11.

Alcohols, Phenols and Ethers

Alcohols, phenols and ethers are the basic compounds for
the formation of detergents, antiseptics and fragrances,
respectively.

vinylic alcohols :-These alcohols contain OH

group bonded to a carbon-carbon double bond i.e.,
to a vinylic carbon or to
aryl alcohols. These alcohols are also known as
phenols .

The subsitution of a hydrogen atom in a hydrocarbon

by an alkoxy or aryloxy group (RO/ArO) yields
another class of compounds known as ethers, for
example, CH3OCH3(dimethyl ether).
11.1 Classification
11.1.1 Mono, Di, Tri or Polyhydric Compounds
Alcohols and phenols may be classified as mono, di,
tri- or polyhydric

(b) Phenols: The simplest hydroxy derivative of

benzene is phenol.
It is its common name and also an accepted
IUPAC name.
in its substituted compounds the terms ortho (1,2disubstituted), meta (1,3-disubstituted) and para
(1,4-disubstituted) are often used in the common
names.

Dihydroxy derivatives of benzene are known as 1,

2-, 1, 3- and 1, 4-benzenediol.

Compounds
containing

Primary, secondary and tertiary alcohols:

respectively as depicted below:

Allylic alcohols :-Allylic alcohols: In these

alcohols, the OH group is attached to an allylic
carbon. For example

Benzylic alcohols: In these alcohols, the OH

group is attached to a carbon atom next to an
aromatic ring. For example

Cyclic alcohols are named using the prefix cyclo and

considering the OH group attached to C1.

(c) 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 ethylmethyl ether.

Allylic and benzylic alcohols may be primary,

secondary or tertiary.

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COMPOUND

COMMON NAME IUPAC NAME

COMPOUND

COMMON NAME

IUPAC NAME

CH3-OH

Methyl alcohol

Methanol

CH3OCH3

Dimethyl ether

Methoxymethane

CH3-CH2-CH2-OH

n-Propyl
alcohol

propan-1-ol

C2H5OC2H5

Diethyl ether

Ethoxyethane

CH3OCH2CH2CH Methyl n-propyl

CH3-CH2-CH2-CH2-OH

Isopropyl
alcohol

propan-2-ol

n-Butyl alcohol

Butan-1-ol

sec-Butyl
alcohol

ether

1-Methoxypropane

C6H5OCH3

Methylphenyl ether
(Anisole)

Methoxybenzene
(Anisole)

C6H5OCH2CH3

Ethylphenyl
ether(Phenetole)

Ethoxybenzene

C6H5O(CH2)6-CH3 Heptylphenyl ether

Butan-2-ol

2-methylpropane-1Isobutyl alcohol ol

tert-Butyl
alcohol

2-Methylpropan-2ol

CH -O-CH -CH OCH

3

Glycerol

Methyl isopropyl
ether

2-Methoxypropane

Phenylisopentyl
ether

3Methylbutoxybenze
ne

1,2-Dimethoxyethne

2-Ethoxy-1,1dimethylcyclohexan
e

Propane-1,2,2triol

Table 11.1: Common and IUPAC Names of Some Alcohols

11.1.2 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 C2H5OC6H5are
unsymmetrical ethers.
The larger (R) group is chosen as the parent
hydrocarbon. The names of a few ethers are given as
examples in Table 11.2.
Intext Question
11.2 Name the following compounds according to
IUPAC system.

1-phenoxyheptane

Table 11.2: Common and IUPAC Names of Some Ethers

Example 11.1
Give IUPAC names of the following compounds:

Solution
(i) 4-Chloro-2,3-dimethylpentan-1-ol
(ii) 2-Ethoxypropane (iii) 2,6-Dimethylphenol
(iv) 1-Ethoxy-2-nitrocyclohexane
11.3 Structure of Functional Groups.

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as addition product. This is oxidised to alcohol

by hydrogen peroxide in the presence of aqueous
sodium hydroxide.

