11.

Alcohols, Phenols and

Ethers

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 Alcohols, Phenols and Ethers
Introduction
• Alcohols and phenols are compounds formed when a hydrogen atom in a hydrocarbon is
replaced by–OH group.
• An alcohol contains one or more hydroxyl (OH) group(s) directly attached to carbon
atom(s) of analiphatic system.
• A phenol contains –OH group(s) directly attached to carbon atom(s) of an aromatic system
(C6H5OH).
• The substitution of a hydrogen atom in a hydrocarbon by an alkoxy or aryloxy group (R-
O/Ar-O) givesanother class of compounds known as ethers.
For example:C2H5-O-C2H5 (Dimethyl ether)
Nomenclature

In case of cyclic compounds, we use the prefix cyclo if the –OH group is
attached to C-1.

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Phenols:

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 Ethers

Structures of Functional Groups

Alcohols
• For alcohols, the –OH group is linked to carbon by a sigma bond.
• The bond is formed by the overlap of sp3 hybridised orbital of carbon with a sp 3
hybridised orbital of oxygen.

• In alcohols, the bond angle is slightly less than the tetrahedral angle (109°-28’)
due to therepulsion between the unshared electron pairs of oxygen.

Phenols
• In phenols, the –OH group is linked to carbon by sp2 hybridisation.
• The C-O bond length (136 pm) in phenol is slightly less than that in methanol.

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• This arises due to:
➢ Partial double bond character on account of the conjugation of unshared electron
pair of oxygenwith the aromatic ring.
➢ sp2 hybridised carbon to which oxygen is linked.

Ethers
• In ethers the two bond pairs and two lone pairs of electrons on oxygen form a
tetrahedralarrangement.
• Due to the repulsive interaction between the two bulky (-R) groups the bond angle
is slightlygreater than the tetrahedral angle.
• The C-O bond length is almost the same like alcohols.

Preparation of Alcohols
From Alkenes

➢ Acid catalysed hydration:

Alcohols are prepared by treating alkenes with water in the presence of acid as
catalyst.

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➢ Hydroboration-oxidation:
Alkenes on treatment with diborane give trialkyl boranes as addition product which
is then oxidised toalcohol by hydrogen peroxide in the presence of aqueous
sodium hydroxide.

The addition of borane to the double bond takes place in such a way that the boron
gets added to thesp2 carbon with more number of hydrogen atoms.

From Carbonyl Compounds

➢ Reduction of Aldehydes & Ketones
• Aldehydes yield primary alcohols whereas ketones give secondary alcohols.

➢ Reduction of Carboxylic acids and Esters

• LiAlH4 is a strong reducing agent and reduces carboxylic acids to primary alcohols
in excellent yields.

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• Alcohols are prepared on a commercial scale by converting acids to esters
followed by reduction with hydrogen in the presence of catalyst.

From Grignard reagents

Grignard reagents on reacting with aldehydes and ketones yield alcohols.

Preparation of Phenols

➢ From Haloarenes
Chlorobenzene on fusing with NaOH at 623 K and 320 atmospheric pressure gives
sodium phenoxidewhich on acidification yields phenol.

➢ From Benzenesulphonic Acid

Benzene on sulphonation with oleum gives benzene sulphonic acid which on heating
with molten sodium hydroxide gives sodium phenoxide. Acidification of the
sodium phenoxide gives phenol.

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 ➢ From Diazonium Salts
Aniline on treatment with nitrous acid at 273-278K gives benzene diazonium
chloride which onhydrolysis with warm water or treatment with dilute acids is
converted to phenols.

➢ From Cumene
Cumene(isopropylbenzene) on oxidation with air gives cumene hydroperoxide
which on treatment with dilute acid is converted to phenol.

Physical Properties

➢ Boiling points

• Boiling points of alcohols and phenols are higher in comparison to other classes
of compounds, namely hydrocarbons, ethers, haloalkanes and haloarenes of
comparable molecular masses. This is because the –OH group in alcohols and
phenols is involved in intermolecular hydrogen bonding.

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• The boiling points of alcohols and phenols increase with increase in the number
of carbon atoms. This is because of increase in van der Waals forces with increase
in the surface area.

• In alcohols, the boiling points decrease with increase in branching in the carbon
chain. This is becauseof decrease in van der Waals forces with decrease in the
surface area.

➢ Solubility

• Alcohols and phenols are soluble in water due to their ability to form hydrogen
bonds with watermolecules.

• The solubility of alcohols decreases with increase in the size of alkyl/aryl

(hydrophobic) groups.

