Since = 1996 = 9414248318,

9468590309, 7791835250

Unit % 11 Alcohols, Phenols and Ethers 1

Marks % 04
Alcohols and phenols are those compounds which are obtained by replacing one or
more hydrogen atoms of aliphatic or aromatic hydrocarbons by appropriate hydroxyl
group. By the structural point of view, in the alcohols, hydroxyl group is attached to
sp hybridized carbon atoms while in phenols hydroxyl group is attached to sp
3 2

hybridize carbon atom. The group of compounds obtained by displacing hydrogen by

alkoxy (−¿) or aryloxy (−OAr ) group by replacement of hydrogen is called ether.
Therefore Ethers are those compounds in which hydrogen of hydroxyl of alcohol or
phenol is displaced by aryl or alkyl group.
Classification and Nomenclature of Alcohols ⇨
On the basis of number of −OH , alcohols are divided in four parts as follows:
1) Monohydric alcohol :
The alcohols in which one −OH group is present are called monohydric alcohol.
They are often displayed by R−OH . The general formula of these compounds is
Cn H 2 n+2 O or Cn H 2 n+1 OH . Nomenclature of monohydric alcohol in common
name systems is Alkyl alcohol. In derived name system nomenclature of
monohydric alcohol is carbinol. In I . U . P . A .C . , they are named as follows:
 Largest carbon chain containing −OH group is selected.
 Numbering is done in this way that the −OH functional group gets the least
number.
 The name is written as:
Substitute ¿¿ If there is ¿+¿ alk +¿ ane +¿ ol
Gen. Structural formula Common Name Derived Typ
formula I . U . P . A .C . e
name
CH 3 OH CH 3 −OH Methyl alcohol Carbinol Methanol 1
°

C2 H 5 OH CH 3 −CH 2−OH Ethyl alcohol Methylcarbinol Ethanol 1

°

C3 H 7 OH CH 3 −CH 2−CH 2 −OH n−¿ Propyl Ethylcarbinol Propan 1

°

alcohol, −1−¿ ol
1 −¿ Propyl
°

alcohol
CH 3 −CH −CH 3 Isopropyl alcohol, Dimethyl Propan 2
°

2 −¿ Propyl carbinol −2−¿ ol

°
OH
alcohol
C 4 H 9 OH CH 3 CH 2 CH 2 CH 2 OH n−¿ Butyl Propylcarbinol Butan 1
°

alcohol, −1−¿ ol
1 −¿ Butyl
°

alcohol
CH 3 −CH −CH 2−CH 3 2 −¿ Butyl
°
Ethyl Butan 2
°

alcohol methylcarbinol −2−¿ ol

OH
CH 3 −CH −CH 2−OH Isobutyl alcohol Isopropyl 2−¿ Methy 1
°

carbinol l
CH 3
propan
−1−¿ ol
CH 3 3 −¿ Butyl
°
Trimethyl 2−¿ Methy 3
°

alcohol carbinol l
CH 3 −C−OH
propan
CH 3 −2−¿ ol
C5 H 11 OH CH 3 CH 2 CH 2 CH 2 CH 2 OH n−¿ Pentyl Butyl carbinol Pentan 1
°

alcohol, −1−¿ ol
1 −¿ Pentyl
°

alcohol
CH 3 −CH −CH 2−CH 2 CH 3 Active 2°−¿ pent Methyl Pentan 2
°

yl alcohol propylcarbinol −2−¿ ol

OH
CH 3 −CH 2−CH −CH 2 CH 3 2 −¿ Pentyl
°
Diethyl carbinol Pentan 2
°

alcohol −3−¿ ol
OH
CH 3 −CH 2−CH −CH 2 OH Activepentyl 2 −¿ Butyl
°
2−¿ Methy 1
°

alcohol carbinol l
CH 3
butan
2
−1−¿ ol
OH 3 −¿ Pentyl
°
Ethyl dimethyl 2−¿ Methy 3
°

CH 3 −CH 2−C−CH 3 alcohol carbinol l

butan
CH 3 −2−¿ ol
CH 3 −CH −CH 2−CH 3 Activeisopentyl Isopropyl 3−¿ Methy 2°
alcohol, 2°−¿ methyl carbinol l
OH CH 3
isopentyl alcohol butan
−2−¿ ol
HO CH 2−CH 2 −CH −CH 3 Isopentyl alcohol Isobutyl 3−¿ Methy 1
°

carbinol l
CH 3
butan
−1−¿ ol
CH 3 Neopentyl alcohol 3 −¿ Butyl
°
2,2−¿ Dime 1°
carbinol thyl
CH 3 −C−CH 2 −OH
Propan
CH 3 −1−¿ ol
Monohydric alcohols are again classified in two types:
i) Monohydric alcohols are classified in three parts on the basis of carbon atom
attached to hydroxyl group:
a) Primary alcohol : The monohydric alcohols in which −OH group is
attached to primary carbon atom are called primary, 1° or p−¿
alcohols. The general formula of these compounds is R−CH 2−OH . In
these −CH 2−OH is the characteristic functional group. Some of the
examples are given in the above table.
b) Secondary alcohols : The monohydric alcohols in which −OH group is
attached to secondary carbon atom are called secondary, 2° or s−¿
alcohols. The general formula of these compounds is R2 CH −OH . In
these CH −OH is the characteristic functional group. Some of the
examples are given in the above table.
c) Tertiary alcohols : The monohydric alcohols in which −OH group is
attached to tertiary carbon atom are called tertiary, 3° or t−¿
alcohols. The general formula of these compounds is R3 C−OH . In
these −C−OH is the characteristic functional group. Some of the
examples are given in the above table.
ii) Monohydric alcohols may be further classified according to the hybridisation
of the carbon atom to which the hydroxyl group is attached:
a) Compounds containing C sp −OH bond : In this class of alcohols, the
3