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 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 unshared electron pair
of oxygen with the aromatic ring (Section 11.4.4) and
(ii) sp2 hybridised state of carbon to which oxygen is
In ether The bond angle is slightly greater than the
tetrahedral angle due to the repulsive interaction
between the two bulky (R) groups.
11.4 Alcohols and Phenols
11.4.1 Preparation of Alcohols
Alcohols are prepared by the following methods:
1. From alkenes
(i) By acid catalysed hydration:
Alkenes react with water in the presence of acid
as catalyst to form alcohols.
In case of unsymmetrical alkenes, the addition
reaction takes place in accordance with
Markovnikovs rule

Mechanism
Step 1: Protonation of alkene to form carbocation by
electrophilic attack of H3O+ .
H2O + H+ H3O+

The alcohol so formed in a way opposite to the

Markovnikovs rule..
2. From carbonyl compounds
(i) By reduction of aldehydes and ketones:
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 acidsv are reduced to primary alcohols in
excellent yields by lithium aluminium hydride, a strong
reducing agent.

3. From Grignard reagents

Alcohols are produced by the reaction of Grignard
reagents with aldehydes and ketones.
The first step of the reaction is the nucleophilic
addition of Grignard reagent to the carbonyl group to
form an adduct. Hydrolysis of the adduct yields an
(ii) By hydroborationoxidation: Diborane
(BH3)2 reacts with alkenes to give trialkyl boranes

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alcohol.

Acidification of the sodium salt gives phenol.

The overall reactions using different aldehydes and

ketones are as follows:

3. From diazonium salts

A diazonium salt is formed by treating an aromatic
primary amine with nitrous acid (NaNO2 + HCl) at 273278 K. Diazonium salts are hydrolysed to phenol

4. From cumene
Cumene (isopropylbenzene) is oxidised in the presence
of air to cumene hydroperoxide. It is converted to phenol
formaldehyde (methanal )produces a primary alcohol and acetone by treating it with dilute acid.
with, a secondary alcohol with other aldehydes and
tertiary alcohol with ketones.
Example11.2
Give the structures and IUPAC names of the
products expected from the following reactions:
(a)
Catalytic
reduction
of
butanal. Intext Questions
(b) Hydration of propene in the presence of dilute 11.4 Show how are the following alcohols prepared by
the reaction of a suitable Grignard reagent on methanal ?
sulphuricacid.
(c) Reaction of propanone with methylmagnesium
bromide
followed
by
hydrolysis.
Solution
11.5 Write structures of the products of the following
reactions:

11.4.2 Preparation of Phenols

Phenol, also known as carbolic acid,
1. From haloarenes
Chlorobenzene is fused with NaOH at 623K and 320
atmospheric pressure. Phenol is obtained by acidification
of sodium phenoxide

2. From benzenesulphonic acid

Benzene is sulphonated with oleum and benzene
sulphonic acid so formed is converted to sodium
phenoxide on heating with molten sodium hydroxide.

11.4.3 Physical Properties

The boiling points of alcohols and phenols increase
with increase in the number of carbon atoms
(increase in van der Waals forces).
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).

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 The OH group in alcohols and phenols is involved

in intermolecular hydrogen bonding as shown below:

It is interesting to note that 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.
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.

11.4.4 Chemical Reactions

Alcohols are versatile compounds. They react both as
nucleophiles and electrophiles. The bond between OH
is broken when alcohols react as nucleophiles.

(ii) The bond between CO is broken when they react as

electrophiles. Protonated alcohols react in this manner.

Based on the cleavage of OH and CO bonds, the

reactions of alcohols and phenols may be divided into
two groups:
(a) Reactions involving cleavage of OH 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.

Solubility
Solubility of alcohols and phenols in water is due to
their ability to form hydrogen bonds with water
molecules as shown.
The solubility decreases with increase in size of
alkyl/aryl (hydro- phobic) groups. Several of the
lower molecular mass alcohols are miscible with
water in all proportions.
In addition to this, phenols react with aqueous sodium
hydroxide to form sodium phenoxides.

Example 11.4.4 Arrange the following sets of

compounds in order of their increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan1-ol, methanol.
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
Solution
(a) Methanol, ethanol, propan-1-ol, butan-2-ol, butan-1ol, pentan-1-ol.
(b) n-Butane, ethoxyethane, pentanal and pentan-1-ol.

