Alcohol Phenol Ether

Alcohols, Phenols, and Ethers
Introducing Alcohols, Phenols and Ethers
What you will learn
• Classification of alcohols and phenols

• Classification of ethers
• Physical properties of alcohols and phenols
• Preparation of alcohols from alkene - (a) Acid
catalysed hydration and it's mechanism (b)
Hydroboration-oxidation and it's mechanism (c)
Using oxidising agents
• Preparation of alcohol from carbonyl compound:
reduction of aldehyde, ketone and carboxylic
acid
Alcohol and Phenol
-H
R H R OH
+ OH
Alcohol
OH
-H
+ OH
Phenol
Alkyl and Aryl Ethers
-H
R H R O R′
+ OR′
O R′
-H
+ OR′
Classification of
alcohols and phenols
Based on number Based on hybridisation

of — OH groups of ‘C’ in C–OH bond
Classification of Alcohols
Based on number
of -OH groups
1 2 3
Monohydric Dihydric Trihydric

Classification of Phenols
Based on number
of -OH groups
1 2 3
Monohydric Dihydric Trihydric

Classification of
alcohols and phenols
Based on number Based on hybridisation

of — OH groups of ‘C’ in C–OH bond
Classification of Alcohols and Phenols
Based on hybridisation
of ‘C’ in C–OH bond
Compounds with Compounds with

sp3 ‘C’ in C–OH sp2 ‘C’ in C–OH
bond bond
Alcohols
Compound containing
sp3 ‘C’ in C–OH bond
Alkyl Allylic Benzylic

alcohol alcohol alcohol
1° 2° 3°
Classification of Alcohols and Phenols
Compounds containing
sp2 ‘C’ in C–OH bond
Vinylic alcohols Phenol

Ethers
Ethers
Symmetrical Unsymmetrical
Symmetrical Ethers
Alkyl or aryl groups attached to either

side of the oxygen atom are same.
Example: C2H5OC2H5
Unsymmetrical Ethers
Alkyl or aryl groups attached to either

side of the oxygen atom are different.
Example: C2H5OCH3
The IUPAC name of the compound is:
CH2 CH CH3
OH
The IUPAC name of the compound is:
NO2
OC2H5
Physical properties
Solubility Boiling point

Solubility
Molecules are capable of forming strong

Miscible in hydrogen bonds with each other.
all proportions
Methanol and water 𝛅-
𝛅+ 𝛅+
Ethanol and water
𝛅-
Propanol and water 𝛅+

Hydrogen bond
Solubility
Ethers are soluble in water

because they form H-bond and
If the carbon chain of an have solubilities comparable
alcohol is long, the alcohol is to alcohols of similar molar mass.
much less soluble in water.
𝛅-
𝛅+ 𝛅+
Decyl alcohol with a chain
of 10 carbon atoms, is very 𝛅-
slightly soluble in water.
𝛅+
Hydrogen bond
Arrange the following sets of compounds in order of their
solubility:
n-Butane Pentanol Butanol

Physical properties
Solubility Boiling point

Boiling Point
Alcohols have much higher

boiling points than ethers
and hydrocarbons of
comparable molar mass.
Boiling Point
Alcohol molecules can associate

with each other through hydrogen
bonding, whereas those of ethers
and hydrocarbons cannot.
Hydrogen bond
Boiling Point
Ethers have boiling point that are roughly

comparable with those of hydrocarbons
of the similar molar mass (M.M.)
B.P. of Diethyl ether

(M.M. = 74 g mol−1) = 34.6 oC
B.P. of Pentane
(M.M. = 72 g mol−1) = 36 C
o
Boiling Point
Boiling points
Molar mass
of alcohols
Compound Boiling point (K)
Methanol 337
Ethanol 351
Propanol 370
Phenol 455
Methoxymethane 248
Preparation of alcohols
From carbonyl From Grignard

From alkene
compound reagent

From alkene
compound reagent
Acid-catalysed hydration
Hydroboration-oxidation

Acid-Catalysed Hydration of Alkenes
Alkenes react with water

in the presence of an acid
catalyst to yield alcohols.
General
reaction
Reagent used dil. H2SO4

Acid-Catalysed Hydration of Alkenes
In case of unsymmetrical
alkenes, the addition of water
takes place in accordance
with Markovnikov’s rule.
Give the major products of the following reactions:
Dil. H2SO4
Dil. H2SO4
Give the major product of the following reaction.
CH3
Dil. H2SO4
H C CH CH2
CH3
Which of the following compounds will give the same major
product on acid-catalysed hydration?
a) b)
c) d)
Solution
Hence, all the compounds will
give the same major product.
Hydroboration-Oxidation
General reaction
i) BH3, THF
ii) NaOH, H2O2

Mechanism of
Hydroboration
Mechanism
Step 1
Four-atom Syn additon

concerted T.S. of H and B
Mechanism
Step 2
CH3 CH CH2
CH3 CH2 CH2 BH2
Alkylborane
(CH3 CH2 CH2)2 BH
Dialkylborane
CH3 CH CH2
(CH3 CH2 CH2)3 B

