ALCOHOLS & PHENOLS

OBJECTIVES

By the end of this module students will be able to;

1.Understand the Nomenclature of alcohols

2.Describe the Preparation of alcohols
3.Describe the chemical and physical Properties of
alcohols.
4.Explain the Uses of alcohols
Introduction:
An alcohol contains one or more hydroxyl (OH) group(s) directly
attached to carbon atom(s), of an aliphatic system (CH 3 OH) while a
phenol contains –OH group(s) directly attached to carbon atom(s) of an
aromatic system (C6H5OH).

Classification:
Mono, Di, Tri or P oly h y dri c
Compounds
Alcohols and phenols may be
classified as mono–, di–, tri- or
polyhydric compounds depending on
whether they contain one, two, three
or many hydroxyl groups respectively
in their structures as indicated in Fig.:
Classification:
Monohydric alcohols may be further classified according to the hybridization
of the carbon atom to which the hydroxyl group is attached.
(i) Compounds containing Csp3- OH bond:
In this class of alcohols, the –OH group is attached to an sp 3 hybridised
carbon atom of an alkyl group. They are further classified as follows:
Primary, secondary and tertiary alcohols:

Allylic alcohols: In these alcohols, the —OH group is attached to a sp3

hybridised carbon next to the carbon-carbon double bond, that is to an allylic
carbon. For example
Classification:
Benzylic alcohols: In these alcohols, the —OH group is attached to a sp3—
hybridised carbon atom next to an aromatic ring. For example

Allylic and benzylic alcohols may be primary, secondary or tertiary.

(ii) Compounds containing Csp2- OH bond:
These alcohols contain —OH group bonded to a carbon-carbon double bond
i.e., to a vinylic carbon or to an aryl carbon. These alcohols are also known
as vinylic alcohols.
Nomenclature:
(a) Alcohols: The common name of an alcohol is derived from the common
name of the alkyl group and adding the word alcohol to it.
For example, CH3OH is methyl alcohol.
• According to IUPAC system, the name of an alcohol is derived from the
name of the alkane from which the alcohol is derived, by substituting ‘e’ of
alkane with the suffix ‘ol’.
• The position of substituents are indicated by numerals. For this, the longest
carbon chain (parent chain) is numbered starting at the end nearest to the
hydroxyl group.
• The positions of the –OH group and other substituents are indicated by
using the numbers of carbon atoms to which these are attached. For
naming polyhydric alcohols, the ‘e’ of alkane is retained and the ending ‘ol’
is added.
• The number of –OH groups is indicated by adding the multiplicative prefix,
di, tri, etc., before ‘ol’.
• The positions of –OH groups are indicated by appropriate locants e.g.,
HO–CH2–CH2–OH is named as ethane–1, 2-diol.
Example:
Nomenclature:
Cyclic alcohols are named using the prefix cyclo and considering the —OH
group attached to C–1.

(b) Phenols: The simplest hydroxy derivative of benzene is phenol.

It is its common name and also an accepted IUPAC name. As structure of
phenol involves a benzene ring, in its substituted compounds the terms ortho
(1,2- disubstituted), meta (1,3-disubstituted) and para (1,4-disubstituted) are
often used in the common names.
Nomenclature:
Dihydroxy derivatives of benzene are known as 1, 2-, 1, 3- and 1, 4-benzenediol.
Structure of Functional Group:
In alcohols, the oxygen of the –OH group is attached to carbon by a sigma (σ )
bond formed by the overlap of a sp3 hybridised orbital of carbon with a sp3
hybridised orbital of oxygen. Fig. depicts structural aspects of methanol and
phenol.

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 –OH group is attached to sp2 hybridised carbon of an aromatic
ring. 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 and (ii) sp 2
hybridised state of carbon to which oxygen is attached.
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 Markovnikov’s rule.
Mechanisam:
Preparation of alcohols
(ii) By hydroboration–oxidation: Diborane (BH3)2 reacts with alkenes
to give trialkyl boranes as addition product. This is oxidised to alcohol by
hydrogen peroxide in the presence of aqueous sodium hydroxide.