The above reactions show that alcohols and phenols

are acidic in nature.
In fact, alcohols and phenols are Brnsted acids i.e.,
they can donate a proton to a stronger base (B:).
Phenols are Arrehenius acid but not alcohol
CH4<NH3 <ROH< H2Ophenols<RCOOH
(ii) Acidity of alcohols: The acidic character of
alcohols is due to the polar nature of OH bond. 5

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Acidic strength of Phenols : Phenols are

stronger acids than alcohols AND WATER.

decreases in the following order:

(iii) Acidity of phenols: The reactions of phenol

with metals (e.g., sodium, aluminium) and sodium
hydroxide indicate its acidic nature.
Reason (i): as depicted in its resonance structures,
causes the oxygen of OH group to be positive.

this positive charge on oxygen make O-H bond weaker ,

and tends to deprotonated to give H+ and become acidic

Reason(ii): Phenoxide ion is more stable than

alkoxide ion due its resonance stabilisation.

Therefore, phenol is more acidic than alcohol.

Alcohols are, however, weaker acids than water. This can

be illustrated by the reaction of water with an alkoxide.

which suggests that alkoxides are stronger bases

(sodium ethoxide is a stronger base than sodium
hydroxide).
Alcohols act as Bronsted bases as well. It is due to
the presence of unshared electron pairs on oxygen,
which makes them proton acceptors.
The ionisation of an alcohol and a phenol takes place as
follows:

Electron-withdrawing substituents (especially at

ortho- and para- positions) increase the acidity of
phenols whereas electron-donating substituents
decrease acidity.
Q 1

Which phenol in each of the following pairs is

more acidic? Justify your choice.
(a) 2,4,6-Trimethylphenol or 2,4,6trinitrophenol
(b) 2-Nitro phenol or 4- Nitro phenol
(c) 3-Nitrophenol or 4-nitrophenol
(d) Phenol or 4-methoxyphenol

(e) 2,5-Dinitrophenol or 2,6-dinitrophenol

ANSWER
(a) 2,4,6-trinitrophenol
(b) 4- Nitro phenol [H-BOND in -2-Nitro phenol]
(c) 4-nitrophenol (d) Phenol
(e) 2,6-dinitrophenol

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

In substituted phenols, the presence of electron

withdrawing groups such as nitro group, enhances the
acidic strength of phenol.
This effect is more pronounced when such a group is
present at ortho and para positions. It is due to the
effective delocalisation of negative charge in
phenoxide ion.
On the other hand, electron releasing groups, such as
alkyl groups, in general, do not favour the formation
of phenoxide ion resulting in decrease in acid
strength.
Cresols, for example, are less acidic than phenol.

COMPOUND

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FORMULA

DPS JODHPUR

PKA

salicylic acid produces aspirin.

o-Nitrophenol

o-O2N-C6H4-OH

7.2

m-Nitrophenol

o-O2N-C6H4-OH

8.3

Phenol

C6H5-oH

10.0

o-Cresol

o-CH3-C6H4- OH

10.2

m-Cresol

m-CH3C6H4-OH

10.1

p-Cresol

p-CH3-C6H4-OH

10.2

Ethanol

C2H5OH

15.9

Table 11.3: pKa Values of some Phenols and

Ethanol
From the above data, you will note that phenol is million
times more acidic than ethanol.
Example 11.4
Arrange the following compounds in increasing order of
their acid strength:
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5dinitrophenol,phenol, 4-methylphenol.
Solution
Propan-1-ol, 4-methylphenol, phenol, 3-nitrophenol, 3,5dinitrophenol,2,4, 6-trinitrophenol.
2. Esterification
Alcohols and phenols react with carboxylic acids, acid
chlorides and acid anhydrides to form esters.