−OH group is attached to an sp 3 hybridised carbon atom of an alkyl

group. They are further classified as follows:
 I Allylic alcohols : In these alcohols, the −OH group is attached
to a sp 3 hybridised carbon next to the carbon-carbon double
bond, that is to an allylic carbon. For example,
CH 3
2 3
sp sp
CH 2=CH −CH 2−OH , CH 2=CH −CH −OH , CH 2=CH −C−OH

CH 3 CH 3
°
1 −¿ Allylic alcohol °
2 −¿ Allylic alcohol °
3 −¿ Allylic
alcohol
Prop −2−¿ en −1−¿ ol But −3−¿ en −2−¿ ol 2−¿
Methylbut −3−¿ en −2−¿ ol
II Benzylic alcohols : In these alcohols, the −OH group is attached
to a sp 3 hybridised carbon atom next to an aromatic ring. For
example,
CH 2−OH CH 3

& CH −OH −C−OH

CH 3 CH 3
°
1 −¿ Benzylic alcohol 2°−¿ Benzylic alcohol °
3 −¿
Benzylic alcohol
1−¿ Phenylmethanol 1−¿ Phenylethan −1−¿ ol 2−¿
Phenylpropan −2−¿ ol
9414248318, 0141-2719117 ,sYdksgkWy]
QhukWy ,oa bZFkj 3
 Since 1996 9414248318, 9468590309, 0141-2719117
Alcohols, Phenols and Ethers
 III Alkylic alcohol : The alcohols except above two, in which −OH
group is attached to sp 3 hybrid carbon are called alkylic alcohols.
For example,
OH OH
CH 3 −CH 2−CH 2 −CH 2−OH , CH 3

Butan −1−¿ ol Cyclohexanol 2−¿ cyclopentanol

b) Compounds containing C sp
−OH
2 bond : In this class of alcohols, the
−OH group is attached to an sp hybridised carbon atom of an alkyl
3

group. They are further classified as follows:

I Aryl alcohol : In these alcohols, −OH group is attached to
benzene cycle. In these alcohols more than one – OH group are
attached to benzene cycle. They are known as Phenols. For
example,
OH OH OH

CH 3 OH

Phenyl alcohol O−¿ Cresol O−¿ Catechol

Phenol 2−¿ Methylphenol Benzene −1,2−¿ diol

II Vinylic alcohol : In these monohydric alcohols, – OH group is

attached to carbon atom of aliphatic double bond. For example,
2 2
sp sp
CH 2=CH −OH , CH 3 −CH =CH −OH
Ethenol ¿¿ Vinyl alcohol ¿ Prop −1−¿ en −1−¿ ol
These alcohols are less stable; they are rearranged in Keto form.
For example,
CH 2=CH −OH ⇌ CH 3 −CH =O
enol form ¿¿ unstable ¿ keto form ¿¿ stable ¿
1) Dihydric Alcohols :
The alcohols in which two – OH groups are attached to two different carbon
atoms are called dihydric alcohols. They are also known as glycols. Their general
formula is Cn H 2 n+2 O2 . They are named in I . U . P . A .C . like monohydric
alcohols. Unlike monohydric alcohols, two – OH groups are also numbered. If
both – OH groups are attached to the close carbon atoms, the naming of these
is done with alkylene glycol and if these – OH groups are attached to
terminated carbon atom of unbranched series, they are named as polymethylene
glycol in common name system, where poly refers to the number of −CH 2−¿
groups. For example,
CH 2−CH 2 CH 3 −CH −CH 2 CH 2−CH 2 −CH 2

OH OH OH OH OH OH
Ehylene glycol Propylene glycol Trymethylene glycol
Ethane −1,2−¿ diol Propane −1,2−¿ diol Propane −1,3−¿ diol
The dihydric alcohols in which two – OH groups are attached to the same
carbon atom are unstable. They combine H 2 O molecule to become stable
carbonyl compounds.
2) Trihydric Alcohols :
The alcohols in which three – OH groups are attached to three different carbon
atoms are called trihydric alcohols. They are also known as Glycerol. Their general
formula is Cn H 2 n+2 O3 . They are named in I . U . P . A .C . like monohydric
alcohols. Unlike monohydric alcohols, three – OH groups are also numbered.
For example,
CH 2−CH −CH 2
 OH OH OH
Propane −1,2,3−¿ triol ¿¿ Glycerol ¿
XI , XII (CBSE
& RBSE)
 4
Isomerism in Alcohols ⇨
Alcohols show four types of isomerism: Chain isomerism, Position isomerism,
Functional group isomerism and optical isomerism
In chain isomerism, the change takes place in the carbon chain i.e. the change takes
place in the number of carbon atoms in main carbon chain. It is noted that only the
alcohols having 4 or more carbon atoms show chain isomerism.
In position isomerism, the change takes place in the position of functional group,
multiple bond or substitutes. The number of carbon atoms is not changed in the main
carbon chain. It is noted that only the alcohols having 3 or more carbon atoms show
chain isomerism.
In functional group isomerism, the change takes place in the difference of functional
group e.g. ethers and alcohols relatively show functional group isomerism. But
CH 3 −OH does not show functional group isomerism because, ether of one carbon is
impossible.
Asymmetric compounds show optical isomerism. It is noted that only the alcohols
having 4 or more carbon atoms show optical isomerism.
Structure of Alcohol Functional Group ⇨
In alcohol, oxygen atom exhibited sp 3 hybridisation. The
oxygen of the −OH group is attached to carbon by a
sigma (σ ) bond formed by the overlap of a sp 3
hybridised orbital of carbon with a sp 3 hybridised
orbital of oxygen and oxygen is attached to hydrogen by a
sigma (σ ) bond formed by the overlap of a s−¿
orbital of hydrogen with a second sp 3 hybridised
orbital of oxygen.
Other two sp hybridised orbital of oxygen do not participate in bonding, because
3