The addition of borane to the double bond takes place in such a manner that
the boron atom gets attached to the sp2 carbon carrying greater number of
hydrogen atoms. The alcohol so formed looks as if it has been formed by the
addition of water to the alkene in a way opposite to the Markovnikov’s rule. In
this reaction, alcohol is obtained in excellent yield.
The Borane Complex:
First off it is very imporatnt to
understand little bit about the structure
and the properties of the borane molecule.
Borane exists naturally as a very toxic gas
and it exists as dimer of the general
formula B2H6 (diborane). Additionally,
the dimer B2H6ignites spontaneously in
air. Borane is commercially available in
ether and tetrahydrofuran (THF), in
these solutions the borane can exist as a
lewis acid-base complex, which allows
boron to have an electron octet.

2BH3→B2H6
Mechanisam:
Step 1
Part 1:
Hydroboration of the alkene. In this
first step the addittion of the borane to
the alkene is initiated and prceeds as a
concerted reaction because bond
breaking and bond formation occurs at
the same time. This part consists of the
vacant 2p orbital of the boron
electrophile pairing with the electron
pair of the pi bond of the nucleophile.
Mechanisam:
Part 2:
The Anti Markovnikov addition of Boron. The boron adds to the less
substituted carbon of the alkene, which then places the hydrogen on the
more substituted carbon. Both, the boron and the hydrogen add
simultaneously on the same face of the double bond (syn addition).
Mechanisam:
Oxidation of the Trialkylborane by Hydrogen Peroxide
Step 2 Part 1:
The first part of this mechanism deals with the donation of a pair of electrons
from the hydrogen peroxide ion. the hydrogen peroxide is the nucleophile in
this reaction because it is the electron donor to the newly formed
trialkylborane that resulted from hydroboration.
Mechanisam:
Part 2: In this second part of the mechanism, a rearrangement of an R group
with its pair of bonding electrons to an adjacent oxygen results in the removal
of a hydroxide ion.
Mechanisam:
Part 3:
This is the final part of the Oxidation process. In this part the trialkylborate
reacts with aqueous NaOH to give the alcohol and sodium borate.
Mechanisam:
Preparation of alcohols
2. From carbonyl compounds:
(i) By reduction of aldehydes and ketones:
Aldehydes and ketones are reduced to the corresponding alcohols by addition
of 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.
Preparation of alcohols
(ii) By reduction of carboxylic
acids and esters: Carboxylic acids
are reduced to primary alcohols in
excellent yields by lithium
aluminium hydride, a strong
reducing agent.

However, LiAlH 4 is an expensive

reagent, and therefore, used for
preparing special chemicals only.
Preparation of Alcohols
(iii)Esterification followed by
reduction:
Commercially, acids are reduced to
alcohols by converting them to the
esters, followed by their reduction
using hydrogen in the presence of
catalyst (catalytic hydrogenation).
Preparation of alcohols:
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
alcohol.
Preparation of Alcohols

Reaction produces a primary alcohol with methanal, a secondary alcohol with other
aldehydes and tertiary alcohol with ketones.
Physical Properties of Alcohols and Phenols:
Alcohols and phenols consist of two parts, an alkyl/aryl group and a hydroxyl
group. The properties of alcohols and phenols are chiefly due to the hydroxyl
group. The nature of alkyl and aryl groups simply modify these properties.
Boiling Points:
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).
Physical Properties of Alcohols and Phenols:
The –OH group in alcohols and phenols is involved in intermolecular
hydrogen bonding as shown below:

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. For example, ethanol and
propane have comparable molecular masses but their boiling points differ
widely. The boiling point of methoxymethane is intermediate of the two
boiling points.
Physical Properties:
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 (hydrophobic) groups. Several of the lower
molecular mass alcohols are miscible with water in all proportions.
Chemical Properties:
Alcohols are versatile compounds. They react both as nucleophiles and
electrophiles. The bond between O–H is broken when alcohols react as
nucleophiles.
Alcohols as nucleophiles:

Protonated alcohols as electrophiles

Chemical Properties:
Based on the cleavage of O–H and C–O bonds, the reactions of alcohols and
phenols may be divided into two groups:
(a) Reactions involving cleavage of O–H 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.
Chemical Properties:
• In addition to this, phenols react with aqueous sodium hydroxide to form
sodium phenoxides.

