UNIT 11

ALCOHOLS, PHENOLS AND ETHER

LEARNING OUTCOMES
• name alcohols, phenols and ethers according to the IUPAC
system of nomenclature;
• discuss the reactions involved in the preparation of alcohols from
alkenes, aldehydes, ketones and carboxylic acids;
• discuss the reactions involved in the preparation of phenols from
haloarenes, benzene sulphonic acids, diazonium salts and cumene;
• discuss the reactions for preparation of ethers from (i) alcohols and (ii) alkyl halides and
sodium alkoxides/aryloxides;
• correlate physical properties of alcohols, phenols and ethers with
their structures;
• discuss chemical reactions of the three classes of compounds on
the basis of their functional groups.
Alcohols, phenols and ethers are the basic compounds for the
formation of detergents, antiseptics and fragrances, respectively.
What are alcohols?
Alcohols are formed when a hydrogen atom in an aliphatic
hydrocarbon is replaced by –OH group. An alcohol contains one or
more hydroxyl (OH) group(s) directly attached to carbon atom(s), of
an aliphatic system (CH3OH).CH3OH
What are phenols?
Phenols are formed when a hydrogen atom in an aromatic
hydrocarbon is replaced by –OH group.
Phenol contains –OH group(s) directly attached to carbon atom(s) of
an aromatic system (C6H5OH).
APPLICATIONS OF ALCOHOL IN INDUSTRY AND DAY -TO-DAY
LIFE.
1. Ordinary spirit used for polishing wooden furniture is chiefly a
compound containing hydroxyl group ethanol.
2. The sugar we eat, the cotton used for fabrics, the paper we use
for writing, are all made up of compounds containing –OH
groups. Just think of life without paper; no note-books, books,
news- papers, currency notes, cheques, certificates, etc.
3. The magazines carrying beautiful photographs and interesting
stories would disappear from our life. It would have been really a
different world.
What are ethers?
The substitution of a hydrogen atom in a hydrocarbon by an alkoxy or
aryloxy group (R–O/Ar–O) yields another class of compounds known
as ‘ethers’. C6H5O
For example → CH3 -O-CH3 (dimethyl ether).
OR
Ethers are compounds formed by substituting the hydrogen atom of
hydroxyl group of an alcohol or phenol by an alkyl or aryl group.
For example → C2 H5 OH (replace H by CH3---> C2H5- O- CH3

Classification

Based on the [Link] -OH groups →Mono,di,tri or Polyhydric Alcohols

Examples: Alcohols→

: Phenols→

Based on the nature of hybridisation of carbon to which -OH group

is attached: Compounds containing C sp3- OH bond→
Primary, secondary and tertiary alcohols

Examples:

Allylic alcohols: The —OH group is attached to sp3

hybridised carbon adjacent to the carbon-carbon double bond, that
is to an allylic carbon.
Example: CH2=CH-CH2- allyl group

Benzylic alcohols: The —OH group is attached to a sp3—hybridised

carbon atom next to an aromatic ring.
Example:

Vinylic alcohol: Alcohols contain —OH group bonded to a

carbon-carbon double bond, i.e., to a vinylic carbon( CH2=CH-) or
to an aryl carbon. CH2 = CH – OH → vinyl alcohol and phenols

All alcohols are classified as primary secondary and tertiary

ETHERS
Ethers are classified as simple or symmetrical, if the alkyl or aryl groups
attached to the oxygen atom are the same, and mixed or unsymmetrical,
if the groups are different. Diethyl ether C2H5 -O- C2H5 is a
symmetrical ether . C2H5 -O -CH3 and C2H5 -O -C6H5 are
unsymmetrical ethers. H

NOMENCLATURE
ALCOHOLS

A
● 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 the IUPAC system , the name of an alcohol is derived
from the name of the alkane, by substituting ‘e’ of alkane with the
suffix ‘ol’. Alkanol ethane di 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.

