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Unit 11
Alcohol, Phenol and Ether
(Concepts, Questions & Exceptions)

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An alcohol contains one or more hydroxyl (OH) group(s) directly attached to carbon atom(s), of

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an aliphatic system (CH� OH) while a phenol contains –OH group(s) directly attached to carbon
atom(s) of an aromatic system (C� H� OH)

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Classification: Mono, Di, Tri or Polyhydric Compounds

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Primary, secondary and tertiary alcohols:

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Allylic alcohols: Benzylic alcohols:

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vinylic carbon or to an aryl carbon.

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Q. Classify the following as primary, secondary and tertiary alcohols:

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 Classification of Ethers:
Simple or symmetrical, if the alkyl or aryl groups attached to the oxygen atom are the same eg.
Diethyl ether, C� H� OC� H�
Mixed or unsymmetrical, if the two groups are different: C� H�OCH� and C� H� OC� H�

Nomenclature:

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Glycerol

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C� H� OCH� Methyl phenyl ether Methoxybenzene (Anisole)

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C� H� OCH� CH� Ethyl phenyl ether Ethoxybenzene (Phenetole)

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Structures of Functional Groups:

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The 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. In phenols, the –OH group is attached to
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sp2 hybridised carbon of an aromatic ring. The carbon– oxygen bond length (136 pm) in phenol is
slightly less than that in methanol.
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This is due to
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a) Partial double bond character on account of the conjugation of unshared electron pair of
oxygen with the aromatic ring and
b) sp2 hybridised state of carbon to which oxygen is attached.
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
 Methods of Preparation:
Preparation of Alcohols:
1. From alkenes (Hydrolysis)
2. From carbonyl compounds (Reductions)
3. From Grignard reagents (with carbonyl compounds)

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1. From alkenes (Hydrolysis)
(i) By acid catalysed hydration:

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1. Alkenes react with water in the presence of acid (H� SO� ) as catalyst to form alcohols.

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2. Carbocation mediated reactions
3. In case of unsymmetrical alkenes, the addition reaction takes place in accordance with

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Markovnikov’s rule

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Mechanism:
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Q. Show how would you synthesise the following alcohols from appropriate alkenes
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Q. The product of acid-catalyzed hydration of 2- phenylpropene is

(a) 3-phenyl-2-propanol (b) 1-phenyl-2-propanol
(c) 2-phenyl-2-propanol (d) 2-phenyl- 1-propanol
 (ii) By hydroboration–oxidation:
1. Diborane (BH�)2 + hydrogen peroxide (H� O� ) + aqueous sodium hydroxide NaOH
2. Addition of water to the alkene in a way opposite to the Markovnikov’s rule
3. Primary alcohols are prepared by this method
4. In this reaction, alcohol is obtained in excellent yield

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2. From carbonyl compounds:

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(i) By reduction of aldehydes and ketones:

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1. Aldehydes and ketones are reduced to the corresponding alcohols
2. Addition of hydrogen in the presence of catalysts (catalytic hydrogenation).

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3. The usual catalyst is a finely divided metal such as platinum, palladium or nickel.
4. By reducing agent eg. sodium borohydride (NaBH� ) or lithium aluminium hydride
(LiAlH� ). om
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5. Aldehydes yield primary alcohols whereas ketones give secondary alcohols
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By reduction of carboxylic acids and esters: by lithium aluminium hydride, a strong reducing
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agent.
LiAlH� is an expensive reagent, and therefore, used for preparing special chemicals only
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Commercially, acids are reduced to alcohols by converting them to the esters, followed by their
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reduction using hydrogen in the presence of catalyst (catalytic hydrogenation).