Trialkylborane
Hydroboration
Hydroboration is regioselective
and it is anti-Markovnikov’s
addition.
The hydrogen atom gets

attached to the carbon atom
with fewer hydrogen atoms.
Hydroboration
99%
1% 2%
98%
Hydroboration
Observation: Reason:
Boron gets Steric factors:

attached to the The bulky boron-
less substituted containing group can
carbon atom of approach the less
the double bond. substituted carbon
atom more easily.
Stereochemistry of Hydroboration
The transition state for hydroboration

requires that the boron atom and the
hydrogen atom be added to the same
face of the double bond.
syn addition
+
Oxidation and Hydrolysis of Alkylboranes
H2O2, aq. NaOH, 25oC

R3B 3 + B(ONa)3
(oxidation and hydrolysis)
Oxidation and Hydrolysis of Alkylboranes
The oxidation and hydrolysis

take place with
retention of configuration
at the carbon initially bearing

boron and ultimately
bearing the hydroxyl group
Mechanism
(CH3 CH2 CH2)3 B
H2O2/OH– Oxidation
3 CH3 CH2 CH2 OH + BO3-

3
Regiochemistry of Hydroboration–Oxidation
Hydroboration–oxidation reactions
are regioselective.
The net result of hydroboration–

oxidation is anti-Markovnikov’s
addition of water to an unsymmetrical
alkene.
Hydroboration–Oxidation
Example
i) BH3, THF
ii) NaOH, H2O2

Summary
Anti-
Markovnikov’s
product
Hydroboration–
Oxidation
No
4 MTS (Member
carbocation,
transition state),
no
stereospecific
rearrangement
(i) B2H6/THF
–
A
(ii) H2O2/OH
True statement about above reaction:
a) Reagent involves stereospecific syn

addition of H and OH species.
b) Product obtained is trans isomer.
c) Boron atom acts as an electrophile.
d) Two stereoisomers are obtained as products.

(i) B2H6/THF
–
A
(ii) H2O2/OH
True statement about above reaction:

a) Reagent involves stereospecific syn
addition of H and OH species.
b) Product obtained is trans isomer.
c) Boron atom acts as an electrophile.

Solution
d) Two stereoisomers are obtained as products.
Hence, options (a), (b), (c) and
(d) are the correct answers.
Preparation of alcohol

From alkene
compound reagent
Acid-catalysed hydration
Hydroboration-oxidation

Preparation of Alcohols from Alkenes
OHˉ
+ KMnO4
H2O, cold
(1) OsO4, pyridine

(2) NaHSO3/H2O
Mechanism
Pyridine NaHSO3
+
H2O
Mechanism
Mechanism for the formation of a

1,2-diol by osmium tetroxide involves
a cyclic intermediate that results in

syn addition of the oxygen atoms

From alkene
compound reagent
Alcohols can be prepared
by reduction of carbonyl
compounds.
From aldehyde
Preparation From ketone

of alcohols
from carbonyl From
compounds carboxylic acid
From ester
55
Reduction of Aldehyde
Reducing
Aldehyde 1° Alcohol
agent
H2, Ni/Pd (C)/Pt
Reagent used
NaBH4/LiAlH4
Reduction of Aldehyde
H2, Ni/
Pd (C)/Pt
1° alcohol
NaBH4/LiAlH4
Reduction of Ketone
Reducing
Ketone 2° Alcohol
agent
H2, Ni/Pd(C)/Pt
Reagent used
NaBH4/LiAlH4
Reduction of Ketone
H2, Ni/
Pd (C)/Pt
2° alcohol
NaBH4/LiAlH4
Reduction of Carboxylic Acid
Reducing
Carboxylic acid 1° Alcohol
agent
(i) LiAlH4 - THF

Reagent used
(ii) H2O
Reduction of Carboxylic Acid
(i) LiAlH4 - THF

(ii) H2O
1° alcohol
Reduction of Ester
Ester Alcohol
Reagent (i) LiAlH4 in Et2O

used (ii) H2O/H2SO4
Reduction of Ester
(i) LiAlH4 in Et2O

(ii) H2O/H2SO4
+
NaBH4/LiAlH4
Aldehyde
or H2, Ni/Pt
NaBH4/LiAlH4
Ketone
or H2, Ni/Pt
Alcohols
(i) LiAlH4 - THF
Carboxylic acid
(ii) H2O
(i) LiAlH4 in Et2O

Ester
(ii) H2O/H2SO4
What you already know
● Preparation of Alcohols From
● Classification of Alcohols and
Alkene - (a) Acid Catalysed
Phenols - (a) Based on Number
Hydration and it's Mechanism
of OH Groups (b) Based on
(b) Hydroboration-oxidation
Hybridization of C in C-OH Bond
and it's Mechanism (c) Using
● Classification of Ethers - (a)
Oxidising Agents
Symmetrical Ether (b)
● Preparation of Alcohol From
Unsymmetrical Ether
Carbonyl Compound -
● Physical Properties of Alcohols
Reduction of Aldehyde,
and Phenols - Boiling Point and
Ketone and Carboxylic Acid
Solubility
What you will learn
● Preparation of Alcohol From Grignard
Reagent
● Preparation of Phenols - (a)
From Haloarenes (Dow Process) (b)
From Benzenesulphonic Acid (c) From
Diazonium Salts (d) From Cumene
● Preparation of Ethers - Dehydration of
Alcohols and it's Mechanism
● Limitations of Intermolecular
Dehydrations
Give the structures of the products of the following
reaction:
NaBH4
How many carbonyl compounds will give secondary alcohol
with molecular formula C5H12O after reduction with LiAlH4?
A and B are respectively are:
NaBH4 H2/Pd
B A
Which optically active compound will give an optically inactive
compound on reduction with LiAlH4?
a) b)
c) d)
Solution
Hence, option (c) is the correct answer.

