Alcohol and Ether:

Alcohol: Introduction:

Alcohols are the compounds in which a hydroxyl (-OH) group is attached to saturated carbon
atom.

Functional group

C OH R OH
General Formula
Saturated carbon

The hydroxyl group is the functional group of alcohols. Alcohols containing one hydroxyl group
are called monohydric alcohols. Alcohols with two, three or more hydroxyl groups are known as
dihydric, trihydric or polyhydric alcohols respectively.

For example:

CH3CH2OH H2C OH H2C OH

H2C OH HC OH
Monohydric
(One -OH group) H2C OH
Dihydric
(Two -OH group) Trihydric
(Three -OH group)

Types of alcohols:

Primary (1˚), Secondary (2˚) and Tertiary (3˚) alcohols: Monohydric alcohols are classified as
primary (1˚), secondary (2˚) or tertiary (3˚) depending upon whether the –OH group is attached
to a 1˚, 2˚ or 3˚-carbon atom.

i.e.

H 1°-carbon R 2°-carbon R 3°-carbon

R C OH R C OH R C OH
H H R

1°-alcohol 2°-alcohol 3°-alcohol

Alcohol-Bsc 1st Year Page 1

Structure of Alcohols:

In methyl alcohol both oxygen and carbon atoms are Sp 3 hybridized. Two of the Sp3 -orbitals of
oxygen are completely filled and cannot take part in bond formation. The C—O bond in methyl
alcohol is formed by the overlap of an Sp 3 -orbital of carbon and Sp3 -orbital of oxygen.

Whereas O—H bond is formed by overlap of an Sp3 -orbital of oxygen and S-orbital of hydrogen.
The C—O—H bond angle is 105˚. It is less than normal tetrahedral angle.

This is because the two completely filled Sp 3 -orbitals of oxygen repel each other. This result in
reduction of the bond angle according to VSEPR- Theory.

Nomenclature:

Common System:

In this system alcohol R—OH are named as alkyl alcohol.

For example:

CH3

CH3 OH CH3CH2CH2OH CH3 C OH

H
Methyl alcohol n-Propyl alcohol Isopropyl alcohol

IUPAC System:

In this system alcohols are named as alkanol.

IUPAC rules are:

i. Select the longest continuous carbon chain containing the –OH group.
ii. Change the name of the alkane corresponding to this chain by dropping the ending ‘e’
and adding the suffix –‘ol’.
iii. Number the chain of carbon carrying the –OH group, the lowest possible number.

For example:

CH3
3 2 1 3 2 1
CH3CH2CH2OH CH3 C OH H2C C CH2 OH
H H
1-Propanol 2-Propanol Prop-2-en-1-ol

Methods of Preparation of Alcohols:

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 1. Hydrolysis of alkyl halides:

Alkyl halide reacts with aqueous sodium hydroxide to form alcohols.

H2O
R X + NaOH R OH + NaX

Alkyl halide Alcohol

H2O
CH3CH2 Br + NaOH CH3CH2 OH + NaBr

Ethyl alcohol

2. Hydration of alkenes:

Alkenes react with sulphuric acid to produce alkyl hydrogen sulphate based upon Markovnikov’s
rule. Alkyl hydrogen sulphate on hydrolysis give alcohols.

For example:

OSO3H

CH3 CH CH2 + HOSO3H CH3 C CH3

H
Sulphuric acid Isopropyl hydrogensulphate
OSO3H H OH
CH3 C CH3 + O H CH3 C CH3 + H2SO4
H H
Isopropyl alcohol

The overall result of the above reaction appear to be Markovnikov’s addition of H2 O (Hydration)
to a double bond.

3. Addition of Grignard Reagent to aldehyde and Ketones:

Addition of Grignard reagents to carbonyl compounds are especially useful because of their
utility in the preparation of primary, secondary, and tertiary alcohols. Formaldehyde yield
primary alcohols, other aldehyde yield secondary and ketone yield tertiary alcohols.