two lone pair electons are present there. Therefore, according to VSPER theory, the
geometry of phenol is angular (V ) . The bond angle in phenol is 108.9° . This bond
angle is slightly less than the tetrahedral angle (109 °−2 8' ) . It is due to the maximum
repulsion between the unshared electron pairs (l p) of oxygen.
Preparation of Alcohols ⇨
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.
+¿¿
H
¿ C=C<¿ +¿ H2O ¿ C−C ¿
H OH
Mechanism:
The mechanism of the reaction involves the following three steps:
Step 1 : Protonation of alkene to form stable carbocation by electrophilic
+¿
attack of H 3 O¿ .
+¿¿ +¿
H2O +¿ H 3 O¿
H
H H
+¿−H +¿<¿
¿ C=C<¿ +¿ +¿ H2O
H −O
¿
¿ C−C¿
Step 2 : Nucleophilic attack of water on carbocation.
H H
+¿<¿
¿ C−C¿ +¿ H−O−H ¿ C−C<¿

+¿−H
H −O¿
Step 3 : Deprotonation to form an alcohol by the presence of water.
H H
+¿−H
¿ C−C<¿ +¿ H−O−H ¿ C−C<¿ +¿
H −O¿
+¿−H
OH H
H −O ¿
 Since 1996 9414248318, 9468590309, 0141-2719117
 Propene reacts with water in the presence of acid like dil H 2 SO 4 or dil
HC l to form 2−¿ propanol.
dil . H 2 SO 4 5
CH 3 −CH =CH 2 +¿ H−O−H CH 3 −CH −CH 2

OH H
Propene 2−¿ propanol
ii) By hydroboration–oxidation : Diborane 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 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.
CH 3 −CH =CH 2
CH 3 −CH =CH 2+¿ H−BH 2 CH 3 −CH −CH 2

H BH 2
CH 3 −CH −CH 2 CH 3 −CH −CH 2
CH 3 −CH =CH 2
H B−CH 2−CH 2−CH 3 H
BH −CH 2−CH 2−CH 3

CH 2−CH 2 −CH 3
Or
1
3CH3—CH=CH2 + B H (CH3—CH2—CH2) 3B
2 2 6
−¿
3H2O2/
OH ¿
(CH3—CH2—CH2) 3B CH3—CH2—CH2—OH + H3BO3
Tripropyl borane Propyl alcohol Boric acid
2) By hydration of Haloalkane :
Haloalkanes on treatment with aqueous KOH or aqueous NaOH or moist Ag 2 O
( Ag 2 O + H 2 O = 2AgOH) give alcohol of same carbon.
R—X + aqueous KOH R—OH + KX
CH 3 — CH 2 —Br + KOH (aq.) CH 3 — CH 2 —OH + KBr
Bromoethane Ethanol
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 by dil H 2 SO 4 or dil HC l . All three types of alcohols are produced
by the reaction of Grignard reagents with aldehydes and ketones.
Formaldehyde gives primary alcohol.
'
R
'
R
H H H2O H
'
C=O+ R −MgX C−OMgX
C−OH
H H −Mg ( X ) OH H
Methanal Alkyl magnesium halide Primary alcohol
Alkyl aldehyde gives secondary alcohol.
'
R
R'
R R H2O R
'
C=O+ R −MgX C−OMgX
C−OH
H H −Mg ( X ) OH H
 Alkanal Alkyl magnesium halide Secondary alcohol
Ketone gives tertiary alcohol.
'
R
R'
R R H2O R
'
C=O+ R −MgX C−OMgX
C−OH
R R −Mg ( X ) OH R
Alkanone Alkyl magnesium halide Tertiary alcohol
XI , XII (CBSE & RBSE) 6
Alcohols, Phenols
and Ethers
 Since 1996 9414248318, 9468590309,
7791835250

4) From carbonyl compounds :

i) By reduction : Aldehydes and ketones are reduced to the corresponding
alcohols by sodium borohydride (NaBH 4 ) or lithium aluminium hydride
(LiA l H 4 ) . Formaldehyde yield methanol, Alkyl aldehydes yield primary
alcohols whereas ketones give secondary alcohols. From this method
tertiary alcohols can not be obtained.
LiA l H 4
H−CHO +¿ 2H CH 3 −OH
Formaldehyde Methanol
LiA l H 4
R−CHO+ ¿ 2H R−CH 2−OH
LiA l H 4
R−C−R+ ¿ 2H R−CH −R

O OH
Ketones Secondary alcohols
ii) By catalytic hydrogenation : Aldehydes and ketones are reduced to the
corresponding alcohols by addition of hydrogen in the presence of
catalysts. The usual catalyst is a finely divided metal such as platinum,
palladium or nickel.
Pt
R−CHO+ ¿ H2 R−CH 2−OH
Pt
R−C−R+ ¿ H2 R−CH −R