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Q. Write structures of the products of the following reactions:

 Q. Catalytic reduction of butanal give?

3. From Grignard reagents:

a) Alcohols are produced by the reaction of Grignard reagents with aldehydes and ketones.
b) Grignard reagents with methanal produces a primary alcohol,
c) Grignard reagents with other aldehydes, secondary alcohols

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d) Grignard reagents with ketones, tertiary alcohols
Mechanism: The first step of the reaction is the nucleophilic addition of Grignard reagent to the

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carbonyl group to form anadduct. Hydrolysis of the adduct yields an alcohol

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Q. Reaction of propanone with methylmagnesium bromide followed by hydrolysis
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Q. Show how are the following alcohols prepared by the reaction of a suitable Grignard reagent
on methanal ?
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Q. Which of the following are the starting materials for the Grignard’s synthesis of t-butanol?
(a) CH3MgBr + CH3COCH3 (b) CH3CH2MgBr + CH3COCH3
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(c) CH3MgBr + CH3CHOHCH3 (d) CH3MgBr + CH3CHO

 Preparation of Phenols: Phenol, also known as carbolic acid
1. From haloarenes

2. From benzenesulphonic acid

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3. From diazonium salts

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4. From cumene (isopropylbenzene):
1) Most of the worldwide production of phenol is from cumene

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2) It is industrial methds (large quantity) of preparation of phenol

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Q. Identify the major products P, Q and R in the following sequence of reactions:

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Physical Properties:
Boiling Points:
1. The boiling points of alcohols and phenols increase with increase in the number of carbon
atoms (increase in van der Waals forces).
 2. In alcohols, the boiling points decrease with increase of branching in carbon chain (because
of decrease in van der Waals forces with decrease in surface area).
3. The high boiling points of alcohols are mainly due to the presence of intermolecular
hydrogen bonding in them which is lacking in ethers and hydrocarbons
4. Boiling points of alcohols and phenols are than hydrocarbons, ethers, haloalkanes and
haloarenes of comparable molecular masses.

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Q. Arrange the following sets of compounds in order of their increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol.

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(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.

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Solubility: Solubility of alcohols and phenols in water is due to their ability to form hydrogen
bonds with water molecules
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The solubility decreases with increase in size of alkyl/aryl (hydrophobic) groups
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Chemical Reaction: They react both as nucleophiles and electrophiles.

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1. The bond between O–H is broken when alcohols react as nucleophiles

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2. The bond between C–O is broken when they react as electrophiles: Protonated alcohols as
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electrophiles
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(a) Reactions involving cleavage of O–H bond

1. Acidity of alcohols and phenols
(i) Reaction with metals: Alcohols and phenols react with active metals such as sodium,
potassium and aluminium to yield corresponding alkoxides/phenoxides and hydrogen
 This reactions show that alcohols and phenols are acidic in nature

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Alcohols and phenols are Brönsted acids i.e., they can donate a proton to a stronger base (B:)

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(ii) Acidity of alcohols: The acidic character of alcohols is due to the polar nature of O–H bond.

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An electron-releasing group (–CH� , –C� H� ) increases electron density on oxygen tending to
decrease the polarity of O-H bond. This decreases the acid strength.

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CH� -OH > CH� CH� -OH > CH� CH� CH� -OH
Alcohols are, however, weaker acids than water.
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1. Water is a better proton donor (i.e., stronger acid) than alcohol

2. Alkoxide ion is a better proton acceptor than hydroxide ion
3. Alkoxides are stronger bases (sodium ethoxide is a stronger base than sodium hydroxide)
4. Alcohols act as bronsted bases as well
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Q. The order of reactivity of alcohols towards Na or K metal is

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(a) Primary > Secondary > Tertiary (b) Primary < Secondary < Tertiary
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(c) Primary < Secondary > Tertiary (d) Primary > Secondary < Tertiary

(iii) Acidity of phenols:

 1. Phenols are stronger acids than alcohols and water due to resonance

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2. The hydroxyl group, in phenol is directly attached to the sp2 hybridised carbon of benzene
ring which acts as an electron withdrawing group

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3. This increases the polarity of O–H bond and results in an increase in ionisation of phenols
than that of alcohols
4. In alkoxide ion, the negative charge is localised on oxygen while in phenoxide ion, the

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charge is delocalised.
5. The phenol molecule is less stable than phenoxide ion due to its resonance structures have

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charge separation

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1. In substituted phenols, the presence of electron withdrawing groups such as nitro group,
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enhances the acidic strength of phenol.
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2. This effect is more pronounced when such a group is present at ortho and para positions.
3. It is due to the effective delocalisation of negative charge in phenoxide ion.
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4. On the other hand, electron releasing groups, such as alkyl groups decrease in acid strength.
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5. Cresols, for example, are less acidic than phenol.

