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ALCOHOLS
Definition
Classification
Nomenclature
Synthesis
Physical Properties
Reactions

DEFINITION
Alcohols are compounds in which a
hydroxyl group (-OH) is attached to a
saturated carbon
C OH
Functional Group
Saturated Carbon
R-OH
General Formula
CH
3
OH CH
3
CH
2
OH
Methyl alcohol
Ethyl alcohol
Examples:
ALCOHOLS
CLASSIFICATION OF ALCOHOLS
ALCOHOLS
Based on number of
OH group
Based on position of
OH group
Monohydroxy Alcohols
Dihydroxy Alcohol
Trihydroxy Alcohols
Polyhydroxy Alcohols
Primary Alcohols
Secondary Alcohol
Tertiary Alcohols

Monohydroxy Alcohols
Methanol H
H C O H CH
3
OH
H
Ethanol H H
H C C O H C
2
H
5
OH
H H
Produced by Fermentation
Glucose zymase Carbon dioxide + Ethanol
C
6
H
12
O
6
CO
2
+ C
2
H
5
OH
Dihydroxy Alcohols
- contain two -OH groups

C
2
H
4
(OH)
2


1,2-ethanediol (ethylene glycol) anti-freeze
- contain three -OH groups
H H H
H C C C H C
3
H
5
(OH)
3

OH OH OH

1,2,3-propanetriol (glycerine or glycerol)
C C
OH
H
H
OH
H
H
Trihydroxy Alcohols
Polyhydroxy Alcohols
CH
2
CH CH
OH OH OH
CH CH C
O
H
OH OH
Glucose---a sugar
(open f ormof molecule)
- contain more than three -OH groups
Primary Alcohols
1-propanol H H H
H C C C OH C
3
H
7
OH
H H H
The above is a primary alcohol
Secondary Alcohols
2-propanol (isopropyl alcohol)
H H H
H C C C H C
3
H
7
OH
H OH H
The above is a secondary alcohol.
The -OH is attached to a C atom which is attached to two others.
Tertiary Alcohols
2-methyl-2-propanol (tertiary butanol)

H
H C H
H H
H C C C H C
4
H
9
OH
H OH H

Tertiary alcohol - the -OH is attached to a C atom which is
attached to three others.
NOMENCLATURE OF ALCOHOLS
Common System
In this system alcohols are named as alkyl alcohols. The
alkyl group attached to the OH group is named and
alcohol is added as a separate word
CH
3
CH
2
CH
2
OH CH
3
CH
2
OH
Propyl alcohol Ethyl alcohol
CH
3
CHCH
3
OH
Isopropyl alcohol
IUPAC System
In this system alcohols are named as alkanols. The IUPAC rules are:

Step 1 Name the longest chain to which the hydroxyl group is
attached. The chain name is obtained by dropping the final e
from the name of the alkane that contains the same number of
carbon atoms, and adding the ending ol.(Alkane e + ol =
Alkanol)

Step 2 Number the longest chain to give the lowest number to the
carbon attached to the hydroxyl group.

Step 3 Indicate the position of the hydroxyl group by the number of
the carbon atom to which is attached.

Step 4 Indicate the position of other substitutients or multiple bonds
by numbers.


CH
3
CH
2
CH
2
OH
CH
3
CH
2
OH
1-propanol
Ethanol
CH
3
CHCH
3
OH
2-propanol
CH
3
OH
Methanol
CH
2
CH
2
OH
2-chloroethanol
Cl
CH
3
CHCH
2
CH
2
CHCH
2
CH
3
CH
3
6-Methyl-3-heptanol
OH
not 2-methyl-5-heptanol
Following examples show how these rules are used:
PROPERTIES OF ALCOHOLS
PHYSICAL PROPERTIES
Boiling Points
Alcohols have higher boiling points than
alkanes of similar molecular weight

Solubility
Low-molecular-weight alcohols are completely soluble in water, but
their alkane counterparts have limited solubility in water
H
3
C OH
non polar pol ar
very soluble in water
H
3
C CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
OH
non polar
insoluble in water
pol ar
CHEMICAL PROPERTIES
1. Reaction with active metals
:Alkoxides are formed
M=Na, Mg, Al, etc.