O OH
5) 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. −COOH group is converted to
−CH 2−OH in this reaction.
( i ) LiA l H 4
R−COOH +¿ 4H R−CH 2−OH
( ii ) H 2 O
( i ) LiA l H 4
R−COOR +¿ 4H R−CH 2−OH +¿ R−OH
( ii ) H 2 O
However, LiA l H 4 is an expensive reagent, and therefore, used for preparing
special chemicals only. Commercially, carboxylic acids are reduced to alcohols by
converting them to the esters, followed by their reduction using hydrogen in the
presence of metal catalyst. Alocohols does not prepared by catalytic
hydrogenation of carboxylic acid. On catalytic hydrogenation carboxylic acides
form alkane.
 H 2 SO 4
R−COOH +¿ '
R −OH R−COOR ' +¿ H2O
Pd
R−COOR ' +¿ H2 R−CH 2−OH +¿ R '−OH
Physical Properties of Alcohols ⇨
1) Solubility in water %
Solubility of alcohols in water is due to their ability to form hydrogen bonds with
water molecules as shown:
−OH group of alcohol is attached with
water molecules by hydrogen bond. So,
this part of alcohol is known as hydrophilic
part. While the carbon chain of alcohol
exhibits steric hinderence to form
 hydrogen bond with water molecule. That’s reason it is known as hydrophobic
part. As the size of hydrophobic part ¿¿ alkyl group ¿ of alcohols increases, it7
prevents the formation of hydrogen bonding with water molecule, and hence
the solubility goes on decreasing with increase in length of carbon chain. That’s
why, lower members of alcohols are highly soluble in water and higher members
of alcohols are less soluble in water.
In isomeric alcohols, as the branching increases, the surface area of hydrophobic
part ¿¿ alkyl group ¿ decreases and therefore the solubility increases with
increase branching. That’s why; branched alcohols are highly soluble in water
than unbranched isomeric alcohols. Therefore,
Tertiary alcohol > Secondary alcohol > Primary alcohol
1) Melting and boiling points %
The −OH group in alcohols is involved in intermolecular hydrogen bonding as
shown below:
R R R R
… O−H … . O−H … . O−H …. O−H … .
Therefore, extra energy will be requiring for cleavage the extra hydrogen bonds.
So, it is interesting to note that boiling points of alcohols are higher in
comparison to other classes of compounds, namely hydrocarbons, ethers,
haloalkanes and haloarenes of comparable molecular masses.
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.
The boiling points of alcohols increase with increase in the number of carbon
atoms, due to increase in van der Waals forces. Therefore, the boiling points of
alcohols increase with increase their molecular weight. 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. So, the boiling points of
branched alcohols are lesser than the unbranched alcohols. Therefore,
Tertiary alcohol < Secondary alcohol < Primary alcohol
Chemical Reactions of Alcohol ⇨
Alcohols are versatile and most reactive compounds due to presence of polar −OH
group. They react both as nucleophiles and electrophiles. Thus, alcohol exhibites two
type of chemical reactions:
 The bond between O−H is broken when alcohols react as nucleophiles.
..
+¿¿ +¿ — C
R — O— H +¿ C — R — ¿ —
O
+¿¿
R — O—C — +¿ H
..
H
Because, alcohol reacts as nucleophiles in cleavage of O−H bond, therefore
size of alcohol should be as such that it exhibites minimum steric hinderence. So,
in primary alcohol, O−H bond is cleavaged easily due to its low steric
hinderence. The increasing order of the reactivity with respect to O−H bond
cleavage in different alcohols is:
Tertiary alcohol < Secondary alcohol < Primary alcohol
 The bond between C−O is broken when they react as electrophiles.
..
−¿ : + ¿−H
+¿ — Br — CH 2 +¿ H2O
: Br
¿
CH 2 — O ¿
..
R H R
Protonated alcohol
Protonated alcohols react as electrophile in this type of reaction. Therefore those
alcohols which are converted into most stable carbonium ion are most reactive
alcohols. So, in tertiary alcohol, C−O bond is cleavaged easily due to its
tendency to convert into most stable 3 °−¿ carbonium ion. The increasing order
of the reactivity with respect to C−O bond cleavage in different alcohols is:
Primary alcohol < Secondary alcohol < Tertiary alcohol
9414248318, 0141-
2719117 8
Reactions involving cleavage of bond
O−H
1) Reaction with metals :
Alcohols react with active metals such as sodium, potassium and aluminium to
yield corresponding alkoxides and hydrogen. Thus, this reactions show that
alcohols are acidic in nature.
2R — OH + 2Na 2R — ONa + H 2
Sodium alkoxide
6CH 2—CH 2—OH + 2A� 2(CH 3CH 2O) 3A� + H 2
Ethanol Aluminium ethoxide
The acidic character of alcohols is due to the polar nature of O−H bond. But
an electron-releasing group R−¿ ¿ increases electron density on oxygen tending
to decrease the polarity of O−H bond. In other words, the bonded electron
of O−H bond is shiffted towards hydrogen atom and hydrogen does not
+¿
separate as H ¿ ion. This decreases the acid strength. For this reason, the acid
strength of alcohols increases in the following order:
Tertiary alcohol < Secondary alcohol < Primary alcohol
Alcohols are, however, weaker acids than water. In alcohol, + I effect of alkyl
group increases electron density on oxygen. So, the bonded electron of O−H
bond is shiffted towards hydrogen atom and hydrogen does not separate as
+¿¿
H ion. While in water, any alkyl group does not present. So due to more
polarity of O−H bond, water is more acidic than the alcohol. This also 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.
−¿¿ −¿
R— O + H—O—H R—O—H + OH ¿
Base Acid Conjugate acid Conjugate base
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.
2) Synthesis of ester :
The reaction with carboxylic acid and acid anhydride is carried out in the
presence of a concentrated sulphuric acid. The reaction is reversible, and
therefore, water is removed as soon as it is formed. This reaction is known as
esterification.
+¿¿
H
R — OH + R’ — COOH R — COOR’ + H2O
+¿¿
H
R — OH + R’ — C — O — C — R’ R — COOR’ + R’ — COOH
O O
The reaction with acid chloride is carried out in the presence of a base ¿¿
pyridine ¿ so as to neutralise HC l which is formed during the reaction. It
shifts the equilibrium to the right hand side. This reaction is known as acylation
and the introduction of acetyl (CH 3 CO) group in alcohols or phenols is known
as acetylation.
Pyridine
R — OH + R’ — COC� R — COOR’ + HC l
Pyridine
C2 H 5 OH +CH 3 COC l CH 3 CO C 2 H 5 + HC l
Acetylation of salicylic acid produces aspirin. This is used as analgesics and
antipyretic medicine.
 COOH COOH
+¿¿
OH CH 3—C—O—C— CH 3 H OCO CH 3
+ + CH 3COOH
O O
Salicylic acid Acetic anhydride Aspirin
9414248318, 9468590309 Alcohols,
Phenols and Ethers
Since :- 1996 9414248318(whatsApp), 9468590309, 01412719117