Preparation of Alcohols
Preparation of Alcohols

From alkene
compound reagent
Addition of Grignard Reagent
– +
+ RMgBr
H2O/H+
H + Mg(OH)Br
– +
OMgX
Reaction of Grignard
reagent with formaldehyde – +
+ RMgX
H+/H2O
+ Mg(OH)X
Find the product of the following reaction:
(i) CH3MgX
(ii) /
How many compounds out of the following will give a
secondary alcohol on treatment with Grignard reagent?
(1) (2) (3)
(4) (5) (6)
Solution
Hence, three compounds give secondary alcohol on treatment

with Grignard reagent.
Which of the following methods would serve to prepare
1-Phenylpropan-2-ol?
a) Addition of benzyl Grignard reagent

to ethanal
b) Addition of phenyl magnesium
bromide with Butanal
c) Addition of methyl Grignard reagent
to phenyl acetaldehyde
Solution d) Addition of phenyl magnesium
Hence, option (a) and (c) are the bromide with Ethanal
correct answer.
Preparation of Phenols
From haloarenes
From benzene via

benzenesulphonic acid
Preparation
of Phenols
From aniline via
diazonium salts
From cumene
From haloarenes
From benzene via

Preparation
of Phenols
From aniline via
diazonium salts
From cumene
Dow Process
Cl
NaOH HCl
623 K
300 atm
From haloarenes
From benzene via

Preparation
of Phenols
From aniline via
diazonium salts
From cumene
Phenol from Benzene via Benzenesulphonic Acid
SO3H SO3Na
H2S2O7 NaOH
(Oleum)
NaOH, Δ Fusion
ONa
HCl
From haloarenes
From benzene via

Preparation
of Phenols
From aniline via
diazonium salts
From cumene
Phenols from Aniline via Diazonium Salts
+ –
NaNO2 H2O, Δ
-
+ HCl
HCl
0-5°C
From haloarenes
From benzene via

Preparation
of Phenols
From aniline via
diazonium salts
From cumene
Phenols from Cumene
(i) O2/Δ
+
(ii) H3O+
Mechanism
Formation of cumene
Step 1
hydroperoxide
O2
95-135oC
Cumene hydroperoxide
Mechanism
Step 2 Treatment with acid
H3O+
50-90oC
+
Phenol Acetone
What are P & Q?
CH3CH2CH2Cl /AlCl3 O2, H3O+

P Q + Phenol
∆
IIT-JEE-2006, 5/184
a) +
b) +
What are P & Q?

P Q + Phenol
∆
IIT-JEE-2006, 5/184
c) +
d) +
∆
+ Phenol
Solution
Hence, option (d) is the correct answer.
The major product U in the following reactions is:
, H+ Radical initiator, O2
T U
High pressure, heat
a) b)
The major product U in the following reactions is:
, H+ Radical initiator, O2
T U
High pressure, heat
c) d)
Solution
Hence, option (b) is the correct answer.

Preparation of Ethers
Dehydration Williamson
of alcohols synthesis
Recall
Alcohols can dehydrate to form alkenes.
Conc. H2SO4
443 K
+ H2O
Dehydration of Alcohols
Primary alcohols can also

dehydrate to form ethers.
Dehydration to form an ether usually

takes place at a lower temperature
than dehydration to the alkene.
HA/∆
R OH + HO R R O R
-H2O
H2SO4
443 K
H2SO4
413 K
Limitations of Intermolecular Dehydrations
Synthesis of ethers using

secondary alcohol is usually
01 unsuccessful because alkenes
are formed very easily.
Synthesis of ethers with tertiary

02 alkyl groups lead exclusively
to the formation of alkenes.
H2SO4
+ + H2O
Δ
Major Minor
Not useful for the preparation of

unsymmetrical ethers from primary
03
alcohols because the reaction leads
to a mixture of products.
ROR
H2SO4 +
ROH + R'OH ROR' + H2O
∆ +
R'OR'
1° Alcohol
Which of the following alcohols gives the best yield of dialkyl
ether on being heated with a trace of sulphuric acid?
a) Pentan-2-ol
b) Cyclopentanol
c) 2-Methyl-2-butanol
d) Pentan-1-ol
Solution

Keep Learning!
Chemical Properties of Alcohols

• Preparation of alcohol from Grignard
reagent
• Preparation of phenols -
• (a) From haloarenes (Dow process)
• (b) From benzenesulphonic acid
• (c) From diazonium salts
• (d) From cumene
• Preparation of ethers - Dehydration of
alcohols and it’s mechanism
• Limitations of intermolecular dehydrations
2
Chemical Properties of Alcohols
What you will learn