1. Methyl alcohol ---- methanol

2.n- propyl alcohol --- propan-1-ol or propanol
[Link] alcohol --- propan-2-ol
4.n-butyl alcohol --- butan-1-ol
[Link] butyl alcohol --- butan-2-ol
[Link] alcohol--- 2-methyl propan-1-ol
[Link] butyl alcohol----- 2-methyl propan-2-ol
[Link] Glycol---- ethane 1,2,diol
[Link] --- propane 1,2,3 triol
Cyclic alcohols are named using the prefix cyclo and considering
the —O OH group attached to C–1.
PHENOLS
● The simplest hydroxy derivative of benzene is phenol.
● It is its common name and also an accepted IUPAC name.
● As the 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.

● Dihydroxy derivatives of benzene are known as 1, 2-, 1, 3- and

1,4 benzenediol.

ETHERS
Alkoxy alkane - methoxy methane- ethoxy ethane
methoxy ethane - wrong name is ethoxy methane
common names of ethers are derived from the names of alkyl/aryl
groups written as separate words in alphabetical order and adding
word ‘ether’ at the end. Example : ethyl methyl ether CH3OC2H5

1. Dimethyl ether ----------> methoxy methane

2. Diethyl ether -------------> Ethoxy ethane
3. Methyl n-propyl ether → Methoxy propane
4. Methyl phenyl ether ----> Methoxy benzene-anisole
5. Ethyl phenyl ether ------> Ethoxy benzene - phenetole
6. Heptyl phenyl ether ----> Phenoxy heptane
7. Methyl isopropyl ether→ 2- methoxy propane
8. Phenyl isopentyl ether→ 3- methyl butoxy benzene
9. 1,2-Dimethoxyethane
10. 2-ethoxy 1,1-dimethyl cyclohexane
R - O - R or Ar - O - Ar or R - O - Ar or R1 - O - R2
If both the alkyl groups are the same, the prefix ‘di’ is added before
the alkyl group.
For example, C2H5 -O -C2H5 is diethyl ether.
According to the IUPAC system of nomenclature, ethers are regarded
as hydrocarbon derivatives in which a hydrogen atom is replaced by
an –OR(alkoxide) or –OAr (phenoxide) group, where R and Ar
represent alkyl and aryl groups, respectively. The larger (R) group is
chosen as the parent hydrocarbon.

TEST YOURSELF
STRUCTURES OF FUNCTIONAL GROUPS
● 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.
● The given picture depicts structural aspects of methanol, phenol
and methoxymethane.

● 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. lplp>lpbp>bpbp
● 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
an unshared electron pair of oxygen with the aromatic ring and
(ii) sp2 hybridised state of carbon to which oxygen is attached.
● In ethers, the four electron pairs, i.e., the two bond pairs and two
lone pairs of electrons on oxygen are arranged approximately in
a tetrahedral arrangement.
● The bond angle is slightly greater than the tetrahedral angle due
to the repulsive interaction between the two bulky (–R) groups.
The C–O bond length (141 pm) is almost the same as in
alcohols.

Alcohols and Phenols

Preparation of Alcohols
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
according to Markovnikov’s rule .

Mechanism

(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 a greater number of hydrogen atoms. The alcohol formed
looks as if it has been formed by the addition of water to the alkene in
a way opposite to Markovnikov's rule. In this reaction, alcohol is
obtained in excellent yield.
2. From carbonyl compounds - C=O
(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) (reducing agent). Aldehydes yield primary alcohols
whereas ketones give secondary 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, LiAlH4 is an expensive reagent, and therefore, used

for preparing special chemicals only. Commercially, acids are
reduced to alcohols by converting them to the ester followed by their
reduction using hydrogen in the presence of catalyst (catalytic
hydrogenation).