Reactivity of ROH: CH
3
OH > 1
o
>2
o
>3
o
Examples:
R OH + M R OM + 1/2 H
2
H
3
C CH
2
OH
Na
H
3
C CH
2
ONa
+ 1/2 H
2
Sodium ethoxide
H
3
C C
CH
3
OH
H
Mg
H
3
C C
CH
3
O
H
2
Mg
Magnesium isopropoxide
H
3
C C
CH
3
OH
H
Al
H
3
C C
CH
3
O
H
3
Al
Aluminium isopropoxide
2. Ester Formation (Esterification)
:The esterification involves cleavage of C-OH bond of
the acid and of the O-H bond of the alcohol
R OH
+ R C
O
OH
Alcohol Carboxylic acid
R C
O
O R +
H
2
O
Ester Water
From alcohol
H
3
C CH
2
OH H
3
C CH
2
+
C
O
OH
H
3
C CH
2
C
O
O
+ H
2
O
Ethanol Propanoic acid
diethyl ester
CH
2
CH
3
Example:
3. Dehydration (Reaction with sulphuric acid)
a. Alkene Formation
At 180
o
C alcohols undergo dehydration with conc. H
2
SO
4
to give alkenes.
C
H
H
C H
H
OH
H
H
2
SO
4(Conc.)
Excess
180
o
C
C C
H
H
H
H
+ H
2
O
Conc.
H
2
SO
4
140
o
C
+ H
2
O
H
3
C CH
2
OH
2
H
3
C CH
2
O CH
2
CH
3
Diethyl ether
Ethanol
b. Ether Formation
At 140
o
C alcohols undergo dehydration with conc. H
2
SO
4
to form ether
3. Dehydration (Reaction with sulphuric acid)
(Continue....)
c. Alkyl Hydrogen Sulphate Formation
At room temperature alcohols react with conc. H
2
SO
4
to form alkyl
hydrogen sulphate
Room
Temperature
+ H
2
O
H
3
C CH
2
OH
Ethanol
+ HO SO
2
OH
H
3
C CH
2
O SO
2
OH
Ethyl hydrogen sulphate
4. Alkyl halides formation (R-X)
a. Reaction with thionyl chloride (SOCl
2
)
+ SO
2
H
3
C CH
2
OH
Ethanol
+ H
3
C CH
2
Cl
Ethyl chloride
SOCl
2 + HCl
4. Alkyl halides formation (R-X)
(Continue...)
b. Reaction with phosphorus halides (PX
3
or PX
5
)
+ POCl
3
H
3
C CH
2
OH
Ethanol
+ H
3
C CH
2
Cl
Ethyl chloride
PCl
5
+ HCl
+ H
3
PO
3
H
3
C CH
2
OH
Ethanol
+
H
3
C CH
2
Cl
Ethyl chloride
PCl
3
3 3
5. Reaction with hydrogen halides (HX)
HCl reacts with alcohols only in the presence of catalyst
(anhydrous ZnCl2). No catalyst is required in the case
of HBr or HI.
H
3
C CH
2
OH
Ethanol
+
H
3
C CH
2
Br
Ethyl bromide
HBr
+ H
2
O
6. Reaction with nitric acid (HNO
3
)
Alkyl nitrates are formed
H
3
C CH
2
OH
Ethanol
+ H
3
C CH
2
O
Ethyl nitrate
HO NO
2
NO
2
+ H
2
O
7. Oxidation
Different types of alcohols give different products on
oxidation. Most widely used oxidizing agents are
KMnO4 + H
2
SO
4
and Na
2
Cr
2
O
7
+ H
2
SO
4