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The greater the pKa

value, the weaker the
acid.
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Q. Arrange the following compounds in increasing order of their acid strength:

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Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, phenol, 4-methylphenol

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Q. Which of the following is most acidic?

(i) Benzyl alcohol (ii) Cyclohexanol (iii) Phenol (iv) m-Chlorophenol
 Q. The correct order of decreasing acidity of nitrophenols will be
(a) m-nitrophenol > p-nitrophenol > o-nitrophenol
(b) o-nitrophenol > m-nitrophenol > p-nitrophenol
(c) p-nitrophenol > m-nitrophenol > o-nitrophenol
(d) p-nitrophenol > o-nitrophenol > m-nitrophenol

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3. Esterification:
a) Alcohols and phenols react with carboxylic acids, acid chlorides and acid anhydrides to

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form esters
b) The introduction of acetyl (CH� CO-) group in alcohols or phenols is known as acetylation

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a) The reaction with carboxylic acid and acid anhydride is carried out in the presence of a
small amount of concentrated sulphuric acid.
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b) The reaction is reversible, and therefore, water is removed as soon as it is formed.
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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
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hand side
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Aspirin possesses
1. Analgesic (reduce pain)
2. anti-inflammatory (reduce swelling)
3. antipyretic (reduce temperature)
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(b) Reactions involving cleavage of carbon – oxygen (C–O) bond in alcohols

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The reactions involving cleavage of C–O bond take place only in alcohols.
Phenols show this type of reaction only with zinc.
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1. Reaction with hydrogen halides:

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1. The difference in reactivity of three classes of alcohols with HCl distinguishes them from
one another (Lucas test).
2. Alcohols are soluble in Lucas reagent (conc. HCl and anhydrous Zn𝐂𝐥𝟐 ) while their
halides are immiscible and produce turbidity in solution.
3. In case of tertiary alcohols, turbidity is produced immediately as they form the halides
easily. Primary alcohols do not produce turbidity at room temperature.
 2. Reaction with phosphorus trihalides: Alcohols are converted to alkyl bromides by reaction
with phosphorus tribromide

Q. Give structures of the products when each of the following alcohol reacts with

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(a) HCl–ZnCl� (b) HBr and (c) SOCl� (i) Butan-1-ol (ii) 2-Methylbutan-2-ol

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4. Dehydration:

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a) Removal of a molecule of water
b) Formation of alkenes take place

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c) Treating with a protic acid e.g., concentrated acid (H� 𝑆O� ) or (H� PO� ), or catalysts
such as anhydrous zinc chloride or alumina.
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d) Carbocation mediated reactions
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e) The relative ease of dehydration of alcohols : Tertiary > Secondary > Primary
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The mechanism of dehydration:

Step 1: Formation of protonated alcohol:
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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

Q. Predict the major product of acid catalysed dehydration of

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(i) 1-methylcyclohexanol and (ii) butan-1-ol

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4. Oxidation:

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a) Oxidation of alcohols involves the formation of a carbon-oxygen double bond with

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cleavage of an O-H and C-H bonds.
b) These are also known as dehydrogenation reactions as these involve loss of dihydrogen
from an alcohol molecule.