3. From Grignard reagents R MgX + aldehyde or ketones

Alcohols are produced by the reaction of Grignard reagents
with aldehydes and [Link] 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.
The reaction produces :
Methanal ----->a primary alcohol
Aldehydes----->a secondary alcohol
ketones--------->tertiary alcohol
TEST YOURSELF :
Give the structures and IUPAC names of the products expected from
the following reactions:
(a) Catalytic reduction of butanal. → butyl alcohol→ Butan-1-ol
(b) Hydration of propene in the presence of dilute sulphuric acid.
→ propan-2-ol
(c) Reaction of propanone with methylmagnesium bromide followed
by hydrolysis.--> tertiary butyl alcohol or 2-methyl propan-2-ol
Preparation of Phenols
Phenol, also known as carbolic acid, was first isolated from coal tar.
Nowadays, phenol is commercially produced synthetically. In the
laboratory, phenols are prepared from benzene derivatives by any of
the following methods:
1. From haloarenes
Chlorobenzene is fused with NaOH at 623K and 320 atmospheric
pressure. Phenol is obtained by acidification of sodium phenoxide so
produced .

2. From benzene sulphonic acid

Benzene is sulphonated with oleum and benzene sulphonic acid so
formed is converted to sodium phenoxide on heating with molten
sodium hydroxide. Acidification of the sodium salt gives phenol.

3. From diazonium salts

A diazonium salt is formed by treating an aromatic primary amine
with nitrous acid (NaNO2 + HCl) at 273-278 K (called
diazotization). Diazonium salts are hydrolysed to phenols by
warming with water or by treating with dilute acids .

.
4. From cumene
Phenol is manufactured from the hydrocarbon cumene. Cumene
(isopropylbenzene → fractional distillation of petroleum) is oxidised
in the presence of air to cumene hydroperoxide. It is converted to
phenol and acetone by treating it with dilute acid. Acetone, a
by-product of this reaction, is also obtained in large quantities by
this method.

TEST YOURSELF

1.(CH3)2CH-MgBr 2. C5H9 (cyclohexyl)

1.CH3 CHOH CH3 → isopropyl alcohol → propan-2-ol
3.CH3-CH2-CH(CH3)-CH2OH
Physical Properties → 1. Structure 2. Hydrogen bonding)
1. Alcohols and phenols consist of two parts, an alkyl/aryl group
and a hydroxyl group.
2. The properties of alcohols and phenols are chiefly due to the
hydroxyl group. (OH)
3. Boiling points of alcohols and phenols increase with increase in
the number of carbon atoms (increase in van der Waals forces).
Linear molecule → larger the surface area → greater the
vander waals force → higher the boiling points → (A-A-A-A-)
(A -A -A) → branched →smaller the surface area → lesser
(A) the van der waals force → lower the boiling point.
4. In alcohols, the boiling points decrease with increase of
branching in the carbon chain (because of decrease in van der
Waals forces with decrease in surface area).
5. The –OH group in alcohols and phenols is involved in
intermolecular hydrogen bonding as shown below:

It is interesting to note that boiling points of alcohols and phenols

are higher than hydrocarbons, ethers, haloalkanes and haloarenes of
comparable molecular masses.(Bpt is due to the existence of
hydrogen bonding → greater the hydrogen bonding → greater bpt
For example, ethanol and propane have comparable molecular
masses but their boiling points differ widely. The boiling point of
methoxymethane is intermediate between the two boiling points.

The high boiling points of alcohols are mainly due to the presence
of intermolecular hydrogen bonding in them which is lacking in ethers
and hydrocarbons.
hydrocarbon<ethers<ketone<acetaldehyde<alcohol<carboxylic acid
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 (hydro-phobic) groups.
Several of the lower molecular mass alcohols are miscible
with water in all proportions.