(b) Reactions involving cleavage of carbon oxygen (C

O) bond in alcohols
The reactions involving cleavage of CO bond 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 halide
ROH + HX RX + H2O
The difference in reactivity of three classes of
alcohols with HCl distinguishes them from one
another (Lucas test).
(Lucas test). Alcohols are soluble in Lucas reagent
(conc. HCl and ZnCl2) while their halides are
immiscible and produce turbidity in solution.
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
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

The reaction with acid chloride is carried out in the
concentrated H2SO4 at 443 K.
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.
The introduction of acetyl (CH3CO) group in alcohols
or phenols is known as acetylation. Acetylation of

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Secondary and tertiary alcohols are dehydrated under

milder conditions. For example

Thus, the relative ease of dehydration of alcohols

follows the following order:
Tertiary > Secondary > Primary
The mechanism of dehydration of ethanol is
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.

The acid used in step 1 is released in step 3. To drive

the equilibrium to the right, ethene is removed as it is
formed.
4. Oxidation: Oxidation of alcohols involves the
formation of a carbon- oxygen double bond with
cleavage of an O-H and C-H bonds.

Depending on the oxidising agent used, a primary

alcohol is oxidised to an aldehyde which in turn is

oxidised to a carboxylic acid.

Strong oxidising agents such as acidified potassium

permanganate are used for getting carboxylic acids
from alcohols directly.
CrO3 in anhydrous medium is used as the oxidising
agent for the isolation of aldehydes.

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.

Secondary alcohols are oxidised to ketones by both

strong or mild oxidizing agent

Tertiary alcohols do not undergo oxidation reaction.

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

tertiaryalcohols with Cu undergo dehydration

because of being heated at 573 K
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 called denatured alcohol.8

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In the body, methanol is oxidised first to methanal

and then to methanoic acid, which may cause
blindness and death.
(c) Reactions of phenols
Following reactions are shown by phenols only.
1. Electrophilic aromatic substitution
In phenols, the reactions that take place on the
aromatic ring are electrophilic substitution reactions
The OH group attached to the benzene ring
activates it towards electrophilic substitution.
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
(i) Nitration: With dilute nitric acid a mixture of ortho
and para nitrophenols.

Br2 withCHCl3 or CS2 and at low temperature,

mono bromophenols are formed.

(b) When phenol is treated with bromine water, 2,4,6tribromophenol is formed as white precipitate.

Example 11.5 Write the structures of the major products

expected from the following reactions:
(a) Mononitration of 3-methylphenol
(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate.
Solution
The combined influence of OH and CH3 groups
determine the position of the incoming group.

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.

2. Kolbes reaction
reaction with sodium hydroxide followed by Ortho
hydroxybenzoic acid is formed as the main reaction
product.

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.

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

(ii) Halogenation: .

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another enzyme, zymase, which is found in yeast.

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

Intext Question
11.6 Give structures of the products you would expect
when each of the following alcohol reacts with (a) HCl
ZnCl2 (b) HBr and (c) SOCl2.
(i) Butan-1-ol
(ii) 2-Methylbutan-2-ol
11.7 Predict the major product of acid catalysed
dehydration of
(i) 1-methylcyclohexanol and
(ii) butan-1-ol
11.8 Ortho and para nitrophenols are more acidic than
phenol. Draw the resonance structures of the
corresponding phenoxide ions.
11.9 Write the equations involved in the following
reactions:
(i) Reimer Tiemann reaction
(ii) Kolbes reaction
11.5 Some Commercially Important Alcohols
Methanol and ethanol are among the two
commercially important alcohols.
1. Methanol
Methanol, CH3OH, also known as wood spirit, was
produced by destructive distillation of wood
hydrogenation of carbon monoxide at high pressure
and temperature and in the presence of ZnO

Cr2O3catalyst
2. Ethanol
in the presence of an enzyme, invertase. Glucose and
fructose undergo fermentation in the presence of

The action of zymase is inhibited once the percentage of

alcohol formed exceeds 14 percent.
11.6 Ethers
11.6.1 Preparation of Ethers
1. By dehydration of alcohols
Alcohols undergo dehydration in the presence of protic
acids (H2SO4, H3PO4).. For example, ethanol is
dehydrated to ethene in the presence of sulphuric acid at
443 K. At 413 K, ethoxyethane is the main product.