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c) Depending on the oxidising agent used, a primary alcohol is oxidised to an aldehyde which
in turn is oxidised to a carboxylic acid
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Strong oxidising agents: such as acidified potassium permanganate are used for getting
carboxylic acids from alcohols directly.
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Weak oxidising agent: Pyridinium chlorochromate (PCC), a complex of chromium trioxide with
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pyridine and HCl

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Secondary alcohols are oxidised to ketones by chromic anhyride (CrO� )

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Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as
strong oxidising agents (KMnO� )) and elevated temperatures, cleavage of various C-C bonds takes
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place and a mixture of carboxylic acids containing lesser number of carbon atoms is formed

Q. The best reagent to convert pent-3-en-2-ol into pent-3-en-2-one is

(a) acidified K � Cr� O� (b) alkaline KMnO�

(c) pyridinium chlorochromate (d) Chromic anhydride in glacial acetic acid

 Q. The suitable reagent to convert CH3–CH=CH–CHO into CH3–CH2–CH2–CH2–OH is

(a) NaBH4 (b) LiAlH4 (c) Zn–Hg/HCl (d) H2/Pd

Oxidation with heated copper at 573 K:

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Q. When vapours of an alcohol are passed over hot reduced copper, it gives an alkene. The alcohol

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(a) Primary (b) Secondary (c) Tertiary (d) None of these

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Biological oxidation of methanol and ethanol in the body produces the corresponding aldehyde

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followed by the acid. At times the alcoholics, by mistake, drink ethanol, mixed with methanol also
called denatured alcohol. In the body, methanol is oxidised first to methanal and then to methanoic
acid, which may cause blindness and death. A methanol poisoned patient is treated by giving

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intravenous infusions of diluted ethanol. The enzyme responsible for oxidation of aldehyde
(HCHO) to acid is swamped allowing time for kidneys to excrete methanol
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Reactions of phenols: Electrophilic aromatic substitution

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a) The –OH group attached to the benzene ring activates it towards electrophilic
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substitution.
b) It directs the incoming group to ortho and para positions in the ring
(i) Nitration: With dilute nitric acid at low temperature (298 K), phenol yields a mixture of ortho
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and para nitrophenols.

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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
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volatile due to intermolecular hydrogen bonding which causes the association of molecules
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With concentrated nitric acid, phenol is converted to 2,4,6-trinitrophenol. The product is

commonly known as picric acid.
 2, 4, 6 - Trinitrophenol is a
strong acid

Nowadays picric acid is prepared by treating phenol first with concentrated sulphuric acid which

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converts it to phenol-2,4-disulphonic acid, and then with concentrated nitric acid to get 2,4,6-
trinitrophenol.

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(ii) Halogenation:

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(a) When the reaction is carried out in solvents of low polarity such as CHCl� or CS� and at
low temperature, monobromophenols are formed.

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The usual halogenation of benzene takes place in the presence of a Lewis acid, such as FeBr�
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which polarises the halogen molecule. In case of phenol, the polarisation of bromine molecule
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takes place even in the absence of Lewis acid. It is due to the highly activating effect of –OH group
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attached to the benzene ring.

(b) When phenol is treated with bromine water, 2,4,6-tribromophenol is formed as white
precipitate.
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Q, Phenol reacts with bromine in carbon disulphide at low temperature to give

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(a) m-bromophenol (b) o- and p-bromophenol

(c) p-bromophenol (d) 2,4,6-tribromophenol
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Q. Write the structures of the major products expected from the following reactions:
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(a) Mononitration of 3-methylphenol

(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate
 Kolbe’s reaction:

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Reimer-Tiemann reaction:

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4. Oxidation and reductions:

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Q. Reaction of phenol with chloroform in presence of dilute sodium hydroxide finally introduces
which one of the following functional group?
(A) –COOH
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Q. When phenol is treated with CHCl3 and NaOH, the product formed is
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(a) benzaldehyde (b) salicylaldehyde (c) salicylic acid (d) benzoic acid
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Commercially important alcohols: Methanol and ethanol

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1. Methanol:
1. Its is also known as ‘wood spirit’, was produced by destructive distillation of wood.
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2. Methanol is a colourless liquid and boils at 337 K.