• Preparation of ethers continued - Williamson synthesis
and it’s mechanism
• Chemical properties of alcohol -
• (a) Alcohols act as electrophiles
• (b) Alcohols act as nucleophiles
• (c) Acidity of alcohols and phenols esterification –
• (a) Reaction of alcohol and phenol with carboxylic
acid
• (b) Reaction of alcohol and phenol with Acid Chloride
• (c) Reaction of Alcohol and Phenol with Acid
Anhydride
• Base-Promoted Hydrolysis of Esters: Saponification
3
Dehydration Williamson
of alcohols synthesis
Williamson Synthesis of Ethers
Synthesis of symmetrical and

unsymmetrical ethers by a
nucleophilic substitution reaction.
General reaction
′
′ Na+ + NaX
Mechanism
The alkoxide ion reacts with the

substrate via SN2 mechanism. +
+ lg
The substrate must be

+ + lg
unhindered
(1° or 2° alkyl halides) and bear a
good leaving group.
What is the major product of the following reaction?
+
Solution
+
For the synthesis of tert-

Butylmethyl ether, can we take the
starting materials as tert-Butyl
halide and methoxide ion?
+
If tert-butyl halide and methoxide ion
are used as reactants, it would result in
an elimination product and little or no
ether.
+ +
In carrying out a Williamson

synthesis of ether:
Less hindered alkyl group should

be provided by the alkyl halide.
More hindered alkyl group should

come from the alkoxide.
To synthesize tert-Butyl methyl ether,

the starting materials should be a
methyl halide and tert-Butoxide ion.
+ +
To prepare alkyl phenyl ether
Phenoxide ion is treated

with alkyl halide
+ NaOH
Predict the product.
+
In which of the following reactions the product obtained
is t-Butyl methyl ether?
Conc. H2SO4
a) +
HO Na+
b) +
In which of the following reactions the product obtained
is
t-Butyl methyl ether?
c) +
d) +
Hence, option (c) is the correct

answer.
In the reaction sequence:
NaOH CH3I HI
A B C+D
350oC
A, B, C and D are given by the set:
a) Sodium phenate, anisole, C6H5I, b) Sodium phenate, phenetole, C2H5I,

CH3OH C6H5OH
c) Sodium phenate, anisole, C6H5OH, d) Sodium phenate, phenetole, C6H5I,

CH3I C2H5OH
Solution
NaOH CH3I HI
A B C+D
350oC
a) Sodium phenate, anisole, C6H5I,

CH3OH
b) Sodium phenate, phenetole, C2H5I,

C6H5OH
Solution
NaOH CH3I HI
A B C+D
350oC
c) Sodium phenate, anisole, C6H5OH,

CH3I
d) Sodium phenate, phenetole, C6H5I,

C2H5OH
answer.
Chemical Properties of Alcohol
Chemical Properties
Reactions Reactions Reactions

of alcohols of phenols of ethers
Alcohol as an Electrophile
Reactions of
alcohols
Polarisation of the C―O bond makes the carbon

atom partially positive, and if it were not for the
fact that OH– is a poor leaving group, this carbon
would be susceptible to nucleophilic attack.
The hydroxyl group can be converted

to a good leaving group, so as to allow
substitution or elimination reactions.
Once the alcohol is converted to a good

leaving group, substitution reactions
become possible (SN2 or SN1, depending
on the class of alcohol).
Hydroxyl group can be

converted to a good
leaving group by
Protonation of alcohol
Conversion of alcohols
into alkyl halides
Conversion to a
sulphonate ester derivative
Protonation of Alcohols
Protonation of an alcohol converts

1 a poor leaving group (OH–) into
a good leaving group (H2O).
+ -
..
.. +
Conversion of Alcohols into Alkyl Halides
With PBr3 and SOCl2, an alcohol

2 converts a poor leaving group (OH–)
into a good leaving group (Br– or Cl–).
+ +
Pyridine
+ SOCl2
Conversion to a Sulphonate Ester Derivative
The hydroxyl group of an alcohol can be

converted into a good leaving group by the
conversion to a sulphonate ester derivative.
where R = -Ms, -Ts, -Tf

Conversion to a Sulphonate Ester Derivative
or Ms –
or Ts –
or MeSO2 –
The mesyl group The tosyl group
or CF3SO2 –
or Tf –
The trifyl group

Alcohol as Nucleophile
The oxygen atom of the hydroxyl

group is nucleophilic in nature.
+
R + R +
Chemical Reactions of Alcohols
Chemical Reactions
of Alcohols
Based on Based on
cleavage of cleavage of
O–H bond C–O bond
Reactions Involving
Cleavage of O–H bond
Acidity of alcohols
Esterification
and phenols
Acidity of Alcohols and Phenols
Reaction with metals
Alcohols and phenols release H2 gas on reaction

with sodium, potassium, or other alkali metals.
This reflects the presence

of acidic hydrogen.
2ROH + 2Na 2RONa +

H2
2 + 2Na 2 + H2
Alcohol reacts with sodium metal to produce hydrogen gas, which shows that
alcohol contains acidic hydrogen.
Arrange the following in the decreasing order of acidic
character: Cyclohexanol (I), acetic acid (II), 2,4,6-
trinitrophenol (III) and phenol (IV).
a) III > II > IV > I
b) II > III > I > IV
c) II > III > IV > I
Hence, option (a) is the correct

answer. d) III > IV > II > I
Find the order of pKa values for the following
compounds:
o-Cresol m-Cresol Phenol