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 H H H
Ether H2O /H
R-MgX + C O R C O MgX R C OH

H H H
Formaldehyde
1°-Alcohol

H H H
Ether H2O /H
R-MgX + C O R C O MgX R C OH

R R
R
Higher aldehyde
2°Alcohol

R R R
Ether H2O /H
R-MgX + C O R C O MgX R C OH

R
R R
Ketone
°
3 -Alcohol

4. Hydrolysis of Esters:
Alcohols may be prepared by base or acid catalysed hydrolysis of esters.

O O
H / OH
R C OR' + H OH R C OH + R' OH

Water Carboxylic acid Alcohol
Ester

5. Hydroboration-Oxidation of alkene:

Akene react with diborane, B2 H6 to form trialkylboranes. Diborane adds as borane (BH3 ). The
positive part of BH3 is the borane, the negative part is Hydrogen.

For example:

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 1
3 CH3 C CH2 + (BH3)2 (CH3CH2CH2)3B
H 2
Propene Tripropyl borane

Trialkylborane are used for making primary alcohol by the reaction with alkaline aqueous
solution of hydrogen peroxide (H2 O2 ).

OH
(CH3CH2CH2)3B + H2O2 3 CH3CH2CH2OH + H3BO3
1-Propanol

Overall,

1
i) 2 (BH3)2
CH3 C CH2 CH3CH2CH2OH
H ii) H2O2 / OH

i.e. above reaction appear to be Anti-Markovnikov’s addition of H2 O molecule to a carbon-

carbon double bond.

6. Oxymercuration-Demercuration of alkenes:

Alkene react with mercuric acetate in a mixture of tetrahydrofuran (THF) and water to produce
hydroxymercurial compound which can be reduced to alcohol with sodium borohydride
(NaBH4 ). This two step method of alcohol preparation is known as oxymercuration-
demercuration reaction.

i.e.

Alcohol-Bsc 1st Year Page 5

 CH3 CH3
Hg (OAc)2 [Oxymercuration]
CH3CH2 C CH2 CH3CH2 C CH2
THF-H2O
OH HgOAc
2-Methylbut-1-ene
Mercury alcohol compound

NaBH4 [Demercuration]

CH3

CH3CH2 C CH2

OH H
2-Methyl-2-butanol

Note: From above reaction shows that water molecule can be adds to carbon-carbon double bond
according to Markovnikov’s orientation i.e. reaction is regioselective.

7. Reduction of Carbonyl compounds:

Aldehyde and ketones can be reduced with H2 /Ni or LiAlH4 to form the corresponding alcohols.
Aldehyde gives primary and ketone gives secondary alcohols.

O
Ni
R C H + H2 R CH2OH

Aldehyde 1°-alcohol

O OH
LiAlH4
R C R + 2 [H] R C R
H
Ketone 2°-alcohol

8. Fermentation of Carbohydrates:

Some alcohols can be prepared by the fermentation of starch and sugar under the influence of
suitable micro-organisms.

For example:

Alcohol-Bsc 1st Year Page 6

 Fermentation
C6H12O6 + Yeast 2 CH3CH2OH + 2 CO2
Glucose Ethyl alcohol

Physical Properties:

Solubility:

Alcohols are polar in nature due to electronegativity difference in between oxygen and hydrogen
and carbon and oxygen. In alcohol alkyl group (-R) is hydropholic (water insoluble) but –OH
group is hydrophilic (water soluble) in nature.

Alkyl group (Hydrophobic part)

+ - +
C O H
R OH

Hydroxyl group (Hydrophilic group) Polar covalent bonds

Fig: An alcohol

Lower alcohol upto C 3 are completely miscible in water. The solubility decrease with increase in
molecular mass. The solubility of alcohols in water is due to the association of alcohol molecule
with water molecule by hydrogen bonding.

H-Bonding

O H O H O H
H R H
Water Alcohol Water

Fig: H-bonds between alcohol and water molecule

Due to presence of such alcohol is soluble in water. The alkyl part (-R) in alcohol is non-polar.
Due to this the solubility in water should decrease with increase in molecular mass i.e. in higher
alcohol the alkyl group in alcohol molecule dominates and hence the solubility gradually
decreases n-decyl alcohol almost insoluble in water.

In case of isomeric alcohols, the solubility of an alcohol increase with the decrease in surface
area of the molecule. Out of isomeric butyl alcohol, n-butyl alcohol is least soluble in water
while tert-butyl alcohol is extremely soluble.

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 CH3 OH
Alcohol: CH3CH2CH2CH2OH CH3 C CH2OH CH3CH2 C CH3
H H
n-Butyl alcohol Iso-butyl acohol
Solubility 12.5
7.9 10
(gm / 100 gm H2O

118 108 99.5

Boiling Point (°C):

Questions: n-Butyl alcohol has much higher boiling point than its isomers, isobutyl alcohol as
well as diethyl ether. Explain with suitable reason?