Chemical Properties
Alcohols react both as nucleophiles and electrophiles.
A) Reactions involving cleavage of O-H bond
(i) Reaction with Metals
Alcohols and phenols react with active metals like Na, K and Al to give
correspondingalkoxides/phenoxides with the evolution of hydrogen.
2R-OH + 2Na → 2R-O-Na + H2

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(ii) Acidity of Alcohols
• The acidity of alcohols depends on the polar nature of O-H bond.
• The electron releasing groups (-CH3, -C2H5) increases the electron density on
oxygen and thus decrease the polarity of O-H bond which decreases the acid
strength.
• The acid strength of alcohols decreases in the following order:

• Alcohols are weaker acids than water which can be seen in the following reaction.

In the reaction, water is a better proton donor (i.e., stronger acid) than alcohol.
Over herethe alkoxide ion is a better proton acceptor than hydroxide ion which
suggests that alkoxides are stronger bases.
• Alcohols act as Bronsted bases as well due to the presence of unshared electron
pairs onoxygen which makes them proton acceptors.

(iii) Acidity of Phenols

• In phenol, the hydroxyl group is directly attached to the sp2 hybridised carbon of
the benzene ring which acts as an electron-withdrawing group. Whereas in

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 alcohols, the hydroxyl group is attached to the alkyl group which has an electron-
releasing inductiveeffect.
• In phenol, the hydroxyl group is directly attached to the sp2 hybridised carbon of
the benzene ring. Whereas in alcohols, the hydroxyl group is attached to the sp3
hybridised carbon of the alkyl group. The sp2 hybridised carbon has higher
electronegativity than the sp3 hybridised carbon. Thus, the polarity of the O–H
bond of phenols is higher than that ofalcohols. Hence, the ionisation of phenols
is higher than that of alcohols.
• The ionisation of an alcohol and a phenol occurs as follows:

• In alkoxide ion, the negative charge is localised on oxygen, while in phenoxide ion,
thecharge is delocalised.

• The delocalisation of the negative charge makes the phenoxide ion more stable
and favoursthe ionisation of phenol. Although there is charge delocalisation in
phenol, its resonance structures have charge separation due to which the phenol
molecule is less stable than the phenoxide ion.

• In substituted phenols, the presence of electron-withdrawing groups such as the

nitro groupenhances the acidic strength of phenol. On the other hand, electron-
releasing groups, suchas alkyl groups, decrease the acidic strength. It is because
electron-withdrawing groups lead to effective delocalisation of the negative
charge in the phenoxide ion.
(iv) Esterification
• Esters are formed when alcohols and phenols react with carboxylic acids, acid
chloridesand acid anhydrides.

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• In case of acid chloride, the reaction is carried out in the presence of base called
pyridine toneutralise the HCl formed and to shift the equilibrium to the right.

B) Reactions involving cleavage of Carbon-Oxygen(C-O) bond in alcohols

Only alcohols show reactions involving cleavage of C-O bond. Phenols exhibit this
type of reactiononly with zinc.

i) Reaction with hydrogen halides

Alcohols on treatment with hydrogen halides form alkyl halides.
ROH + HX → R-X + H2O
How to distinguish between Primary, Secondary and Tertiary Alcohols?
Lucas reagent test

• If it is a primary alcohol, then no turbidity appears at room temperature. Turbidity

appears onlyon heating.
• If it is a secondary alcohol, then turbidity appears in 5 minutes.
• If it is a tertiary alcohol, then turbidity appears immediately.
ii) Reaction with Phosphorus trihalides
Alcohols get converted into alkyl bromides on treatment with PBr 3.
3R-OH + PBr3 → 3R-Br + H3PO3
iii) Dehydration
• Alcohols undergo dehydration to form alkenes in the presence of conc. H 2SO4 or
H3PO3 orcatalysts such as anhydrous zinc chloride or alumina.

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• Primary alcohol undergoes dehydration by heating it with conc. H2SO4 at 443K.
• Secondary and tertiary alcohols undergo dehydration in milder conditions.

• Thus the ease of dehydration of alcohols follows the order:

Tertiary > Secondary > Primary

iv) Oxidation
• The oxidation of alcohols results in the formation of a carbon-oxygen double bond
with the cleavage of an O-H and C-H bonds. The reaction is known as
dehydrogenation reaction as it involves loss of dihydrogen from an alcohol
molecule.

• Use of strong oxidising agents like acidified KMnO4 is done to obtain carboxylic
acids from alcohols directly. CrO3 in anhydrous medium is used for obtaining
aldehydes.