The formation of ether is a nucleophilic bimolecular

reaction (SN2) involving the attack of alcohol molecule
on a protonated alcohol, as indicated below:

The method is suitable for the preparation of ethers

having primary alkyl groups only because with
higher degree of alkyl favours elimination to the
form alkene
2. Williamson synthesis
it is preparation of symmetrical and unsymmetrical
ethers.
In this method, an alkyl halide is allowed to react
with sodium alkoxide.

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10

The reaction involves SN2 attack of an alkoxide ion on

primary alkyl halide.

net dipole moment.

The large difference in boiling points of alcohols and

ethers is due to the presence of hydrogen bonding in
alcohols.
The miscibility of ethers with water resembles those
of alcohols of the same molecular mass.
Limitation:- R of RX can not be 30 and Ar-X
It is because 30RX gives elimination more than
substitution Rn
Ar-X can not give substitution reactions because
partial double bond between Cand X
Example 11.6 The following is not an appropriate
reaction for the preparation of t-butyl ethyl ether.

11.6.3 Chemical Reactions

1. Cleavage of CO bond in ethers
Ethers are the least reactive of the functional groups.
The cleavage of C-O bond in ethers takes place under
drastic conditions with excess of hydrogen halides.
The reaction of dialkyl ether gives two alkyl halide
molecules.
R-O-R + HX &RARR; RX + R-OH
R-OH + HX &RARR; R-X + H2O
The reaction of an ether with concentrated HI starts
with protonation of ether molecule.
SN2Step 1:

(i) What would be the major product of this reaction ?

(ii) Write a suitable reaction for the preparation of tbutylethyl ether.
Solution
(i) The major product of the given reaction is 2methylprop-1-ene. It is because sodium ethoxide is a
strong nucleophile as well as a strong base. Thus
elimination reaction predominates over substitution.
Phenols are also converted to ethers by this method. In
this, phenol is used as the phenoxide moiety.

Phenols are also converted to ethers by this method. In

this, phenol is used as the phenoxide moiety.

The reaction takes place with HBr or HI because

these reagents are sufficiently acidic.
Step 2:

Step 3:

11.6.2 Physical Properties

However, when one of the alkyl group is a tertiary group,
The C-O bonds in ethers are polar and thus, ethers have a the halide formed is a tertiary halide.

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11

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.

In case of anisole, methylphenyl oxonium ion,

is formed by protonation of ether. The

bond between OCH3 is weaker than the bond between
OC6H5 because the carbon of phenyl has a partial
double bond character.
Therefore the attack by I ion breaks OCH3 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.

(i) Halogenation: .

(ii) Friedel-Crafts reaction: Anisole react with alkyl

halide and acyl halide in the presence of anhydrous
aluminium chloride (a Lewis acid) as catalyst.

case 1 if any Of R in (ROR) is 3o reaction is SN1 and

I- nucleophile is bonded with higher degree carbon
case 2 if any Of R in (ROR) is 1 0 or zero0 reaction
is SN2and I- nucleophile is bonded with lesser
degree carbon
case 3 if any of R is Ar (C6H5-) H5C6-O bond can
not break as it is partially doubly bonded due to
resonance stabilization
in given ex. bond will break between R-O

Ethers with two different alkyl groups are also

cleaved in the same manner.
R-O-R + HX -> R- X + R OH
The order of reactivity of hydrogen halides is as
follows:
HI > HBr > HCl. The cleavage of ethers takes place
with concentrated HI or HBr at high temperature.
Example 11.7
Give the major products that are formed by heating
each of the following ethers with HI.

Solution

(iii) Nitration: Anisole reacts with a mixture of

concentrated sulphuric and nitric acids to yield a mixture
of ortho and para nitroanisole.

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12

CHEMICAL TEST

1
acid]

OHgroup [alcohol, phenol and carboxylic

(i) Na -metal : evolves H2 gas with.