• The above reactions show that alcohols and phenols are acidic in nature.
In fact, alcohols and phenols are Brönsted acids i.e., they can donate a
proton to a stronger base (B:).
Chemical Properties:
(ii) Acidity of alcohols: The acidic character of alcohols is due to the polar
nature of O–H bond. 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
decreases in the following order:

Alcohols are, however, weaker acids than water. This can be illustrated by the
reaction of water with an alkoxide. This reaction shows that water is a better
proton donor (i.e., stronger acid) than alcohol. Also, in the above reaction, we
note that an alkoxide ion is a better proton acceptor than hydroxide ion,
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.
Chemical Properties:
(iii) Acidity of phenols:
The reactions of phenol with metals (e.g., sodium, aluminium) and sodium
hydroxide indicate its acidic nature. The hydroxyl group, in phenol is directly
attached to the sp2 hybridised carbon of benzene ring which acts as an electron
withdrawing group. Due to this, the charge distribution in phenol molecule, as
depicted in its resonance structures, causes the oxygen of –OH group to be
positive.
Chemical Properties:
The reaction of phenol with aqueous sodium hydroxide indicates that
phenols are stronger acids than alcohols and water.

Let us examine how a compound in which hydroxyl group attached to an

aromatic ring is more acidic than the one in which hydroxyl group is
attached to an alkyl group.
The ionisation of an alcohol and a phenol takes place as follows:
Chemical properties:
Due to the higher electronegativity of sp2 hybridised carbon of phenol to which
–OH is attached, electron density decreases on oxygen. This increases the
polarity of O–H bond and results in an increase in ionisation of phenols than
that of alcohols. Now let us examine the stabilities of alkoxide and phenoxide
ions. In alkoxide ion, the negative charge is localised on oxygen while in
phenoxide ion, the charge is delocalised. The delocalisation of negative charge
(structures I-V) makes phenoxide ion more stable and favours the ionisation
of phenol. Although there is also charge delocalisation in phenol, its resonance
structures have charge separation due to which the phenol molecule is less
stable than phenoxide ion.
Chemical Properties:
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.
Chemical Properties:

pKa Values of some Phenols and Ethanol

Compound Structure pKa
o-Nitrophenol 7.2
m-Nitrophenol 8.3
p-Nitrophenol 7.1

Phenol 10.0

o-Cresol 10.2
m-Cresol 10.1
p-Cresol 10.2
Ethanol C2H5-OH 15.9

From the above data, you will note that phenol is more acidic than ethanol
Chemical Properties:
2. Esterification:
Alcohols and phenols react with carboxylic acids, acid chlorides and acid
anhydrides to form esters.
Chemical Properties:
The reaction with carboxylic acid
and acid anhydride is carried out in
the presence of a small amount of
concentrated sulphuric acid. The
reaction is reversible, and therefore,
water is removed as soon as it is
formed. The reaction with acid
chloride is carried out in th
e 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 salicylic
acid produces aspirin.
(b) Reactions involving cleavage of C–O
bond in alcohols:
The reactions involving cleavage of C–O 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 halides.
ROH + HX → R–X + H2O
The difference in reactivity of three classes of
alcohols with HCl distinguishes them from one
another (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.
Lucas Test:
Chemical Properties:
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.
• 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
Mechanisam:
Chemical Properties:
4. Oxidation:
Oxidation of alcohols involves the formation of a carbonoxygen double bond
with cleavage of an O-H and C-H bonds.

Such a cleavage and formation of bonds occur in oxidation reactions. These

are also known as dehydrogenation reactions as these involve loss of
dihydrogen from an alcohol molecule. Depending on the oxidising agent used,
a primary alcohol is oxidised to an aldehyde which in turn is oxidised to a
carboxylic acid.
Chemical Properties:
• 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 chromic anhyride (CrO3).

