Alcohols

Alcohols
General Methods of Preparation of Alcohols
1. From haloalkanes:
It is to be noted that in this method, primmy haloalkanes give a

good yield of alcohols. Secondary haloalkanes undergo
simultaneous dehydrohalogenation and give a mixture of
alcohols and alkenes. Tertiary haloalkanes undergo mainly
dehydrohalogenation and give mainly alkenes as shown below.
2. By reduction of carbonyl compounds :
a) Reduction of aldehydes :
b) Reduction of ketones :
C) Reduction of carboxylic acids
d) Reduction of esters :
3) From Grignard reagents :
a) Preparation of 1 ° alcohols :
Primary ( 1 ° ) alcohols can be obtained by treating Grignard reagents
with form aldehyde followed by hydrolysis by a dilute acid.
b) Preparation of 2° alcohols :
Secondary (2°) alcohols can be prepared by treating

Grignard reagents with any aldehyde except
formaldehyde and hydrolysing the addition product
with a dilute acid.
c) Preparation of 3° alcohols :
Tertiary (3 °) alcohols are obtained by the action of
Grignard reagents on a ketone followed by hydrolysis
with a dilute acid.
4) By hydrolysis of esters:
5) From aliphatic primary amines :
Industrial Preparation of
Alcohols
1. Hydration of alkenes :
a) By acid catalysed hydration :
b) Indirect addition of water :
In case of unsymmetrical alkenes, addition of sulphuric acid takes pl ace

in accordance to the Markownikoffs rule.
c) Indirect anti-Markownikoff's addition of water
Hydroboration-oxidation process:
 In this process , the alkene is treated with diborane (B2H6) and
the product obtained is oxidised with alkaline hydrogen
peroxide. For example:
2) Fermentation of carbohydrates :
 The slow decomposition of large molecules of certain organic

compounds into simpler ones under catalytic influence of
enzymes is known as fermentation.
Physical Properties
of Alcohols
Several properties of alcohols such as solubility in water, high boiling
points, high viscosity, etc. ,are due to the capability of alcohols to form
intermolecular hydrogen bonding.
 The presence of a partial positive charge on hydrogen and a

partial negative charge on oxygen permit alcohol molecules
to undergo the formation of intermolecular hydrogen bonds
as shown below.
The lower members of the alcohol family are
completely miscible with water. >>This is due to
their capability of forming intermolecular hydro
gen bonds with water molecules. Alcohols being
polar can easily form hydrogen bonds with water
molecules which are also polar in nature.
The solubility of alcohols in water decreases with increase in molecular

mass , i.e. , with increase in the size of the alkyl group . Alkyl groups are
hydrophobic groups and are insoluble in water. In lower alcohols , the
alkyl group is small and the - OH group of the alcohol is effective in
making the molecule water soluble. As the size of alkyl group increase s
in higher alcohols , the hydrophobic nature of alky l group dominates
over the hydrophilic nature of - OH group .
Boiling points :
The boiling points of alcohols are considerably higher

than those of corresponding hydrocarbons, haloalkanes,
ethers, etc.
Ans. The higher boiling points of alcohols are due to
existence of strong hydrogen bonding between their
molecules
The boiling points of alcohols increase with increase
in the molecular mass.
Ans. Due to increase in
Size of chain van der
Waal’s force increases.
For isomeric alcohols , the boiling points decrease with
branching.
 Primary (1 °) alcohol > Secondary (2°) alcohol > Tertiary (3°) alcohol.
Chemical Properties of
Alcohols
A. Reactions involving cleavage of O-H bond
Acidic character of alcohols :

The acidic nature of alcohols is due to the polarity of
O-H bond. o atom being more electronegative pulls the
shared pair of electrons of O-H bond. On account of
this , the shared pair shifts towards O atom and the O-
H bond becomes weak. This facilitates the release of a
proton (H +) from the molecule. This is way alcohols
behave as weak acids. Their acidic strength is even less
than that of wate1·
Ques. Alcohols are weaker
acids than water :
Alkyl Groups Are Electron Releasing (Electron Repelling)
Groups And Increase The Electron Density At The O-atom
D u e To + I - e f f e c t . T h e r e f o r e , I n A l c o h o l s , T h e O x y g e n A t o m
S h o w s L e s s e r Te n d e n c y To A t t r a c t T h e S h a r e d E l e c t r o n s O f
O-h Bond. This Decreases The Polarity Of O-h Bond.
Thus, The O-H Bond In Alcohols Is Less Polar As Compared

To T h a t I n Wa t e r. D u e To L o w P o l a r i t y. O f O - H B o n d , T h e
Release Of H+ Ions In Alcohols Becomes More Difficult As
C o m p a r e d To T h a t I n Wa t e r.
Relative acidic strength of 1 °, 2° and 3° alcohols :
2· Reaction with active metals
3. Reaction with carboxylic acids (Esterification) :
Example:
Mechanism:
4. Reaction with acid chlorides and acid
anhydride (Acylation) :
[B] Reactions Involving
Cleavage of C-OH Bond
Higher the number of alkyl groups attached to the
carbon carrying -OH group, more is the polarity of
C-O bond and easier is its cleavage ; consequently
greater is the reactivity of the alcohol. Thus, the
reactivity of alcohols follows the order:
1.Reaction with hydrogen halides :
In this reaction , the order of reactivity of alcnh0l is:

3° alcohol >2° alcohol > 1° alcohol
And that of hydrocarbon halide:
HI >HBr >HCI.
2. Reaction with phosphorus halides & thionyl chloride :
[C]Reactions Involving Both
Alkyl as well as
Hydroxyl Groups
1. Dehydration :
Formation of alkenes : When alcohols are heated

with cone. H2S04 (or H3P0 4) at 433 K, they undergo
dehydration (i.e lose a molecule of water) to form
alkenes:
Mechanism :
lnterconvcrsion of Alcohol
Conversion of a lower alcohol Into a higher

alcohol: (Ascent of the series)
Conversion of a higher alcohol into a lower
alcohol (Descent of the series) :
Conversion of a primary alcohol to a
secondary alcohol:
Conversion of a secondary alcohol to a
tertiary alcohol :
Conversion of a primary alcohol to a
tertiary alcohol :

Alcohols

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Alcohols

General Methods of Preparation of Alcohols

1. From haloalkanes:

It is to be noted that in this method, primmy haloalkanes give a

Secondary (2°) alcohols can be prepared by treating

b) Indirect addition of water :

In case of unsymmetrical alkenes, addition of sulphuric acid takes pl ace

 The slow decomposition of large molecules of certain organic

 The presence of a partial positive charge on hydrogen and a

The solubility of alcohols in water decreases with increase in molecular

The boiling points of alcohols are considerably higher

Acidic character of alcohols :

Thus, The O-H Bond In Alcohols Is Less Polar As Compared

In this reaction , the order of reactivity of alcnh0l is:

Formation of alkenes : When alcohols are heated

Conversion of a lower alcohol Into a higher

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