(ii) Lucas test: (anhydrous ZnCl2 /
fConcentrated HCl)
3 Formation of turbidity immediate
2 Formation of turbidity within 5 minutes.
1 No turbidity appears
2 Phenolic group
[i]Phenol gives violet colour with alc. FeCl3
[ii] Phenol gives white precipitate with Br2water

Since compound A contains a total of 8 carbon atoms, each

of B and C contain 4 carbon atoms.
Again, on dehydration, alcohol C
gives but-1-ene. Therefore, C is
of straight chain and hence, it is
butan-1-ol.
On oxidation, Butan-1-ol gives butanoic acid. Hence, acid
B is butanoic acid. Hence, the ester with molecular formula
C8H16O2 is butylbutanoate.
All the given reactions can be explained by the following
equations.

The Iodoform Test alcohols with following structure

undergo the iodoform reaction and give yellow

precipitate confirms the presence alcohols with above
structure
Give chemical test for folloing pairs
QPredict the products of the following reactions:

Methyl alcohol and ethyl alcohol

Iodoform test[NaOH+I2] , Yellow ppt with ethyl alcohol

(i)

Ethyl alcohol and n-propyl alcohol

Iodoform test[NaOH+I2] Yellow ppt with ethyl alcohol

n-Propyl alcohol and iso-propyl alcohol

(ii)

Iodoform test[NaOH+I2] Yellow ppt with iso-propyl alcohol

Butane-1-oland Butane-2-ol
Iodoform test[NaOH+I2] Yellow ppt with Butane-2-ol
0

(iii)

1 alcohol and 3 alcohol

Lucas test [conc-HCl+ ZnCl2] White turbidity with 30 alcohol

An alcohol and a phenol

(iv)
Answer

Neutral FeCl3 Violet colour with phenol

Phenol and

acetic acid [carboxylic acid]

Sodium bicarbonate ,Effervescence of CO2 with acetic acid

CID problems
An organic compound (A) (molecular formula C8H16O2)
was hydrolysed with dilute sulphuric acid to give a
carboxylic acid (B) and an alcohol (C). Oxidation of (C)
with chromic acid produced (B). (C) on dehydration
gives but-1-ene.Write equations for the reactions
involved.
Answer
An organic compound A with molecular formula C8H16O2
gives a carboxylic acid (B) and an alcohol (C) on hydrolysis
with dilute sulphuric acid. Thus, compound A must be an
ester. Further, alcohol C gives acid B on oxidation with
chromic acid. Thus, B and C must contain equal number of
carbon atoms.

MUKESH SHARMA

DPS JODHPUR

13

Intext Questions
11.10 Write the reactions of Williamson synthesis of 2ethoxy-3-methylpentane starting from ethanol and 3methylpentan-2-ol.
11.11 Which of the following is an appropriate set of
reactants for the preparation of 1-methoxy-4nitrobenzene and why?

11.12 Predict the products of the following reactions:

(i) b> d > c > a > e

7. Mark the correct increasing order of reactivity of the
following compounds with HBr/HCl.

Ans (i) b < c < a

8. Arrange the following compounds in increasing order
of boiling point. Propan-1-ol, butan-1-ol, butan-2-ol,
pentan-1-ol
9. name the reagent are used to convert RCHO into
RCH2OH?
Ans (i) H2/Pd (ii) LiAlH4 (iii) NaBH4
18. Complete the reactions

Some problems
1. Monochlorination of toluene in sunlight followed by
hydrolysis with aq. NaOH yields.
Ans Benzyl alcohol
2. How many alcohols with molecular formula C4H10O
are chiral in nature?
Ans 1
3. What is the correct order of reactivity of alcohols in
the following reaction?
Ans 3 > 2 > 1
4. CH3CH2OH can be converted into CH3CHO by
______________.
Ans treatment with pyridinium chlorochromate
5. Phenol is less acidic than ______________.
(i) ethanol (ii) o-nitrophenol
(iii) o-methylphenol (iv) o-methoxyphenol
6. Mark the correct order of decreasing acid strength of
the following compounds.

