of which have the formula C6H12O6 ), in the presence of an enzyme,
invertase.
b.​ Ethanol is a colourless liquid with boiling point 351 K. It is used as a solvent in the paint
industry and in the preparation of a number of carbon compounds.
c.​ The commercial alcohol is made unfit for drinking by mixing in it some copper sulphate (to give
it a colour) and pyridine (a foul smelling liquid). It is known as denaturation of alcohol.
Nowadays, large quantities of ethanol are obtained by hydration of ethene

Ethers
Preparation of Ethers
1. By dehydration of alcohols Alcohols undergo dehydration in the presence of protic acids (H2SO4 ,
H3PO4 ). The formation of the reaction product, alkene or ether depends on the reaction conditions.
For example, ethanol is dehydrated to ethene in the presence of sulphuric acid at 443 K. At 413 K,
ethoxyethane is the main product.
Order of reactivity- 30<20<10

The formation of ether is a nucleophilic bimolecular reaction (SN2) involving the attack of alcohol
molecule on a protonated alcohol, as indicated below:
 1. Protonation of alcohol

2. Nucleophilic attack of alcohol to form protonated ether

3. Deprotonation to form ether

Limitations
1.​ The method is suitable for the preparation of ethers having primary alkyl groups only.
2.​ The alkyl group should be unhindered and the temperature be kept low. Otherwise the
reaction favours the formation of alkene.
3.​ The reaction follows SN1 pathway when the alcohol is secondary or tertiary about which you
will learn in higher classes.
4.​ However, the dehydration of secondary and tertiary alcohols to give corresponding ethers is
unsuccessful as elimination competes over substitution and as a consequence, alkenes are
easily formed.
5.​ The method is not suitable for preparation of unsymmetrical ethers as it often gives a mixture
of ethers

2. Williamson synthesis
1.​ It is an important laboratory method for the preparation of symmetrical and unsymmetrical
ethers.
2.​ In this method, an alkyl halide is allowed to react with sodium alkoxide.
3.​ Ethers containing substituted alkyl groups (secondary or tertiary) may also be prepared by
this method.
4.​ The reaction involves SN2 attack of an alkoxide ion on primary alkyl halide.

5.​ Better results are obtained if the alkyl halide is primary.

6.​ In case of secondary and tertiary alkyl halides, elimination competes over substitution.
7.​ If a tertiary alkyl halide is used, an alkene is the only reaction product and no ether is formed.
8.​ It is because alkoxides are not only nucleophiles but strong bases as well. They react with
alkyl halides leading to elimination reactions.
9.​ Phenols are also converted to ethers by this method. In this, phenol is used as the phenoxide
moiety.
 10.​It should be noted that the reaction of aryl halides and sodium alkoxide is not feasible, as the
halogen carbon bond in aryl halides can't be broken easily. Thus the reaction of
chlorobenzene with sodium methoxide is not feasible.
11.​Similarly diphenyl ethers can’t be prepared by williamson ether synthesis.

Physical Properties

1.​ Polarity-The C-O bonds in ethers are polar and thus, ethers have a net dipole moment.
2.​ Boiling points- The weak polarity of ethers do not appreciably affect their boiling points which
are comparable to those of the alkanes of comparable molecular masses but are much lower
than the boiling points of alcohols as shown in the following cases:

3.​ The large difference in boiling points of alcohols and ethers is due to the presence of hydrogen
bonding in alcohols.
4.​ Solubility -The miscibility of ethers with water
resembles those of alcohols of the same molecular mass.
Both ethoxyethane and butan-1-ol are miscible to almost
the same extent i.e., 7.5 and 9 g per 100 mL water,
respectively while pentane is essentially immiscible with
water. This is due to the fact that just like alcohols, oxygen
of ether can also form hydrogen bonds with water
molecules as shown.

Chemical Properties of Ethers

1. Cleavage of C–O bond in ethers
a.​ Ethers are the least reactive of the functional groups.
b.​ The cleavage of C-O bond in ethers takes place under drastic conditions with excess of
hydrogen halides.
c.​ The reaction of dialkyl ether gives two alkyl halide molecules.

d.​ Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the more stable aryl-oxygen
bond. The reaction yields phenol and alkyl halide.
 e.​ Ethers with two different alkyl groups are also cleaved in the same manner

f.​ The order of reactivity of hydrogen halides is as follows: HI > HBr > HCl.
g.​ The cleavage of ethers takes place with concentrated HI or HBr at high temperature.

The reaction of an ether with concentrated HI starts with protonation of an ether molecule.
Step 1: The reaction takes place with HBr or HI because these reagents are sufficiently acidic.