TEST YOURSELF:
Arrange the following sets of compounds in order of their increasing
boiling points:
(a) Pentan-1-ol(5), butan-1-ol(5), butan-2-ol(4), ethanol(2),
propan-1-ol(3),Methanol.(i)
(b) Pentan-1-ol(4), n-butane(1), pentanal(3), ethoxyethane(2).
Chemical Reactions
Alcohols are versatile compounds. They react both as nucleophiles
and electrophiles. The bond between O–H is broken , alcohols
behave as nucleophiles. The bond between C- O is broken alcohols
react or behave as electrophiles.
Alcohols as nucleophiles:- R-O-H →R-O-(Negative nucleophile)+ H+

(ii) The bond between C–O is broken when they react as

electrophiles. Protonated alcohols react in this manner.
Protonated alcohols as electrophiles:-R-OH → R+(positive) + OH-

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.
In addition to this, phenols react with aqueous sodium hydroxide to
form sodium phenoxides.

These reactions show that alcohols and phenols are

acidic in nature. Alcohols and phenols are Brönsted
acids i.e., they can donate a proton (H+) to a stronger base (B:).

(ii) Acidity of alcohols: R -O -H, R(NO2) O -H , R (Cl) OH

The acidic character of alcohols is due to the polar nature of the O–H
bond (how fast the H+ is moving away from O , highly acidic).
An electron-releasing group (–CH3, –C2H5) increases electron
density on oxygen(between O and H) and to decrease the polarity of
the O-H bond, decreases the acid strength.
Electron-withdrawing group (NO2, Halogens , CN ) decreases the
electron density on oxygen and increases acidic strength. For this
reason, the acid strength of alcohols decreases in the following
order:

This reaction shows that water is a better proton donor (i.e.,

stronger acid) than alcohol. 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.(GR)
(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 hybridized carbon of benzene
ring which acts as an electron withdrawing group (GR). Due to this,
the charge distribution in phenol molecule, as depicted in its
resonance structures, causes the oxygen of –OH group to be
positive.
The reaction of phenol with aqueous sodium hydroxide indicates that
phenols are stronger acids than alcohols and water.
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:

● 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.
● On comparing the stabilities of alkoxide and phenoxide
ions, phenoxide ion is more stable.
● 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 is 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.

● 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 when
substituent is at ortho or para position.
● 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 are less acidic
than phenol. Ka > strongly acidic- lower the pKa value

The greater the pKa value, the weaker the acid.

TEST YOURSELF:-
Arrange the following compounds in increasing order of their
acid strength:
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol,3,5-dinitrophenol,
phenol, 4-methylphenol
propan-1 -ol <4-methyl phenol <phenol<3-nitrophenol<3,5
dinitrophenol< 2,4,6,tri Nitro phenol
2. Esterification
Alcohols and phenols react with
[Link] acids(CH3-COOH),
2 .acid chlorides (CH3 - CO - Cl) and
[Link] anhydrides (CH3 - CO - O - CO - CH3) to form esters.

● 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 the 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 introducing an acetyl (CH3CO) group in alcohols or
phenols are known as acetylation.
● Acetylation of salicylic acid produces aspirin.
THE EQUATION IS GIVEN AS FOLLOWS: salol ,acetylsalicylic acid

(b) Reactions involving cleavage of carbon – oxygen (C–O) bond

in alcohols : R → OH
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 (Refer Unit 10, Class XII).
ROH + HX → R–X + H2O
The difference in reactivity of three classes of alcohols (pri , sec,
tert.)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.
TEST TO DISTINGUISH BETWEEN THREE ALCOHOLS
Tertiary alcohols with Lucas reagent turbidity (R3X)are produced
immediately as they form the halides easily.
Secondary alcohols with lucas reagent produces turbidity(RCH(X)R)
after 10 min tert>sec>pri→ order of reactivity towards L TEST
Primary alcohols do not produce turbidity at room [Link]
2. Reaction with phosphorus trihalides: Alcohols are converted to
alkyl bromides by reaction with phosphorus tribromide (Refer Unit
10, Class XII).
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 .

Ethanol undergoes dehydration by heating it with concentrated

H2SO4 at 443 K.