Reactions involving cleavage of C−O bond 9

1) Synthesis of Alkyl halide :
i) Reaction with halogen acids :
HC� reactivity is lowest in all the halogen acids, then alcohol reacts with
HC� in presence of dry ZnC� 2. Mixture of HC� and dry ZnC� 2 is called Lucas
reagent.
dry ZnC� 2
CH 3—CH 2—OH + HC� CH 3—CH 2—C� + H 2O
Ethyl alcohol Ethyl chloride
In this reaction C—O bond fission take places for alcohol. So the decresing
order of reactivity for different alcohols are t- > s- > p- . The difference in
reactivity of three classes of alcohols with Lucas reagent distinguishes
them from one another ¿¿ Lucas test ¿ . In case of tertiary alcohols,
turbidity is produced immediately as they form the halides easily and
secondary alcohols turbidity is produced after 5 minite. Primary alcohols
do not produce turbidity at room temperature.
Bromoalkanes are often prepared by heating of alcohol and hydrobromic
acid ¿¿ HBr ¿ in presence of catylist con. H 2SO 4. Here, HBr prepared by
the reaction of con. H 2SO 4 and KBr or NaBr .
con. H 2SO 4
CH 3—CH 2—OH + HBr CH 3—CH 2—Br + H 2O
Iodoalkanes are also be prepared by heating of alcohol and hydroiodic
acid ¿¿ HI ¿ in presence of catylist con. H 3PO 4 . Like HBr , HI also be
prepared by the reaction of con. H 3PO 4 and KI or NaI during the reaction.
con. H 3PO 4
CH 3—CH 2—OH + HI CH 3—CH 2—I + H 2O
ii) Reaction with phosphorus halides :
CH 3—CH 2—O— H + PC� 5 CH 3—CH 2—C� + POC� 3 + HC�
C�—PC� 3—C� Ethyl chloride Phosphorus
Ethyl alcohol oxy chloride
R—OH C�
R—OH + P C� 3R—C� + H 3PO 3
R—OH C� Orthophosphorus acid
 iii) Reaction with thionyl chloride :
pyredene
CH 3—CH 2—O— H + SOC� 2 CH 3—CH 2—C� + SO 2 + HC�
C�— SO —C� Ethyl chloride
2) Dehydration :
Alcohols undergo dehydration ¿¿ removal of a molecule of water ¿ to form
alkenes on treating with a protic acid e.g., concentrated H 2 SO 4 or H 3 PO 4 .
On the basis of stability of carbonium ion during the dehydration, the relative
ease of dehydration of alcohols follows the following order:
Tertiary alcohol > Secondary alcohol > Primary alcohol
Primary alcohol undergoes dehydration by heating it with concentrated
H 2 SO 4 at 443 K . For example,
Con. H 2 SO 4
CH 3 −C H 2−OH CH 2=C H 2 + H 2 O
443 K
The mechanism of dehydration of ethanol involves the following steps:
Mechanism
Step 1 : Formation of protonated alcohol.
Fast
+¿¿ +¿−H
CH 3 −C H 2−O−H +¿ ¿
H CH 3 −C H 2−O

H
Protonated ethanol
 Since 1996 9414248318, 9468590309,
7791835250
 Step 2 : Formation of stable carbocation from protonated alcohol. It is the
slowest step and hence, the rate determining steps of the reaction.
Slow
+¿−H +¿
CH 3 −CH ¿2 +¿ H−O−H
CH 3 −C H 2−O¿