The correct order of acidity for the following
compounds is:
I II
III IV
The correct order of acidity for the following
compounds is:
a) I > II > III > IV
b) III > I > II > IV
c) III > IV > II > I
Hence, option (a) is the correct d) I > III > IV > II

answer.
Reactions Involving
Cleavage of O–H Bond
Acidity of alcohols
Esterification
and phenols
Esterification
From
carboxylic acid
From
Esterification
acyl chloride
From carboxylic
acid anhydride
Esterification
General reaction
HA
+
Mechanism
Mechanism
..
Step 1 +
+
Step 2
-
Mechanism
..
..
Step 3
-H3O+
+H3O+
Acid-Catalysed Esterification
Esterification proceeds very slowly

in the absence of strong acids.
When an acid and an alcohol react with

a small amount of conc. H2SO4 or HCl,
they reach equilibrium within few hours.
Acid-Catalysed Esterification
Yield of esterification can be increased by
The use of an excess of either

1 carboxylic acid or the alcohol.
By removing water from the

2
reaction mixture as it is formed
Steric Factors
Tertiary alcohols
react so slowly in acid-catalysed
esterifications that they usually
undergo elimination instead.
However, they can be safely

converted to esters by using
acyl chlorides and anhydrides
Esterification
From
carboxylic acid
From
Esterification
acyl chloride
From carboxylic
acid anhydride
Esters from Acyl Chlorides
General reaction
-HCl
+
Pyridine is often added to the reaction

mixture to react with the HCl that forms.
Esterification
From
carboxylic acid
From
Esterification
acyl chloride
From carboxylic
acid anhydride
Esters from Carboxylic Acid Anhydride
General reaction
+
Note
Ester synthesis is best

accomplished by the
reaction of an alcohol with
an acyl chloride or
acid anhydride.
Esters from Acyl Chloride or
Anhydride
These reagents avoid the use

of a strong acids, which is normal
for acid-catalysed esterification.
A strong acid may cause side

reactions depending on what
other functional groups are present.
Application
H+
+ (CH3CO)2O + CH3COOH
Salicylic Acetylsalicylic acid

acid (Aspirin)
Base-Promoted
Hydrolysis of Esters:
Saponification
Saponification
Refluxing an ester with aqueous

sodium hydroxide, produces an alcohol
and the sodium salt of the acid
H2O
+ +
Mechanism
Mechanism
Step 1
Step 2
Mechanism
Step 3 +
+
Note
Base-promoted
hydrolysis of an
ester, as a result,
is an essentially
irreversible reaction.
The reaction given below is called:
H+ or OHˉ
RCOORʹ + RʹʹOH (excess) RCOORʹʹ + RʹOH
a) Esterification
b) Trans-esterification
c) Saponification
Hence, option (b) is the correct

answer. d) Hydrolysis
Conc.
+ (X)
Conc.
+ (Y)
a) (X) is optically active, while (Y) is optically c) Both (X) and (Y) are optically
inactive inactive
b) Both (X) and (Y) are optically active d) (X) is optically inactive, while (Y) is
optically active
Conc.
+ (X)
Solution
Conc.
+ (Y)
a) (X) is optically active, while (Y) is optically

inactive
Hence, option (a) is the correct b) Both (X) and (Y) are optically active
answer.
Keep Learning!
Continuing Chemical Properties of
Alcohols and Phenols
● Preparation of ethers continued

● Chemical properties of alcohol
● Esterification - (a) reaction of alcohol and phenol with
carboxylic acid (b) reaction of alcohol and phenol with
acid chloride (c) reaction of alcohol and phenol with
acid anhydride
● Base-promoted hydrolysis of esters: saponification
Continuing Chemical Properties of
Alcohols and Phenols
What you will learn
● Chemical reactions of alcohols -

reaction involving cleavage of C-O
bond
● Oxidation of alcohols
● Reactions of phenol - (a) oxidation
of phenol (b) electrophilic
substitution reaction
● Preparation of picric acid
Chemical reactions
of alcohols
Based on Based on
cleavage of cleavage of
O–H bond C–O bond
4
Reaction with HX
Reactions involving
Reaction with PX3
cleavage of C–O bond
Dehydration
5
PCl3
HI
Conc. H2SO4
∆
Oxidation of
Alcohols
Oxidation of Primary Alcohols
Primary alcohols can be oxidised

to aldehydes and carboxylic acids.
[O] [O]
1° Alcohol Aldehyde Carboxylic acid

The oxidation of aldehydes to carboxylic

acids in aqueous solutions is easier than the
oxidation of primary alcohols to aldehydes.
It is difficult to stop the oxidation of

a primary alcohol at the aldehyde stage,
unless specialised reagents are used.
An excellent reagent for converting

a primary alcohol into an aldehyde is
pyridinium chlorochromate (PCC).
PCC is formed when CrO3 is dissolved

in HCl and then treated with pyridine.
PCC
CrO3 + HCl +
Pyridinium
chlorochromate (PCC)
PCC
PCC, when dissolved in methylene chloride

(CH2Cl2), will oxidise a primary alcohol to an
aldehyde, and stop at that stage.
PCC
CH2Cl2
Primary alcohol Aldehyde

PCC
PCC will also oxidise a

secondary alcohol to a ketone.
PCC
CH2Cl2
Secondary alcohol Ketone

PCC
PCC does
not attack
double bonds.
What is the product of the following reaction?
PCC
Oxidation of 1o Alcohols to Carboxylic Acids
Primary alcohols can be oxidised to carboxylic

acids by potassium permanganate (KMnO4) or
chromic acid (H2CrO4).
KMnO4 or H2CrO4
RCH2OH RCOOH
Oxidation of 1o Alcohols to Carboxylic Acids
KMnO4, OH‒ H3O+

H2O, Δ
+ MnO2
The reaction with KMnO4 is usually carried out

in basic aqueous solution, wherein MnO2
precipitates as the oxidation takes place.
On oxidising ethanal using a strong oxidising agent, carboxylic
acid is obtained. Which of the following statements is correct
regarding the formed carboxylic acid?
a) Number of C atoms in the formed carboxylic acid

will be one greater than that of aldehyde taken
b) Number of C atoms in formed carboxylic acid will

be one less than that of aldehyde taken
c) Number of C atoms in formed carboxylic acid will

be same as that of aldehyde taken
Solution d) None of these
Hence, option c is the correct answer.