All reaction form phenol except iv

10.Name reagents can be used to oxidise primary
alcohols to aldehydes?
ans (i) Pyridinium chlorochromate. (ii) Heat in the
presence of Cu at 573K.
11. Phenol can be distinguished from ethanol by the
reactions with _________.
Ans (i) Br2/water (iii) Neutral FeCl3
convert the phenol into asprin

MUKESH SHARMA

DPS JODHPUR

14

Interconversions
How are the following conversions carried out?
(i) Propene Propan-2-ol
(ii)Benzyl chloride Benzyl alcohol
(iii) Ethyl magnesium chloride Propan-1-ol.
(iv) Methyl magnesium bromide 2-Methylpropan2-ol.
Answer
(i) If propene is allowed to react with water in the
presence of an acid as a catalyst, then propan-2-ol is
obtained.

(i)
(ii)
The given alcohols can be synthesized by applying
Markovnikovs rule of acid-catalyzed hydration of
appropriate alkenes.
(i)

(ii)
(ii) If benzyl chloride is treated with NaOH (followed
by acidification) then benzyl alcohol is produced.

(iii) When ethyl magnesium chloride is treated with

methanal, an adduct is the produced which gives
propan-1-ol on hydrolysis.

(iv) When methyl magnesium bromide is treated with

propane, an adduct is the product which gives 2methylpropane-2-ol on hydrolysis.

Q3
Give names of the reagents to bring about the
following
transformations:
(i) Hexan-1-ol to hexanal (ii) Cyclohexanol to
cyclohexanone
(iii) p-Fluorotoluene to p-fluorobenzaldehyde
(iv) Ethanenitrile to ethanol (v) Allyl alcohol to
propenal
(vi) But-2-ene to ethanol
A

Q 4 Alcohols are comparatively more soluble in water

than hydrocarbons of comparable molecular masses.
Explain this fact.
A4 Alcohols form H-bonds with water due to the presence
of OH group. However, hydrocarbons cannot form Hbonds with water.

As a result, alcohols are comparatively more soluble in

water than hydrocarbons of comparable molecular masses.

Q2 Show how would you synthesise the following

alcohols from appropriate alkenes?

Q5 Arrange the following compounds in the increasing

order of their boiling points:
15

MUKESH SHARMA

DPS JODHPUR

A 6The molecular masses of these compounds are in the

range of 72 to74. Since only butan-1-ol molecules are
associated due to extensive intermolecular hydrogen
bonding, therefore, the boiling point of butan-1-ol would be
the highest. Butanal is more polar than
ethoxyethane. Therefore, the intermolecular dipole-dipole
attraction is stronger in the former. n-Pentane molecules
have only weak van
der Waals forces Hence increasing order of boiling points
of the given compounds is as follows:

(b) n-Butane, ethoxyethane, pentanal and pentan-1ol

Q9

Arrange the following compounds in increasing

order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3

A9
CH3CH2CH3 < CH3OCH3 < CH3CHO <
CH3CH2OH
.Q10 Explain why is ortho nitrophenol more acidic
than ortho methoxyphenol?

Q6

While separating a mixture of ortho and para

nitrophenols by steam distillation, name
the isomer which will be steam volatile. Give
reason.

A6

Intramolecular H-bonding is present in onitrophenol and p-nitrophenol. In p-nitrophenol, the

A11
The nitro-group is an electron-withdrawing group.
molecules are strongly associated due to the
The presence of this group in the ortho position decreases
presence of intermolecular bonding. Hence, othe electron density in the OH bond. As a result, it is
nitrophenol is steam volatile.
easier to lose a proton. Also, the o-nitrophenoxide ion
formed after the loss of protons is stabilized by resonance.
Hence, ortho nitrophenol is a stronger acid.
On the other hand, methoxy group is an electron-releasing
group. Thus, it increases the electron density in the OH
bond and hence, the proton cannot be given out easily.

Q7

Give reason for the higher boiling point of

ethanol in comparison to methoxymethane.

A7
Ethanol undergoes intermolecular H-bonding due to
the presence of OH group, resulting in the association of
molecules. Extra energy is required to break these hydrogen
bonds. On the other hand, methoxymethane does not
undergo H-bonding. Hence, the boiling point of ethanol is
higher than that of methoxymethane.