H
Ehyl carbonium ion
Step 3 : Formation of ethene by elimination of a proton. The acid used in step
1 is released in this step. To drive the equilibrium to the right, ethene is
removed as it is formed.
H H H H
+¿ +¿¿
H−C−C ¿ C=C +¿ H
H H H H
Secondary and tertiary alcohols are dehydrated under milder conditions.
80 H 3 PO 4
CH 3 −CH −OH CH 3 −CH =CH 2 +¿ H−O−H
440 K
CH 3
CH 3
20 H 3 PO 4
CH 3 −C−OH CH 3 −C=CH 2 +¿ H−O−H
358 K
CH 3 CH 3
Oxidation
Oxidation of alcohols involves the formation of a C−O double bond with cleavage
of an O−H bond from hydroxyl group and C−H bond from the α −¿ carbon.
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, defferent oxidation
reactions are possible as follows:
1) Oxidation under strong oxidising agent :
Strong oxidising agents such as acidified potassium permanganate or potassium
dichromate are used for getting carboxylic acids from alcohols directly.
A primary alcohol is easily oxidised to give first aldehyde and then aldehyde is
oxidised to a carboxylic acid in same conditions. The aldehyde and carboxylic
acid formed contain the same number of carbon atoms as the primary alcohol.
H H OH
Acidic KMn O4 [O]
R—C—O + [O] R—C ¿ O R—C ¿ O
−¿ H 2O
H H
Secondary alcohols are oxidised to ketones of same number of carbon atoms as
the secondary alcohol.
R R
Acidic KMn O4
R—C—O + [O] R—C ¿ O
−¿ H 2O
H H
If ketones are oxidised under strong oxidising agent and elevated temperatures,
then it may be further oxidised to form a mixture of carboxylic acids, which
contain lesser number of carbon atoms as the starting alcohol.
Acidic K MnO4 [O]
CH 3 −CH −OH CH 3 −C−CH 3 CH 3 −COOH +¿
CO2 +¿ H2O
[O]
CH 3 O
45\32, Kiran Path, Near Electricity Office, Man Sarover
& 60, Shiv Colony, Near Arjun Nagar Phatak, Kisaan Marg
XII, XI (CBSE & RBSE) Alcohols, Phenols and 11
Ethers
Tertiary alcohols do not undergo oxidation reaction, due to absence of α −¿
hydrogen. Under strong reaction conditions such as strong oxidising agents 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.
CH 3 CH 3 CH 3

Acidic KMn O4 [O]

CH 3 —C—OH CH 3 —C= CH 2 CH 3 —C ¿ O +
HCHO
−¿ H 2O
CH 2 H
CH 3
Acidic KMn O4
CH 3 —C ¿ O CH 3 —C OOH + HCOOH
[O]
H —C—OH Acidic KMn O4 HO —C—OH
CO2 + H2O
O [O] O
Carbonic acid ¿¿ unstable ¿
2) Oxidation by chromic anhydride :
Primary alcohols are oxidised to alcohols and secondary alcohols are oxidised to
ketones by chromic anhydride. Due to absence of α −¿ hydrogen, tertiary
alcohols do not oxidise by this weak oxidising agent.Therefore, CrO 3 in
anhydrous medium is used as the oxidising agent for the isolation of aldehydes.
The mixture of chromic anhydride and pyridine is called as Collins reagent.
CrO 3
R— CH 2 —OH + [O] R—C HO
−¿ H 2O
R R
CrO 3
R—CH—OH + [O] R—C ¿ O
−¿ H 2O
3) Oxidation by pyridinium chlorochromate ( PCC) :
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 HC l .
PCC
CH 3 −CH 2−OH CH 3 −CHO
PCC
CH 2=CH −CH 2−OH CH 2=CH −CHO
Allyl alcohol Acryl aldehyde
4) Dehydrogenation :
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.
Cu, 573 K
R— CH 2 —OH R—C HO
−¿ H2
R R
Cu, 573 K
R—CH—OH R—C ¿ O
−¿ H2
CH 3 CH 3
Cu, 573 K
 CH 3 —C—OH CH 3 —C= CH 2
−¿ H 2O
CH 2 H
Note %& 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 formaldehyde to
acid is swamped allowing time for kidneys to excrete methanol.
45\32, Kiran Path, Near Electricity Office, Man Sarover
& 60, Shiv Colony, Near Arjun Nagar Phatak, Kisaan Marg
12
 Since 1996  9414248318, 9468590309,
7791835250
By haloform reaction :
Heating with Iodine and alkaline, organic compounds which have CH 3 — CH(OH) —
or CH 3 — CO — groups gives yellow ppt. of iodoform. It is known as iodoform test.
CH 3 CH 2 —OH +4 I 2 +¿ 6NaOH CHI 3 + HCOONa+¿ 5NaI +¿ 5
H2O
Ethyl alcohol Iodoform
Chemically difference between methanol & ethanol, 1−¿ propanol & 2−¿
propanol etc. can be done by the iodoform test. Because, ethanol, 2−¿ propanol are
formed yellow ppt. of iodoform, while methanol, 1−¿ propanol does not form
iodoform.
Methanol ⇨
Methanol, 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 −Cr2 O3
catalyst.
573−673 K , 200−300 atm
CO+2 H 2 CH 3 −OH
ZnO −Cr2 O3
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.
Ethanol ⇨
Ethanol 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, in the presence of an enzyme, invertase.
Invertase( yeast)
C12 H 22 O11 +¿ H2O C6 H 12 O6 +¿ C6 H 12 O6
Succrose Glucose Fractose
Glucose undergoes fermentation in the presence of another enzyme, zymase, which is
found in yeast. The action of zymase is inhibited once the percentage of alcohol
formed exceeds 14 .
Zymase ( yeast)
C6 H 12 O6 2C 2 H 5 OH +¿ 2CO 2
Glucose Ethyl alcohol
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 absence of air. If air gets into fermentation mixture, the oxygen of air
oxidises ethanol to ethanoic acid which in turn destroys the taste of alcoholic drinks.
Carbon dioxide is released during fermentation.
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.
A little amount of ethanol acts on the central nervous system. In moderate amounts, it
affects judgment and lowers inhibitions. Higher concentrations cause nausea and loss
of consciousness. Even at higher concentrations, it interferes with spontaneous
respiration and can be fatal.
Classification and Nomenclature of Phenols ⇨
Phenols are those hydroxyl compounds in which −OH group is attached with
benzene ring. They are generally represented by Ar −OH where Ar represents the
aromatic hydrogen group. Naming of phenols is done in the form of a derivative of a
general member of phenol family. This is also known as the carbolic acid. The 13
substitute in aromatic ring with respect to −OH group is represented as ortho
O−¿
¿ for 1,2 position, meta m−¿ ¿ for 1,3 position, para p−¿ ¿ for 1,4
position. In I . U . P . A .C . , mono, di, or trihydroxy phenol are written in the form of
hydroxy derivative. On the basis of number of −OH groups, phenols are classified
in the following manner:
1) Monohydric Phenol :
The Phenol, in which only one – OH group is present, is called monohydric
phenol. They are generally represented by Ar −OH or ∅−OH . For example,
OH OH OH OH
CH 3
CH 3
Carbolic acid O−¿ Cresol m−¿ Cresol CH 3
p−¿ Cresol
Phenol 2−¿ Methylphenol 3−¿ Methylphenol 4−¿
Methylphenol
2) Dihydric Phenol :
The Phenol, in which two – OH groups are attached to two different carbon
atoms of benzene ring are called dihydric phenol. For example,
OH OH OH
OH
OH
Catechol Resorcinol OH Hydroquinone or quinol
Benzene −1,2−¿ diol Benzene −1,3−¿ diol Benzene −1,4−¿ diol
Structure of Phenol ⇨
In phenol, oxygen atom exhibited sp 3 hybridisation. The oxygen of the −OH group
is attached to carbon by a sigma (σ ) bond formed by the overlap of a sp 2
hybridised
orbital of benzene ring carbon with a sp 3 hybridised
orbital of oxygen and oxygen is attached to hydrogen by a
sigma (σ ) bond formed by the overlap of a s−¿ orbital
of hydrogen with a second sp 3 hybridised orbital of
oxygen.
Other two sp 3 hybridised orbital of oxygen do not participate in bonding, because
two lone pair electons are present there. Therefore, according to VSPER theory, the
geometry of alcohol is angular (V ) .
The C−O bond length (136 pm ) in phenol is slightly less than that in methanol
(142 pm) . This is due to following two reasons:
(i) In phenol, the C−O bond gets partial double bond characteristic due to
resonance. As a result, the bond length reduces.
(ii) sp
2
hybridised state of carbon to which oxygen is attached. Therefore the
bond length reduces due to excess of %s character.
Preparation of Phenols ⇨
1) From Haloarene :
When aryl halide is heated with aqueous solution of NaOH at about 623 K
and under a pressure of 300 atmospheric pressure gives sodium phenoxide,
which on acidification gives phenol.
623 K∧¿ 300 atm dil . HC l
C6 H 5 — C l + NaOH C6 H 5 — ONa
C6 H 5 — OH
−HC l −NaC l
2) From Benzene diazonium salt :
Phenol is obtained by reacting benzene diazonium salt with hot water.
+¿ ≡ N −¿
C6 H 5 — ¿ . C l ¿ + H—OH C6 H 5 — OH + N2 + H
N
Cl
3) From Cumene :
Cumene is oxidised in cumene hydroperoxide in the presence of air. 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.
CH 3 CH 3
CH C — O — OH OH
CH 3 CH 3 +¿¿
H
+ O2 HOH + CH 3 CO CH 3