Secondary and tertiary alcohols are dehydrated under milder

conditions. For example

The order of dehydration (reactivity)of alcohols follows the following

order:
Tertiary > Secondary > Primary
The mechanism of dehydration of ethanol involves the following
steps:
Mechanism
Step 1: Formation of protonated alcohol.
Step 2: Formation of carbocation: It is the slowest step and hence,
the rate determining step of the reaction.

Step 3: Formation of ethene by elimination of a proton.

The acid used in step 1 is released in step 3. To drive the equilibrium

to the right, ethene is removed as it is formed.
4. Oxidation:
Oxidation of alcohols involves the formation of a carbon-
oxygen 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.(same no of carbon atoms as in alcohol)

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 ketone by chromic anhydride

(CrO3).

● Tertiary alcohols do not undergo oxidation reaction. (due to the

absence of alpha hydrogen atoms)
● Under strong reaction conditions such as strong oxidising
agents (KMnO4) 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 heated copper at 573 K, dehydrogenation takes
place and an aldehyde or a ketone is formed while tertiary
alcohols undergo dehydration.
Biological oxidation of methanol and ethanol in the body produces
the corresponding aldehyde followed by the acid.
At times the alcoholics, by mistake, drink ethanol, mixed with
methanol also called denatured alcohol.
In the body, methanol is oxidised first to methanal and then to
methanoic acid, which may cause blindness and death. A methanol
poisoned patient is treated by giving intravenous infusions of
diluted ethanol.
The enzyme responsible for oxidation of aldehyde (HCHO) to acid
is swamped allowing time for kidneys to excrete methanol.
Reactions of phenol
Electrophilic aromatic substitution
The reactions that take place on the aromatic ring are called
electrophilic substitution reactions (Unit 13, Class XI).
The –OH group attached to the benzene ring activates it towards
electrophilic substitution. OH group directs the incoming group to
ortho and para positions in the ring as these positions become
electron rich due to the resonance effect caused by –OH group.
(i) Nitration:
With dilute nitric acid low temperature (298 K), phenol yields a
mixture of ortho and para nitrophenols.
The ortho and para isomers can be separated by → steam
distillation.
o-Nitrophenol is → steam volatile → due to intramolecular hydrogen
bonding (easily changes into vapours, causes dissociation) while
p-nitrophenol → is less volatile due to intermolecular hydrogen
bonding which causes the association of molecules.

With concentrated nitric acid, phenol is converted to

2,4,6-trinitrophenol. The product is commonly known as picric
acid. The yield of the reaction product is poor.

Since the yield is poor , picric acid is prepared by an alternate

method.
Step I
phenol first with concentrated sulphuric acid which converts it to
phenol-2,4-disulphonic acid.
Step II
With concentrated nitric acid to get 2,4,6-trinitrophenol.
[Link]
Halogenation:
On treating phenol with bromine, different reaction products are
formed under different experimental conditions.
(a) When the reaction is carried out in solvents of low polarity
such as CHCl3 or CS2 and at low temperature, monobromo phenols
are formed

The usual halogenation of benzene takes place in the benzene ring

presence of a Lewis acid, such as FeBr3 ,which polarises the
halogen molecule. In the case of phenol, the polarisation of bromine
molecules takes place even in the absence of Lewis acid. It is due to
the highly activating effect of –OH group attached to the benzene
ring. Br2---> Br+ + Br- FeBr3 +Br- ---> FeBr4- + Br+
(b) When phenol is treated with bromine water, 2,4,6-tribromophenol
is formed as white precipitate. DIstinguish between phenol any
compound