3. It is highly poisonous in nature. Ingestion of even small quantities of methanol can cause
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blindness
4. Used as a solvent in paints, varnishes and chiefly for making formaldehyde
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Q. Methanol is industrially prepared by

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(a) Oxidation of CH4 by steam at 900o C (b) Reduction of HCHO using LiAlH4
(c) Reaction HCHO with a solution of NaOH (d) Reduction of CO using H2 and ZnO- Cr2O3

2. Ethanol:
1. It is obtained commercially by fermentation
2. Fermentation takes place in anaerobic conditions i.e. in absence of air.
3. Carbon dioxide is released during fermentation
 1. The action of zymase is inhibited once the percentage of alcohol formed exceeds 14
percent.

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2. If air gets into fermentation mixture, the oxygen of air oxidises ethanol to ethanoic acid
which in turn destroys the taste of alcoholic drinks
3. Ethanol is a colourless liquid with boiling point 351 K.

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4. It is used as a solvent in paint industry and in the preparation of a number of carbon
compounds.

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5. 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

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alcohol.
6. Ingestion of ethanol acts on the central nervous system

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Q. The enzyme which converts glucose to ethyl alcohol is

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(a) zymase (b) invertase (c) maltase (d) diastase

Ethers

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Diethyl ether has been used widely as an inhalation anaesthetic. But due to its slow effect and an
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unpleasant recovery period, it has been replaced, as an anaesthetic, by other compounds
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Preparation of Ethers:
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1. By dehydration of alcohols:
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Mechanism:
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1. The formation of ether is a nucleophilic bimolecular reaction (SN2)

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2. This method for the preparation of symmetrical ethers only

3. Only primary alcohol is used to prepare ether
4. The reaction follows SN1 pathway when the alcohol is secondary or tertiary
5. Acidic dehydration of alcohols, to give an alkene is also associated with substitution
reaction to give an ether
 2. Williamson synthesis:
1. It is an important laboratory method for the preparation of symmetrical and unsymmetrical
ethers.
2. Ethers containing substituted alkyl groups (secondary or tertiary) may also be prepared by
this method.
3. The formation of ether is a nucleophilic bimolecular reaction (SN2)

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4. Better results are obtained if the alkyl halide is primary.

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5. In case of secondary and tertiary alkyl halides, elimination competes over substitution.
6. If a tertiary alkyl halide is used, an alkene is the only reaction product and no ether is

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formed.

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Q. Write the names of reagents and equations for the preparation of the following ethers by
Williamson’s synthesis:
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(i) 1-Propoxypropane
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(ii) Ethoxybenzene
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(iii) 2-Methoxy-2-methylpropane
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(iv) 1-Methoxyethane
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Q. Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol

and 3-methylpentan-2-ol.
 Q. The major product obtained when tert-butyl bromide is heated with sodium ethoxide is
(a) 2 - Methyl -1-propene (b) Ethene (c) tert - Butyl methyl ether (d) Diethyl ether

Physical Properties: Boiling point and water solubility

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Chemical Reactions: 1. Cleavage of C–O bond in ethers
1. Ethers are the least reactive of the functional groups.

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2. The cleavage of C-O bond in ethers takes place under drastic conditions with excess of
hydrogen halides.

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3. The reaction of dialkyl ether gives two alkyl halide molecules

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a) The order of reactivity of hydrogen halides is as follows: HI > HBr > HCl.
b) The cleavage of ethers takes place with concentrated HI or HBr at high temperature
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Cleavage of unsymmetrical ether:

However, when one of the alkyl group is a tertiary group, the halide formed is a tertiary halide
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Q. Give the major products that are formed by heating each of the following ethers with HI
 Electrophilic substitution Reactions: The alkoxy group (-OR) is ortho, para directing and
activates the aromatic ring towards electrophilic substitution in the same way as in phenol

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(i) Halogenation:

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(ii) Friedel-Crafts reaction:

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(iii) Nitration:
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Q. Predict the products of the following reactions

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 Q. Which of the following is an appropriate set of reactants for the preparation of 1-methoxy-4-
nitrobenzene and why?

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Q. Write the equation of the reaction of hydrogen iodide with:
(i) 1-propoxypropane

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(ii) methoxybenzene

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(iii) benzyl ethyl ether

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Note: Do all Intex Questions, Back Exercise Questions, Solved Examples

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