Questions: Account for the fact that ‘Alcohols have much higher boiling point than that of
hydrocarbons.’’

Reactions of Alcohols:

The chemical properties of an alcohol, ROH are determined by its functional group –OH. The
oxygen atom of an alcohol polarized both C—O bond and the O—H bond.

+ - +
C O H

An alcohol

Due to this reason, alcohols undergo reactions involving either C—OH or CO—H bond
cleavage.

1. Reaction involving cleavage of C—OH bond:

i. Reaction with halogen halides:

Gaseous hydrogen halide (HX) when bubbled through boiling alcohols react to produced
alkyl halides.

R OH + HX R X + H2O
Alcohol Alkyl halide

Mechanism:

Alcohol-Bsc 1st Year Page 8

This reaction is a typical example of nucleophilic substitution apparently involving displacement
of a very poor leaving group –OH. However, in the presence of acid the alcohol undergoes
protonation to form the oxonium ion in which the –OH2 + become a good leaving group (as a
stable water molecule).

R O + H R O H
H From acid H Oxonium Ion
Alcohol

This oxonium ion is converted into alkyl halide either by S N1 or SN2 mechanism.

SN1 -mechanism: Secondary and tertiary alcohols react by this mechanism.

i.e.

R OH2 R + H2O
Carbocation

R + X R X
Alkyl halide

SN2 -mechanism: Methanol and most of the primary alcohols react by this mechanism in which
the backside attack by the nucleophilic halide ion accompanied by the removal of H 2 O molecule
from front side attack takes place in a concerted manner. Evidently, this reaction involves a
transition state.

- +
X + R OH2 X R OH2 X R + H2O
Nucleophile Alkyl halide
Transition State

From above, the fact that an S N1 -reaction is accompanied by a carbocation rearrangement, if it is

suitably substituted whereas, no such rearrangement takes place in an S N2 -reaction.

i.e.

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 CH3 CH3
H HCl H2
H3C C C CH3 H3C C C CH3 [ Rearrange Product]
H
OH Cl
2-Chloro-2-methyl butane
3-Methyl-2-butanol

Mechanism:

Carbocation rearrangement may be:

CH3 H CH3 H
H
H3C C C CH3 H3C C C CH3
Acidification
H OH H OH2
Heterolytic Bond Cleavage
Alcohol
CH3 H

H3C C C CH3

H
2°-Carbocation

Rearrangement Hydride Shift

CH3 H
CH3 H
Cl
H3C C C CH3
H3C C C CH3
H
Cl H
3°-Carbocation

Questions: Predict the product and write the mechanism of following reactions:

CH3

H3C C OH + HBr ?
CH3

2. Dehydration of alcohols:

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 Elimination of a molecule of water from a molecule of a alcohol is called dehydration.
Dehydration of alcohol yield alkenes. It can be carried out either by heating the alcohol
with sulphuric acid or phosphoric acid or by passing alcohol vapour over heated alumina
(Al2 O 3 ).

Reagent H2O
C C C C +

H OH Alkene
Alcohol

The ease of dehydration of various alcohols has been found the order:
3˚-alcohol > 2˚-alcohol > 1˚-alcohol
95% H2SO4
CH 3 CH 2 OH CH2 CH2 + H2O
For example: 170°C Ethylene
Ethyl alcohol
Mechanism: Dehydration
1° of alcohol is an example of an E1 reaction and its mechanism
involves three distinct steps:
CH3CH2CH2CH2OH 75% H2SO4
CHand CHCH3 + CH3CH2CH
3CHcatalyzing
CH2
Step I: It is fast acid-base reaction between the alcohol
140°C acid to give
n-Butyl alcohol 2-Butene 1-Butene
protonated alcohol and conjugated base of the acid.
(Chief product)

C C + HB C C + B

H OH H OH2
Protonated alcohol

Step II: Protonated alcohol under goes heterolysis forming the carbocation and water.

C C
C C + H2O

H
H OH2
Carbocation
Step III: The carbocation loses a proton to the base to yield alkene.