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TEST YOURSELF:
Write the structures of the major products expected from the
following reactions:
(a) Mononitration of 3-methylphenol→ ortho nitro methyl phenol + p
nitro methyl phenol
(b) Dinitration of 3-methylphenol→
(c) Mononitration of phenyl methanoate→
Kolbe’s reaction (carboxylation→introducing CO2 group)
Phenoxide ion generated by treating phenol with sodium hydroxide
is even more reactive than phenol towards electrophilic aromatic
substitution. (COOH)
It undergoes electrophilic substitution with carbon dioxide, a weak
electrophile.
Ortho hydroxybenzoic acid is formed as the main reaction product.
Reimer-Tiemann reaction(formylation→introducing-CHO group)
On treating phenol with chloroform in the presence of sodium
hydroxide, a –CHO group is introduced at ortho position of benzene
ring. This reaction is known as Reimer - Tiemann reaction.
The intermediate substituted benzyl chloride is hydrolysed in the
presence of alkali to produce salicylaldehyde.

. .
Reaction of phenol with zinc dust
Phenol is converted to benzene on heating with zinc dust.

Oxidation
Oxidation of phenol with chromic acid produces a conjugated
diketone known as benzoquinone. In the presence of air, phenols
are slowly oxidised to dark coloured mixtures containing quinones.

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Intext Questions:
11.6 Give structures of the products you would expect when each of
the following alcohol reacts with (a) HCl –ZnCl2(b) HBr and (c)SOCl2
(i) Butan-1-ol (ii) 2-Methylbutan-2-ol 1- chlorobutane
11.7 Predict the major product of acid catalysed dehydration of
(i) 1-methylcyclohexanol and (ii) butan-1-ol
11.8 Ortho and para nitrophenols are more acidic than phenol. Draw
the resonance structures of the corresponding phenoxide ions.
11.9 Write the equations involved in the following reactions:
(i) Reimer - Tiemann reaction (ii) Kolbe’s reaction
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ETHERS
Preparation of Ethers
By dehydration of alcohols
Alcohols undergo dehydration in the presence of protic acids (H2SO4
, H3PO4). The formation of the reaction product, alkene or ether
depends on the reaction conditions. For example, ethanol is
dehydrated to ethene in the presence of sulphuric acid at 443 K.
At 413 K, ethoxyethane is the main product.

The formation of ether is a nucleophilic bimolecular reaction (SN2)

involving the attack of alcohol molecule on a protonated alcohol, as
indicated below:
● Acidic dehydration of alcohols, to give an alkene is also
associated with a substitution reaction to give an ether.
● The method is suitable for the preparation of ethers having
primary alkyl groups only.
● The alkyl group should be unhindered and the temperature be
kept low. Otherwise the reaction favours the formation of alkene.
● The reaction follows the SN1 pathway when the alcohol is
secondary or tertiary.
● The dehydration of secondary and tertiary alcohols to give
corresponding ethers is unsuccessful as elimination competes
over substitution and as a consequence, alkenes are easily
formed.
● Can you explain why is bimolecular dehydration not appropriate
for the preparation of ethyl methyl ether?
Williamson synthesis
It is an important laboratory method for the preparation of
symmetrical and unsymmetrical ethers. In this method, an alkyl
halide is allowed to react with sodium alkoxide.

Ethers containing substituted alkyl groups (secondary or tertiary)

may also be prepared by this method. The reaction involves SN2
attack of an alkoxide ion on primary alkyl halide.

Better results are obtained if the alkyl halide is primary. In case

of secondary and tertiary alkyl halides, elimination competes
over substitution. If a tertiary alkyl halide is used, an alkene is
the only reaction product and no ether is formed. For example,
the reaction of CH3ONa with (CH3)3C–Br gives exclusively
2-methylpropene.

It is because alkoxides are not only nucleophiles but strong

bases as well. They react with alkyl halides leading to
elimination reactions.
The following is not an appropriate reaction for the
preparation of t-butyl ethyl ether.

(i) What would be the major product of this reaction ?

(ii) Write a suitable reaction for the preparation of t-butyl ethyl
ether.
Phenols are also converted to ethers by this method. In this, phenol
is used as the phenoxide moiety.