Oxidation of 2o Alcohols to Ketone
Both KMnO4 and H2CrO4 can also be used to

oxidise a secondary alcohol to a ketone.
H2CrO4
2° Alcohol Ketone
Acidic KMnO4 & K2Cr2O7 as Oxidising Agents
Ketones are difficult to oxidise.

They are oxidised only on heating
with a strong oxidising agent.
Cleavage of C–C bonds takes

place and a mixture of carboxylic
acids containing lesser number
of carbon atoms is formed.
Oxidation of Ketone
KMnO4, H+
Δ
+
Oxidation of 2o Alcohols
Oxidation of 2° alcohols
usually stops at the ketone
stage because further
oxidation requires the
breaking of a C–C bond.
Jones Reagent
Chromic acid is usually prepared

by adding Cr(VI) oxide (CrO3) or
sodium dichromate (Na2Cr2O7)
to aqueous sulfuric acid.
The mixture is known

as Jones reagent
Jones Reagent
Oxidations of secondary alcohols

are generally carried out by adding
Jones reagent to a solution of the
alcohol in acetone or acetic acid.
This procedure rarely

affects double bonds
present in the molecule.
Jones Reagent
Jones reagent
Oxidation
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
Oxidation
Dehydrogenation
Cu/Δ
573 K
Cu/Δ
573 K
Dehydration
Cu/Δ
573 K
The major product formed in the following reaction is:
O
2º PCC
3º
CH2Cl2
O
1º
OH
PCC only oxidises primary and secondary –OH but no effect on tertiary
–OH group.
The alcohol refusing to generate a carbonyl compound on
oxidation with acidified KMnO4 is:
a) b)
c) d)
Solution

Identify product (Q) in the given reaction.
PCC
(Q)
CH2Cl2
The most suitable reagent for the conversion of
RCH2OH RCHO is:
a) KMnO4
b) K2Cr2O7
c) CrO3
Solution
d) PCC (Pyridinium chlorochromate)
Chemical properties
Reactions Reactions Reactions

of alcohols of phenols of ethers
1 Oxidation
2 Electrophilic aromatic substitution
Reactions
3 Kolbe reaction
of Phenols
4 Reimer–Tiemann reaction
5 Reaction of phenols with zinc dust

Oxidation of Phenol
Na2Cr2O7
H2SO4, H2O
Benzoquinone
Electrophilic Aromatic Substitution
General reaction
+ E+ + H+
-OH group acts as a powerful

activating group (+M) and an
ortho–para director
Nitration
Phenol reacts with dilute nitric acid to yield

a mixture of o- and p-Nitrophenol
20% HNO3
25oC
+
30-40%
15%
Nitration
Yield is relatively low (because

1
of oxidation of the ring)
Ortho and para isomers can be

2
separated by steam distillation
Nitration
o-Nitrophenol p-Nitrophenol
Intramolecular Intermolecular
H-bonding H-bonding
More volatile Less volatile
Passes over Remains in the

with the steam distillation flask
Intramolecular H-bonding
in o-nitrophenol
Intermolecular H-bonding
in p-nitrophenol
Nitration
Phenol with conc. nitric acid gives picric acid

in low yield (because of oxidation of ring).
Conc. HNO3/
H2SO4
Picric acid
Preparation of Picric acid
Conc. H2SO4 Conc. HNO3

Bromination
Phenol reacts with bromine in

aqueous solution to yield
2,4,6-tribromophenol.
Lewis acid is not required for the

bromination of this highly activated ring.
Bromination
3Br2
H2O
+ 3HBr
2,4,6-Tribromophenol
(≈ 100%)
Bromination
Monobromination of phenols can be achieved by

carrying out the reaction in carbon disulfide
at a low temperature, a condition that reduces
the electrophilic reactivity of bromine.
The major product is the para isomer.

Bromination
Br2
+ HBr
CS2, 5 oC
p-Bromophenol
(80-84%)
Bromination of Phenol
Br2 3Br2
CS2, 5 oC H2O
Observe the following reaction. Y is:
dil. HNO3
(X) + (Y)
Steam distillation
(Y) Low boiling point

a) b)
Solution
c) d)
Ortho-nitro phenol has low boiling
point than para-nitro phenol due to
intramolecular H-bonding.

answer.
In the reaction, the intermediate(s) is/are:
NaOH(aq.)/Br
a) b)
In the reaction, the intermediate(s) is/are:
NaOH(aq.)/Br2
c) d)
Solution
Hence, option (a), (b) and (c) are
the correct answers.
Important Name Reactions of Phenol
What you will learn