Cumene Cumene hydroperoxide Phenol Acetone

14
4) From benzenesulphonic 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.
SO 3
C6 H 5 — H + H 2 SO 4 C6 H 5 — SO 3 H + H2O
Benzene Benzene sulphonic acid
C6 H 5 — SO 3 H + NaOH C6 H 5 — SO 3 Na + H2O
Sodium benzene sulphonate
C6 H 5 — SO 3 Na + NaOH C6 H 5 — ONa + NaHSO3
dil . HC l
C6 H 5 — ONa C6 H 5 — OH + NaC l
Sodium phenoxide Phenol
Physical Properties of Phenol ⇨
1) Solubility in water :
They do not form strong intermolecular hydrogen bonds because of the bigger
size of phenyl group. Due to this reason, they are less soluble in water.
2) Melting and boiling points %
The −OH group in phenols is involved in intermolecular hydrogen bonding as
shown below:
C6 H 5 C6 H 5 C6 H 5 C6 H 5

… O−H … . O−H … . O−H …. O−H … .

Therefore, extra energy will be required to cleavage the extra hydrogen bonds.
So, it is interesting to note that boiling points of phenols are higher in
comparison to other classes of compounds.
Chemical Properties of Phenol ⇨
Reactions of O−H group
1) Acidic nature of phenol :
Due to resonance, phenol is acidic. Phenol has following resonance structures:
´
: OH ´
+ OH ´
+ OH ´
+ OH
´
: OH

❑⊖ ❑⊖

⊖
❑
Due to this, the charge distribution in phenol molecule, as depicted in its
resonance structures, causes the oxygen of −OH group to be positive.
Therefore, oxygen strongly attracts electrons of O−H bond and releases
+¿
hydrogen in the form of H ¿ ion.
The other reason of phenol acidic nature is that the phenoxide ion obtained by
ionisation of phenol also shows resonance and its resonance structures are
more stable than phenols. Therefore phenol forms stable phenoxide ion after
+¿
ionisation and releases hydrogen in the form of H ¿ . The stability of phenoxide
ion is understood by its resonance structures:
O:−¿ O:−¿
: Ó : Ó : Ó
: ´¿ : ´¿