C C + HB
C C
Alkene
H
Base
Orientation of dehydration is strongly Zaitsev’s, i.e. if there is a probability of the
formation of more than one alkenes, the highly substituted alkene is the preferred
product.
For example: OH

H
CH3 CH2 CH CH3 CH3 CH CH CH3 + CH3 CH2 CH==CH2
2-Butene 1-Butene
Alcohol-Bsc 1st Year
2-Butanol (Major product) Page 11
 3. Reaction with phosphorus halides: Alcohol can be converted into alkyl halide by treating
with phosphorus tri or penta halides.

Reaction Involving Cleavage of O—H bond:

i. Reaction with active metals: Acidic Nature:

Alcohols behave as weak acids. The slight acidic character of alcohol can be explained on the
basis of the fact that hydrogen atom is attached to electronegative oxygen atom, which attracts
the pair of electrons of the O—H bond. Due to this attraction there is a tendency for the loss of
hydrogen as a proton.

In other words, the acidic character of alcohol is due to the ability of oxygen to accommodate
negative charge after the loss of a proton. Thus, they react with strong electropositive me tals
evolving hydrogen gas.

1
R OM + H2
R O H + M 2
Alcohol Metal Metal alkoxide

Alcohols are stronger acids than terminal acetylene but weaker than water. This fact shows that
alkoxide are converted into alcohols when treated with water whereas acetylides are decomposed
by alcohol to liberate acetylene.

R O Na + H2O R OH + NaOH

Strong acid Weak acid

+ R OH R C C H + R OM
R C CM
Strong acid Waek acid

The main structural feature that makes them weaker acids than water is the presence of electron-
releasing alkyl group which tends to intensify the negative charge on the oxygen. This makes the
alkoxide ion less stable than hydroxide ion. It is further supported by the fact that the order of
acid strength of various types of alcohols are:

Alcohol-Bsc 1st Year Page 12

 Primary (1˚) > Secondary (2˚) > Tertiary (3˚)

The tertiary alcohol being weakest because of the presence of three electron releasing alkyl
groups on the carbon atom attached to oxygen.

Questions: Explain why alcohols show both acidic and basic properties.

OR

Questions: What reactions show that alcohol can acts as both acids and bases. [TU 2071]

Oxidation of alcohols:

The oxidation of an alcohol involves the loss of one or more hydrogen from the carbon bearing
the –OH group. The product formed depends upon the nature of the oxidizing agent used and the
type of alcohol. Commonly used oxidizing agents are KMnO 4 /H+ , K2 Cr2 O7 /H+ etc.

a) Primary (1˚) alcohol: Primary alcohols are is 1st oxidized to aldehyde and then to
carboxylic acid containing the same number of carbon atom as the original alcohol.

H H O
KMnO4 / H KMnO4 / H
R C OH R C O R C OH
[O] [O]
H Aldehyde Carboxylic acid
1°-Alcohol

b) Secondary (2˚) alcohol: Secondary alcohols are oxidized to ketone having the same
number of carbon atom as the original alcohol.

R R
KMnO4 / H
R C OH R C O
[O]
H Ketone
2°-Alcohol

c) Tertiary (3˚) alcohol: Tertiary alcohol arenot oxidized by neutral or alkaline oxidizing
agents but acidic oxidizing agent oxidize them. A first alkene is formed due to
dehydration which is them oxidized to give a mixture of aldehyde ketone and acids.

Alcohol-Bsc 1st Year Page 13

 R
Neutral KMnO4
R C OH No reaction

R
3°-Alcohol

Questions:

1. Give the products for the following reactions; also mention this cause of reaction.

a) RCH2OH + KMnO4 ?

b) R2CHOH + K2Cr2O7 ?
HCl + ZnCl2
c) CH3CH2CH2OH ?


Questions: Describe the mechanism when primary alcohol is treated with alkaline KMnO 4 ?

Or, Write the reaction and mechanism when primary alcohol is treated with alkaline KMnO 4 .

Solution: When primary alcohol is treated with alkaline KMnO 4 , it is oxidized into aldehyde and
then into carboxylic acid.

Mechanism: It involves as follows;

H H H

R C O H + OH R C O R C O + HMnO4-2
MnO4
H From Base H An Aldehyde

1°-Alcohol
OH (From Base)

H
-
MnO4
R C O R C O

OH OH

A Carboxylic acid

Alcohol-Bsc 1st Year Page 14