● Reactions of phenol continued
● Chemical reactions of alcohol
● Commercially important alcohol
● Oxidation of alcohols
● Preparation, properties and
● Reactions of phenols
uses of methanol and ethanol
● Preparation of picric acid
● Reactions of ethers
1 Oxidation
2 Electrophilic aromatic substitution
Reactions
3 Kolbe reaction
of phenols
4 Reimer–Tiemann reaction
5 Reaction of phenol with zinc dust

Kolbe Reaction
Kolbe reaction is carried out by

allowing sodium phenoxide
to absorb carbon dioxide.
Acidification of the resulting

mixture produces salicylic acid.
Kolbe Reaction
(i) NaOH (ii) CO2

(iii) HCl
The phenoxide ion is even more

susceptible to electrophilic aromatic
substitution than the phenol itself.
Mechanism
Na+
Step 1
Na+
Tautomerisation
Na+
Mechanism
Step 2
Na+ H O+ OH
3
Assertion: Phenol undergoes Kolbe reaction, ethanol does not.
Reason: Phenoxide ion is more basic than ethoxide ion.
a) Both assertion and reason are correct, and the

reason is a correct explanation of the assertion.
b) Both assertion and reason are correct, but the

reason is not a correct explanation of the assertion.
Assertion: Phenol undergoes Kolbe reaction, ethanol does not.
Reason: Phenoxide ion is more basic than ethoxide ion.
c) The assertion is correct, but the reason is

incorrect.
d) Both the assertion and reason are incorrect.
Solution
Hence, option (c) is the correct answer.

Reimer–Tiemann Reaction
(i) CHCl3/NaOH/Δ
+
(ii) H+
Minor Major
An important way of making

ortho-substituted phenols
Mechanism
Step 1 Formation of carbene
Step 2 Attack of carbene

on phenol
𝝰-Elimination
KOH + _
+ :
Dichlorocarbene
_ _
HO
Mechanism
Step 1 Formation of carbene
Step 2 Attack of carbene

on phenol
Mechanism
Reaction of Phenol with Zinc Dust
Δ
+ Zn + ZnO
Which of following statements is correct?
a) In Reimer–Tiemann reaction, dichlorocarbene

intermediate is produced.
b) Reimer–Tiemann reaction is an example of

electrophilic substitution reaction.
c) Highly reactive ring like aniline and highly

deactivated ring like nitrobenzene, cyanobenzene
do not give Friedel–Crafts reaction.
Solution
Hence, option (d) is the d) All of these

correct answer.
Identify the intermediates of the following reaction.
Δ
+ CHCl3 + NaOH
Identify the intermediates of the following reaction.
a) b)
c) d)
Solution
Hence, option (a) and (b)
are the correct answer.
In the following reaction, the product(s) formed is(are):
a) b)
In the following reaction, the product(s) formed is(are):
Solution c) d)
Hence, options (a), (b) and

(c) are the correct answer.
Some Commercially
Important Alcohols
Important alcohols
Methanol Ethanol
22
Methanol
Earlier, methanol was produced by

the destructive distillation of wood
(i.e., heating wood to a high
temperature in the absence of air).
Hence, it was also known

as wood alcohol.
Preparation of Methanol
Heating wood to 450°–550°C in

the absence of oxygen causes it
to decompose. Gases (carbon Boiling tube
dioxide, carbon monoxide, and
methane), liquids, and a solid Saw dust Mixtures of
residue (charcoal) are produced gases
as a result of this process. As a
mixture of steam and gases, the
gaseous and liquid components
separate; and when the mixture
is cooled, a distillate is obtained. Water
Consecutively, the distillate
splits into pyro-ligneous acid
and wood tar.
Methanol
Now, most methanol is prepared by

the catalytic hydrogenation of CO.
ZnO–Cr2O3
CO + 2H2 CH3OH
300–400 oC
200–300 atm
Uses of Methanol
It is used in
1
making formaldehyde.
It is used as a
2
solvent in paints.
Harmful Effects
Methanol is toxic. Ingestion of even

small quantities of methanol can cause
blindness; large quantities cause death.
Methanol poisoning can also occur

by inhalation of the vapours or by
prolonged exposure to the skin.
Ethanol
Ethanol can be made by

the fermentation of sugars.
Synthesis of ethanol in the form of wine by

the fermentation of the sugars of fruit juices
was probably the first accomplishment in
the field of organic synthesis.
Preparation
Fermentation is usually carried

out by adding yeast to a mixture
of sugar and water.
Yeast contains enzymes that promote

a long series of reactions that ultimately
convert a simple sugar (C6H12O6) to
ethanol and carbon dioxide.
Preparation
Invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Glucose Fructose
Zymase
C6H12O6 2C2H5OH + 2CO2
Ethanol
Fermentation does not produce

beverages with an ethanol content
greater than 12–15%.
Enzymes of the yeast are deactivated

at higher concentrations.
To produce beverages of higher

alcohol content, the aqueous
solution must be distilled.
Industrial Preparation
Acid
+ H2O
About 5% of the world’s ethanol

supply is produced this way.
Phenol is distilled with zinc dust followed by Friedel–Crafts
alkylation with propyl chloride in the presence of AlCl3 to
give a compound (B). B is oxidised in the presence of air to
form compound C. The structural formula of C is:
a) b)
Phenol is distilled with zinc dust followed by Friedel–Crafts
alkylation with propyl chloride in the presence of AlCl3 to
give a compound (B). B is oxidised in the presence of air to
form compound C. The structural formula of C is:
c) d)
Solution