a. Primary alcohols are oxidized to aldehydes
H
3
C CH
2
OH
Ethyl alcohol
+ H
3
C C H
Acetaldehyde
(O)
Na
2
Cr
2
O
7
/ H
+
O
(O)
H
3
C C OH
Acetic acid
O
Na
2
Cr
2
O
7
/ H
+
b. Secondary alcohols are oxidized to ketones
H
3
C CH CH
3
Isopropyl alcohol
+
H
3
C C CH
3
Acetone
+ H
2
O
(O)
Na
2
Cr
2
O
7
/ H
+
O
OH
c. Tertiary alcohols don not undergo oxidation under normal conditions
H
3
C C CH
3
tert-butyl alcohol
+ NO REACTION ( NR)
(O)
Na
2
Cr
2
O
7
/ H
+
OH
CH
3
PREPARATION OF ALCOHOLS
1. Hydrolysis of alkyl halides with aqueous NaOH
Alcohols are prepared by:
+ NaOH H
3
C CH
2
Br
Ethyl bromide
H
2
O
+ NaBr
H
3
C CH
2
OH
Ethyl alcohol
2. Hydration of alkenes
Alkenes react with conc. H
2
SO
4
to form alkyl hydrogen sulphates
(Markovnikov rule is followed) which on hydrolysis yield alcohols.
H
3
C CH
Isopropyl alcohol
CH
2
H
3
C CH CH
3
OH
+ H
2
SO
4
Propene
+ HOSO
3
H H
3
C CH CH
3
Isopropyl hydrogen sulphate
OSO
3
H
H
3
C CH CH
3
OSO
3
H
+
O
H
H
H
3
C CH CH
2
Propene
+ H OH
H+
Isopropyl alcohol
H
3
C CH CH
3
OH
H
3
C CH
Isopropyl alcohol
CH
2
H
3
C CH CH
3
OH
+ H
2
SO
4
Propene
+ HOSO
3
H H
3
C CH CH
3
Isopropyl hydrogen sulphate
OSO
3
H
H
3
C CH CH
3
OSO
3
H
+
O
H
H
3. Addition of Grignard Reagents (RMgX) to aldehydes and ketones
H
2
O
+ MgX(OH)
C
O
+ R MgX C
OMgX
R
H
+
C
OH
R
Aldehyde
or ketone
Grignard
reagent
Addition
compound
Alcohol
Primary alcohols are obtained by treating Grignard reagents with formaldehyde
+ RMgX
H C H
Formaldehyde
O
C
OMgX
H H
R
H
2
O
H
+
C
OH
H H
R
1
O
Alcohol
Secondary alcohols are obtained by treating Grignard reagents with other aldehyde
+ RMgX
H
3
C C H
Acetalldehyde
O
C
OMgX
H
3
C H
R
H
2
O
H
+
C
OH
H
3
C H
R
2
O
Alcohol
Tertiary alcohols are obtained by treating Grignard reagents with ketones
+ RMgX
H
3
C C CH
3
Acetone
O
C
OMgX
H
3
C CH
3
R
H
2
O
H
+
C
OH
H
3
C CH
3
R
3
O
Alcohol
4. Reduction of aldehydes and ketones with H
2
/ Ni or lithium
aluminium hydride (LiAlH
4
)
Aldehydes give primary alcohols, ketones give secondary alcohols.
LiAlH
4
+ H
2 H
3
C C H
Acetaldehyde
O
H
3
C C CH
3
Acetone
O
CH
2
H
3
C
Ni
OH
Ethyl alcohol (1
o
)
CH H
3
C CH
3
Isopropyl alcohol (2
o
)
OH
5. Reduction of acids with lithium aluminium hydride (LiAlH
4
)
H
3
C C OH
Acetic acid
O
CH
2
H
3
C
LiAlH
4
OH
Ethyl alcohol


6. Acid-hydrolysis of esters
H
3
C C OC
2
H
5
Ethyl acetate
O
C
2
H
5
OH
Ethyl alcohol
+ H
3
C C OH
O
H+
H OH
+
Acetic acid
IMPORTANT INDIVIDUAL ALCOHOLS
Methanol (methyl alcohol, wood alcohol)

In industry, it is used as the raw material for
making formaldehyde (which is used to make
polymer), as a solvent, and as a denaturant
(poison) for ethanol. It is also used as the fuel in
Sterno, as well as in burners for fondue pots.
Most methanol is made by the reaction of carbon
monoxide with hydrogen under high pressure
and temperature

Ethanol (ethyl alcohol, grain alcohol)

Some ethanol is made by the fermentation of
sugars, but most is synthesize by the addition of
water to ethane in the presence of catalyst. A 70
% (v/v) solution of ethanol in water is used as
disinfectant.
In industry, ethanol is used as a solvent and to
prepare pharmaceuticals, perfumes, lotions, and
rubbing compounds
2-Propanol (isopropyl alcohol)

2-propano is a common substitute for ethanol for giving back rubs. It is twice as
toxic as ethanol, and in solutions with concentrations from 50 to 99% (v/v) it is
used as a disinfectant.
2 H
2
+ CO
3000 lb/ in.
2
T=350-400oC
Catalyst=ZnO-Cr
2
O
3
H
3
C OH
1,2-Ethanediol (ethylene glycol), and
1,2-propanediol (propylenglycol). Ethylene
and propylene glycol are the chief
components in permanent-type antifreezes
CH
2
CH
2
OH OH
1,2-Ethanediol
(ethylene glycol)
1,2,3-Propanetriol (glycerol, glycerin). Glycerol,
a colorless, syrupy liquid with a sweet taste, is freely
soluble in water and insoluble in nonpolar solvents
CH
2
CH CH
2
OH OH OH
1,2,3-Propanetriol
(glycerol)
Sugars. All carbohydrates consist of polyhydroxy
compounds.
CH
2
CH CH
OH OH OH
CH CH C
O
H
OH OH
Glucose---a sugar
(open f ormof molecule)