• Pyridinium chlorochromate (PCC), a complex of chromium trioxide with pyridine

and HCl isa better oxidizing agent for oxidation of primary alcohols to aldehydes
in good yield.

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 • CrO3 is used to oxidize secondary alcohols to ketones.

• Tertiary alcohols do not undergo oxidation reaction. In presence of strong

oxidizing agents(KMnO4) and elevated temperatures, cleavage of C-C bonds takes
place and a mixture of carboxylic acids containing lesser number of carbon atoms
is formed.
• On passing vapours of a primary or a secondary alcohol over heated copper at
573K, dehydrogenation takes place and an aldehydes or a ketone is formed
whereas tertiaryalcohols undergo dehydration.

Characteristics of Phenols
• Phenols show electrophilic substitution reactions.
• The –OH group activates the benzene ring towards electrophilic substitution and
also directs the incoming group to ortho and para positions in the ring as these
positions become electron rich due tothe resonance effect caused by –OH group.
(i) Nitration
Phenol on treatment with dil.HNO3 at low temperature yields a mixture of ortho
and para nitrophenols.

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(ii) Halogenation

(a) Bromine in CHCl3 or CS2

Monobromophenols are formed when phenol is treated with bromine in CHCl 3 or
CS2 at low temperature.

(b) Action of Bromine water

On treating phenol with bromine water, a white precipitate of 2, 4, 6-
tribromophenol is formed.

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(iii) Kolbe’s Reaction
Phenols on treatment with NaOH produces phenoxide ion which is even more
reactive than phenol towards electrophilic aromatic substitution and therefore it
undergoes electrophilic substitution with carbon dioxide. Ortho hydroxybenzoic
acid is obtained as the main product.

(iv) Reimer-Tiemann Reaction

Phenols on treatment with chloroform in the presence of NaOH, a –CHO group is
introduced at ortho position of benzene ring. The substituted benzal chloride
formed as intermediate on hydrolysis with alkali produce salicylaldehyde.

(v) Action of Zinc dust

Phenol on heating with zinc dust produces benzene.

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 (vi)Oxidation
Phenols on oxidation with chromic acid gives out conjugated diketone known as
benzoquinone.

Some Commercially Important Alcohols

Methanol and ethanol are two commercially important alcohols.
Methanol
• Methanol also known as ‘wood spirit’ was produced by destructive distillation of
wood.
• Now methanol is produced by catalytic hydrogenation of carbon monoxide at high
pressure andtemperature in the presence of ZnO-Cr2O3 catalyst.

Ethanol
• It is commercially obtained by fermentation from sugars.
• The sugar in molasses, sugarcane or fruits like grapes is converted to glucose and
fructose in thepresence of an enzyme invertase.
• Glucose and fructose undergo fermentation in the presence of another enzyme,
zymase, which isfound in the yeast.

Preparation of Ethers

➢ By Dehydration of Alcohols
• Alcohols on dehydration with protic acids like H2SO4, H3PO4 give alkene or ether
depending on thereaction conditions.

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 ➢ Williamson Synthesis
• This method is used for the preparation of symmetrical and unsymmetrical ethers.
• In this reaction, an alkyl halide is allowed to react with sodium alkoxide.

• Phenols can also be converted into ethers using this method. In this, phenol is
used as thephenoxide moiety.

Physical Properties of Ethers

➢ Miscibility
Miscibility of ethers with water resembles those of alcohols of the same
molecular mass. This is because similar to alcohols; oxygen of ether can also
form hydrogen bonds with the water molecule.

➢ Boiling points
Ethers have much lower boiling points than alcohols. This is due to the presence
of hydrogen bondingin alcohols. Hydrogen bonding is absent in ethers.

Chemical Properties of Ethers

A. Cleavage of C–O bond in ethers

• Since ethers are least reactive of the functional groups, the cleavage of C-O

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bond in etherstakes place in excess of hydrogen halides.
• The cleavage of ethers with two different alkyl groups also takes place in the
same manner.

• In phenolic ethers, the cleavage occurs with the formation of phenol and
alkyl halide.

B. Electrophilic Substitution
The alkoxy group (-OR) is ortho, para directing and activates the benzene ring for
aromatic substitution.

(i) Halogenation

Phenyl alkyl ethers undergo halogenation reaction.

(ii) Friedel-Crafts reaction

In this reaction the alkyl groups and acyl groups are introduced at ortho and para
position by treating anisole with alkyl halide and acyl halide in the presence of

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anhydrous chloride ascatalyst.

(iii) Nitration
Anisole on treating with a mixture of sulphuric acid and nitric gives a mixture of
ortho andpara nitroanisole.

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