answer.
The product obtained from the reaction is:
(i) NaOH
(ii) CO2
(iii) Hydrolysis
a) Benzene b) Toluene
Solution
c) Salicylic acid d) Benzoic acid
answer.
Chemical properties
Reactions of Reactions of Reactions of

alcohols phenols ethers
Chemical reactions of ethers
1 2
Cleavage of Electrophilic
C–O bond in substitution
ethers reaction
Ethers
Ethers are unreactive towards

most bases, but they can react
under extremely acidic conditions.
A protonated ether can

undergo substitution with
the expulsion of an alcohol.
Reaction with HX
Ethers react with conc. HBr and HI

because these reagents are sufficiently
acidic to protonate the ethers.
Bromide and iodide are good nucleophiles

for the substitution reaction.
Reaction with HX
General reaction
+
+ HI
I– Δ
I +
SN2 Reaction of Ethers
+H Br + Br
Then the mechanism

If R or R′ is 3º will be SN1; otherwise,
it will be SN2
Mechanism
Step 1: Protonation
+
+ H Br + Br
Attack of Nucleophile
Step 2: Attack of nucleophile
+ Br
+ Br
Note
If HBr is present in excess,

the ethanol (just formed)
reacts with the HBr (present
in excess) to form a second
molar equivalent of ethyl
bromide.
SN1 Reaction of Ethers
General reaction
+ HI
I + CH3OH
Mechanism
Step 1: Preparation of carbocation
H H3
.. +
.. + H+ .. +
H3
Mechanism
Step 2: Attack of the nucleophile
H3
+ + I I
H3
Alkyl Aryl Ether
Alkyl aryl ethers

are cleaved at the
alkyl–oxygen bond
due to the more stable
aryl–oxygen bond.
Alkyl Aryl Ether
HBr
Br‒
+ Br
The major product of this reaction is:
HBr
excess
Excess HI
Excess HI
Electrophilic Substitution Reaction
General reaction
+ E
+
+ H+
The alkoxy group (-OR) is ortho–para

directing and activates the aromatic
ring towards electrophilic substitution.
Halogenation
+ Br2 +
Minor
Major
Friedel–Crafts Reaction
Anhyd. AlCl3
+
CS2
Minor
+ CH3Cl
Major
Friedel–Crafts Reaction
Anhyd. AlCl3
+
+ CH3COCl
Minor Major
The ether that undergoes electrophilic substitution reactions
is:
a) CH3OC2H5
b) C6H5OCH3
c) CH3OCH3
Solution
d) C2H5OC2H5
Hence, option (b) is the correct
answer.
In Reimer–Tiemann reaction, molecular weight of phenol
increases by:
a) 28
b) 29
c) 30
Solution
Hence, option (a) is the correct d) 31
answer.
Which among the following ethers will produce methyl alcohol
on treatment with HI?
a)
b)
Which among the following ethers will produce methyl alcohol
on treatment with HI?
c)
d) None of these
Solution
Hence, option (a) is the correct
answer.
Keep Learning!

Alcohol Phenol Ether

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Alcohol Phenol Ether

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Alcohols, Phenols, and Ethers

Introducing Alcohols, Phenols and Ethers

What you will learn

• Classification of alcohols and phenols

Based on number Based on hybridisation

Monohydric Dihydric Trihydric

Monohydric Dihydric Trihydric

Based on number Based on hybridisation

Compounds with Compounds with

Alkyl Allylic Benzylic

Vinylic alcohols Phenol

Alkyl or aryl groups attached to either

Alkyl or aryl groups attached to either

Solubility Boiling point

Molecules are capable of forming strong

Methanol and water 𝛅-

Propanol and water 𝛅+

Ethers are soluble in water

n-Butane Pentanol Butanol

Solubility Boiling point

Alcohols have much higher

Alcohol molecules can associate

Ethers have boiling point that are roughly

B.P. of Diethyl ether

Compound Boiling point (K)

From carbonyl From Grignard

From carbonyl From Grignard

Using oxidising agents

Alkenes react with water

Reagent used dil. H2SO4

ii) NaOH, H2O2

Four-atom Syn additon

(CH3 CH2 CH2)3 B

The hydrogen atom gets

Boron gets Steric factors:

The transition state for hydroboration

H2O2, aq. NaOH, 25oC

The oxidation and hydrolysis

at the carbon initially bearing

(CH3 CH2 CH2)3 B

3 CH3 CH2 CH2 OH + BO3-

The net result of hydroboration–

ii) NaOH, H2O2

True statement about above reaction:

a) Reagent involves stereospecific syn

b) Product obtained is trans isomer.

c) Boron atom acts as an electrophile.

d) Two stereoisomers are obtained as products.

True statement about above reaction:

b) Product obtained is trans isomer.

c) Boron atom acts as an electrophile.

From carbonyl From Grignard

Using oxidising agents

(1) OsO4, pyridine

Mechanism for the formation of a

a cyclic intermediate that results in

From carbonyl From Grignard

Preparation From ketone

H2, Ni/Pd (C)/Pt

(i) LiAlH4 - THF

(i) LiAlH4 - THF

Reagent (i) LiAlH4 in Et2O

(i) LiAlH4 in Et2O

(i) LiAlH4 in Et2O