Step 2: Iodide is a good nucleophile. It attacks the least substituted carbon of the oxonium ion
formed in step 1 and displaces an alcohol molecule by SN2 mechanism. Thus, in the cleavage of
mixed ethers with two different alkyl groups, the alcohol and alkyl iodide formed, depending on the
nature of alkyl groups.

When primary or secondary alkyl groups are present, it is the lower alkyl group that forms alkyl
iodide (SN2 reaction). When HI is in excess and the reaction is carried out at high temperature,
ethanol reacts with another molecule of HI and is converted to ethyl iodide.
Step 3:

Points to Note
1.​ When one of the alkyl group is a tertiary group, the halide formed is a tertiary halide.
2.​ It is because in step 2 of the reaction, the departure of the leaving group (HO–CH3 ) creates
a more stable carbocation [(CH3 )3C+], and the reaction follows SN1 mechanism.

3.​ In case of anisole, methylphenyl oxonium ion is formed by protonation of ether.

4.​ The bond between O–CH3 is weaker than the bond between O–C6H5 because the carbon of
phenyl group is sp2 hybridised and there is a partial double bond character.
5.​ Therefore the attack by I– ion breaks O–CH3 bond to form CH3I. Phenols do not react further
to give halides because the sp2 hybridised carbon of phenol cannot undergo nucleophilic
 substitution reaction needed for conversion to the halide.

Think Tank 🤔
11.​Assertion-Diphenyl ether reacts with HI @ 373K to give phenol and iodobenzene
Reason- The Csp2- O bond of diphenyl ether can't be broken due to partial double bond
character.
12.​Assertion-benzyl methyl ether reacts with HI @ 373K to give benzyl iodide and methanol
Reason- Benzyl cation is resonance stabilised.
2. Electrophilic substitution The alkoxy group (-OR) is ortho, para directing and activates the
aromatic ring towards electrophilic substitution in the same way as in phenol.

(i) Halogenation: Phenyl Alkyl ethers undergo usual halogenation in the benzene ring, e.g., anisole
undergoes bromination with bromine in ethanoic acid even in the absence of iron (III) bromide
catalyst. It is due to the activation of benzene rings by the methoxy group. Para isomer is obtained in
90% yield.

(ii) Friedel-Crafts reaction: Anisole undergoes Friedel-Crafts reaction, i.e. the alkyl and acyl groups
are introduced at ortho and para positions by reaction with alkyl halide and acyl halide in the presence
of anhydrous aluminium chloride (a Lewis acid) as catalyst.

(iii) Nitration: Anisole reacts with a mixture of concentrated sulphuric and nitric acids to yield a
mixture of ortho and para nitroanisole.
Uses of Ethers

1.​ Diethyl ether has been used widely as an inhalation anaesthetic. But
due to its slow effect and an unpleasant recovery period, it has been replaced,
as an anaesthetic, by other compounds.
2.​ It is a widely used industrial solvent. Under dry conditions it is used for
preparation of grignard reagent, in Wurtz reaction etc
3.​ Used as a refrigerant.
4.​ They are used as flavouring agent, eg Vanillin

Extended learning-Out of Box

Out of Box - Oxymercuration Demercuration Involves an electrophilic attack on the double bond by
the positively charged mercury species. The product is a mercurinium ion, an organometallic cation
containing a three-membered ring. With mercuric acetate, the product is 3-methyl-2-butanol
(Markonikov’s addition with no rearrangement, oxymercuration-demercuration reaction)

Phenols can also be prepared by the decarboxylation of Sodium salt of Salicylic acid.

Similarly, an ethereal solution of Phenylmagnesium bromide when bubbled with oxygen gives
phenol.

- The reduction of aldehydes, ketones and carboxylic acids with Sodium in Ethanol is
Out of Box

known as Bouveault Blanc reduction.

Answers to Think Tank questions

1 2 3 6 7 9 10 11 12

B C D B A B A C A

4. A- HCHO, B- CH3CH2CH2OMgI, C- Mg(OH)I

5. a. First convert nitrobenzene to aniline by reduction with H2,Ni. Then aniline is diszotised
using NaNO2+ HCl at 0-5°C, followed by treatment with H2O that gives phenol.
b. Treatment with oleum followed by hydrolysis with NaOH
c. Diazotize using NaNO2+ HCl at 0-5°C, followed by treatment with H2O that gives phenol.
8. 4-methylphenol<Phenol<3-nitrophenol<3,5-dinitrophenol<2,4,6-trinitrophenol

Prepared by Mr. P.Eazhilan, PGT-Chemistry, Velammal Vidhyashram, Surapet, Tilak wing