Q8

Arrange the following sets of compounds in

order of their increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan1-ol, methanol.
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
.A 8
(a) Methanol, ethanol, propan-1-ol, butan-2-ol,
butan-1-ol, pentan-1-ol.

For this reason, ortho-nitrophenol is more acidic than orthomethoxyphenol

Q12 Preparation of ethers by acid dehydration of
secondary or tertiary alcohols is not a suitable method.
Give reason.
A12
The formation of ethers by dehydration of alcohol
is a bimolecular reaction (SN2) involving the attack of an
alcohol molecule on a protonated alcohol molecule. In the
method, the alkyl group should be unhindered. In case of
secondary or tertiary alcohols, the alkyl group is hindered.
As a result, elimination dominates substitution. Hence, in
place of ethers, alkenes are formed.
A13
The nitro-group is an electron-withdrawing group.
The presence of this group in the ortho position decreases
the electron density in the OH bond. As a result, it is
easier to lose a proton. Also, the o-nitrophenoxide ion
formed after the loss of protons is stabilized by resonance.
Hence, ortho nitrophenol is a stronger acid.
On the other hand, methoxy group is an electron-releasing
group. Thus, it increases the electron density in the OH
bond and hence, the proton cannot be given out easily. 16

MUKESH SHARMA

DPS JODHPUR

For this reason, ortho-nitrophenol is more acidic than ortho- (i) What would be the major product of this reaction ?
methoxyphenol.
(ii) Write a suitable reaction for the preparation of tbutylethyl ether.
Q15 Preparation of ethers by acid dehydration of
A17
(i) The major product of the given reaction is 2secondary or tertiary alcohols is not a suitable
methylprop-1-ene. It is because sodium ethoxide is a strong
method. Give reason.
nucleophile as well as a strong base. Thus elimination
reaction predominates over substitution.
A1
The formation of ethers by dehydration of alcohol
is a bimolecular reaction (SN2) involving the attack of an
alcohol molecule on a protonated alcohol molecule. In the
Ii
method, the alkyl group should be unhindered. In case of
Q18 The treatment of alkyl chlorides with aqueous
secondary or tertiary alcohols, the alkyl group is hindered.
KOH leads to the formation ofalcohols but in the
As a result, elimination dominates substitution. Hence, in
presence of alcoholic KOH, alkenes are major
place of ethers, alkenes are formed.
products. Explain.
Q16Explain the fact that in aryl alkyl ethers
A19
In an aqueous solution, KOH almost completely

(i) The alkoxy group activates the benzene ring towards ionizes to give OH ions. OH ion is a strong nucleophile,
which leads the alkyl chloride to undergo a substitution
electrophilic substitution and
reaction to form alcohol.
(ii) It directs the incoming substituents to ortho and
para positions in benzene ring.

A16

On the other hand, an alcoholic solution of KOH contains

alkoxide (RO) ion, which is a strong base. Thus, it can
abstract a hydrogen from the -carbon of the alkyl chloride
and form an alkene by eliminating a molecule of HCl.

(i)

In aryl alkyl ethers, due to the +R effect of the alkoxy

group, the electron density in the benzene ring increases as
shown in the following resonance structure.

Q30

Which of the following is an appropriate set of

reactants for the preparation of 1-methoxy-4nitrobenzene and why?

Thus, benzene is activated towards electrophilic substitution

by the alkoxy group.
(ii) It can also be observed from the resonance structures
that the electron density increases more at the ortho and
para positions than at the meta position. As a result, the
incoming substituents are directed to the ortho and para
positions in the benzene ring.
Q17 The following is not an appropriate reaction for
the preparation of
t-butyl ethyl ether.

(i)

(ii)

A30
Set (ii) is an
appropriate set of
reactants for the
preparation of 1methoxy-4nitrobenzene.
In set (i), sodium methoxide (CH3ONa) is a strong
nucleophile as well as a strong base. Hence, an elimination
reaction predominates over a substitution reaction.

MUKESH SHARMA

DPS JODHPUR

17

MUKESH SHARMA

DPS JODHPUR

18