Physical Properties Cl<---Be---->Cl

The C-O bonds in ethers are polar and thus, ethers have a net dipole
moment. The weak polarity of ethers do not appreciably affect their
boiling points which are comparable to those of the alkanes of
comparable molecular masses but are much lower than the boiling
points of alcohols as shown in the following cases:
Formula :- CH3(CH2)3CH3 C2H5-O-C2H5 CH3(CH2)3-OH
n-Pentane Ethoxyethane Butan-1-ol
b.p./K :- 309.1 307.6 390
The large difference in boiling points of alcohols and ethers is
due to the presence of hydrogen bonding in alcohols.
The miscibility of ethers with water resembles those of alcohols of
the same molecular mass. Both ethoxyethane and butan-1-ol are
miscible to almost the same extent i.e., 7.5 and 9 g per 100 mL
water, respectively while pentane is essentially immiscible with water.
This is due to the fact that just like alcohols, oxygen of ether can also
form hydrogen bonds with water molecule as shown:

Chemical Reactions
Cleavage of C–O bond in ethers
Ethers are the least reactive of the functional groups. The cleavage
of C-O bond in ethers takes place under drastic conditions with
excess hydrogen halides. The reaction of dialkyl ether gives two alkyl
halide molecules.

Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the
more stable aryl-oxygen bond. The reaction yields phenol and alkyl
halide.

Ethers with two different alkyl groups are also cleaved in the same
manner.(Halogen will go with smaller alkyl group -- primary)
CH3 - O- CH2 CH3 + HI → CH3I + CH3 - CH2 - OH

The order of reactivity of hydrogen halides is as follows:

HI > HBr > HCl. The cleavage of ethers takes place with
concentrated HI or HBr at high temperature.
When one of the alkyl group is a tertiary group, the halide
formed is a tertiary halide. (pri and sec 0r tert→ X will go with tert)

It is because in step 2 of the reaction, the departure of leaving group

(HO–CH3) creates a more stable carbocation [(CH3)3C+], and the
reaction follows SN1 mechanism. In case of anisole, methylphenyl
oxonium ion is formed by protonation of ether. The bond between
O–CH3 is weaker than the bond between O–C6H5 because the
carbon of the phenyl group is sp2 hybridised and there is a partial
double bond character.
Therefore the attack by I- ion breaks the O–CH3 bond to form CH3I.
Phenols do not react further to give halides because the sp2
hybridized carbon of phenol cannot undergo nucleophilic substitution
reaction needed for conversion to the halide.
Give the major products that are formed by heating each of the
following ethers with HI.

Electrophilic substitution reactions

The alkoxy group (-OR) is ortho, para directing and activates the
aromatic ring towards electrophilic substitution in the same way as
in phenol.

Halogenation
Phenyl Alkyl ethers undergo usual halogenation in the benzene ring,
e.g., anisole undergoes bromination with bromine in ethanoic acid
even in the absence of iron (III) bromide catalyst. It is due to the
activation of benzene rings by the methoxy group. Para isomer is
obtained in 90% yield.

Friedel-Crafts reaction
Anisole undergoes Friedel-Crafts reaction, i.e., the alkyl (R) and acyl
(COCH3)groups are introduced at ortho and para positions by
reaction with alkyl halide and acyl halide in the presence of
anhydrous aluminium chloride (a Lewis acid) as catalyst.

Nitration
Anisole reacts with a mixture of concentrated sulphuric
and nitric acids to yield a mixture of ortho and para nitroanisole.
Intext Questions
11.10 Write the reactions of Williamson synthesis of
2-ethoxy-3-methylpentane starting from ethanol and
3-methylpentan-2-ol.
CH3CH2Cl +CH3-CH2-CH(CH3)-CH(ONa)-CH3→
11.11 Which of the following is an appropriate set of reactants for the
preparation of 1-methoxy-4-nitrobenzene and why?

11.12 Predict the products of the following reactions:

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