Chemical Properties:
• Tertiary alcohols do not undergo
oxidation reaction. Under strong
reaction conditions such as strong
oxidising agents (KMnO 4 ) and
elevated temperatures, cleavage
of various C-C bonds takes place
and a mixture of carboxylic acids
containing lesser number of
carbon atoms is formed. When
the vapours of a primary or a
secondary alcohol are passed over
heatedcopperat573K,
dehydrogenation takes place and
an aldehyde or a ketone is formed
while tertiary alcohols undergo
dehydration
Commercially Important Alcohols:
1. Methanol
Methanol, CH3OH, also known as ‘wood spirit’, was produced by destructive
distillation of wood. Today, most of the methanol is produced by catalytic
hydrogenation of carbon monoxide at high pressure and temperature and in
the presence of ZnO – Cr2O3 catalyst.

Methanol is a colourless liquid and boils at 337 K. It is highly poisonous in

nature. Ingestion of even small quantities of methanol can cause blindness
and large quantities causes even death. Methanol is used as a solvent in paints,
varnishes and chiefly for making formaldehyde.
Commercially Important Alcohols:
2. Ethanol
Ethanol, C 2 H 5 OH, is obtained commercially by fermentation, the oldest
method is from sugars. The sugar in molasses, sugarcane or fruits such as
grapes is converted to glucose and fructose, (both of which have the formula
C 6 H 12 O 6 ), in the presence of an enzyme, invertase. Glucose and fructose
undergo fermentation in the presence of another enzyme, zymase, which is
found in yeast.
Commercially Important Alcohols:
• In wine making, grapes are the source of sugars and yeast. As grapes ripen,
the quantity of sugar increases and yeast grows on the outer skin. When
grapes are crushed, sugar and the enzyme come in contact and
fermentation starts. Fermentation takes place in anaerobic conditions i.e.
in absence of air. Carbon dioxide is released during fermentation. The
action of zymase is inhibited once the percentage of alcohol formed exceeds
14 percent. If air gets into fermentation mixture, the oxygen of air oxidises
ethanol to ethanoic acid which in turn destroys the taste of alcoholic drinks.

• Ethanol is a colourless liquid with boiling point 351 K. It is used as a

solvent in paint industry and in the preparation of a number of carbon
compounds. The commercial alcohol is made unfit for drinking by mixing
in it some copper sulphate (to give it a colour) and pyridine (a foul smelling
liquid). It is known as denaturation of alcohol. Nowadays, large quantities
of ethanol are obtained by hydration of ethene.
REFERENCES

Prescribed textbooks
1. Brown, William H., Introduction to Organic Chemistry, 1st
edition, Saunders College Publishing.
2. Carey, Francis A., Organic Chemistry, 5th edition, 2003,
McGraw Hill, NewYork, USA. 3. Vogel’s Textbook of Practical
Organic Chemistry 5 th edition

Recommended Textbooks
1. Mcmurry, John, Organic Chemistry, 6th Edition, 2004,
Thomson Learning Inc. USA
SAMPLE QUESTIONS (MCQs)
1. The compound which reacts fastest with Lucas reagent at room temperature is
(a) Butan-1-ol
(b) Butan-2-ol
(c) 2-Methyl propan-1-ol
(d) 2-Methylpropan-2-ol
2. Acid catalyzed hydration of alkenes except ethene leads to the formation of
(a) primary alcohol
(b) secondary or tertiary alcohol
(c) mixture of primary and secondary alcohols
(d) mixture of secondary and tertiary alcohols
3. Ethylene reacts with Baeyer’s reagent to give
(a) ethane
(b) ethyl alcohol
(c) ethylene glycol
(d) None of these
4. Alkenes convert into alcohols by
(a) hydrolysis by dil. H2SO4
(b) hydration of alkene by alkaline KMnO4
(c) hydrolysis by water vapours and conc. HNO3
(d) hydration of alkene by aqueous KOH
SAMPLE QUESTIONS (MCQs)
5. By which of the following methods alcohol can be prepared in excellent yield?
(a) From alkenes
(b) By hydroboration-oxidation
(c) From carbonyl compounds
(d) From Grignard reagent
SAMPLE QUESTIONS (MCQs)