❑⊖ ❑⊖

⊖
❑
It is clear from the above resonance structures that the delocalisation of
negative charge 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.
The reactions of phenol with metals and sodium hydroxide indicate its acidic
nature.
1
C6 H 5 OH + Na C6 H 5 ONa +¿ H2
C6 H 5 OH + NaOH C6 H 5 ONa +¿
2
H2O
15
Since :- 1996 9414248318(whatsApp), 9468590309, 01412719117
 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:
+¿
C2 H 5 OH −¿+ H ¿
C2 H 5 O¿
Stable Less stable
−¿ +¿
C6 H 5 OH C 6 H 5 O¿ +H¿
Less stable More stable
The phenoxide obtained by ionisation of phenol is more stable than phenol due
to resonance. Therefore phenol easily form stable phenoxide ions by losing
protons whereas the ethoxide obtained by ionisation of ethanol does not show
resonance, even it is unstable because of the negative charge is localised on
oxygen. Therefore, ethanol does not lose proton easily.
The −I effect of phenyl group of phenol is less than ¿ C=O group of
carboxylic group. Therefore phenols are weak acid than carboxylic acid. So,
phenols can’t release CO2 gas by reacting with weak alkaline like, sodium
carbonate or sodium bicarbonate. While carboxylic acids are released CO2 gas
by reacting with sodium carbonate or sodium bicarbonate.
C6 H 5 OH + Na 2 CO 3 C6 H 5 ONa +¿ NaH CO 3
C6 H 5 OH + NaH CO 3 No reaction.
RCOOH + Na 2 CO 3 RCOONa +¿ NaH CO 3
RCOOH + NaH CO 3 RCOONa +¿ CO2 +¿ H2O
This reaction is used in the classification of carboxylic acid and phenol. It is clear
from the above whole theory that Phenols are more acidic than alcohols but less
acidic than carboxylic acids. The strength of acids is the following way:
C H 3 COOH > C6 H 5 OH > C2 H 5 OH
Acidity of substituted phenols : as it is clear that stability of phenoxide ion is
higher than that of phenol. Therefore a substitute that increases the stability of
phenoxide ion by increasing the displacement of negative charge increases the
acidity of phenol. On the other side, the substitute that increases the electron
density on the benzene ring reduces the stability of phenoxide ion. As a result,
the acidity of phenol is decreased.
i) In substituted phenols, the presence of electron withdrawing groups such
as −NO 2 ,−CN , −X , −CHO etc, enhances the acidic strength of
phenol. This effect is more pronounced when such a group is presenting at
ortho and para positions. It is due to the effective delocalisation of
negative charge in phenoxide ion. For example,
p−¿ Nitrophenol > O−¿ Nitrophenol > m−¿ Nitrophenol > Phenol
In addition to this in phenol, as much electron attracting groups are
attached to ortho and para positions as it increases the acidic nature of
phenol. For example,
2,4,6−¿ Trinitrophenol > 2,4−¿ Dinitrophenol > 4−¿ Nitrophenol
That is why 2,4,6−¿ Trinitrophenol and 2,4−¿ Dinitrophenol is more
acidic than carbonic acid. Therefore, in aqueous solution of Na2 CO 3 or
NaH CO 3 it forms a respective salt and releases CO2 .
ii) The electron donor group like alkyl group reduces the stability of
phenoxide ion in comparison to phenol. As a result, if electron donor
group is present at the benzene ring reduces its acidic nature. That’s
 tendancy is more effective when these groups are attached to ortho and
para positions.
Phenol > m−¿ Cresol > p−¿ Cresol or O−¿ Cresol
16
2) Synthesis of ester :
The reaction with carboxylic acid and acid anhydride is carried out in the
presence of a concentrated sulphuric acid. The reaction is reversible, and
therefore, water is removed as soon as it is formed. This reaction is known as
esterification.
+¿¿
H
C6 H 5 OH +¿ R−COOH R−COO C 6 H 5 + H2O
+¿¿
H
C6 H 5 OH +¿ R−¿ C — O — C — R R−COO C 6 H 5 +¿
R−COOH
O O
The reaction with acid chloride is carried out in the presence of a base ¿¿
pyridine ¿ so as to neutralise HC l which is formed during the reaction. It
shifts the equilibrium to the right hand side. This reaction is known as acylation
and the introduction of acetyl (CH 3 CO) group in alcohols or phenols is known
as acetylation.
Pyridine
C6 H 5 OH +¿ R−COC l R−COO C 6 H 5 +¿ HC l
Pyridine
C6 H 5 OH +CH 3 COC l CH 3 CO C 6 H 5 + HC l
Phenol Acetyl chloride Aceto phenone
2) Reaction with phosphorus halides :
C 6H 5—O H + PC� 5 C 6H 5—C� + POC� 3 + HC�
C�—PC� 3—C� Choloro benzene Phosphorous
oxychloride
C 6H 5—OH C�
C 6H 5—OH + P C� 3C 6H 5—C� + H 3PO 3
C 6H 5—OH C� Ortho phosphorous acid
3) Reduction %
Phenol is converted to benzene on heating with zinc dust.
C 6H 5—OH + Zn C 6H 5—H + ZnO
Electrophilic aromatic substitution
In phenols, the reactions that take place on the aromatic ring are electrophilic
substitution reactions. The −OH group attached to the benzene ring activates it
towards electrophilic substitution. Phenol shows the following resonance structures:
´
: OH ´
+ OH ´
+ OH ´
+ OH
´
: OH

❑⊖ ❑⊖

❑⊖
In phenol resonance structures, the electron density on ortho and para positions is
more than meta position. It directs the incoming group to ortho and para positions in
the ring as these positions. Common electrophilic aromatic substitution reactions
taking place in phenol are as follows:
1) Halogenation :
The usual halogenation of benzene takes place in the presence of a Lewis acid,
which polarises the halogen molecule. In case of phenol, the polarisation of
halogen molecule 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. On
treating phenol with bromine, different reaction products are formed under
different experimental conditions.
i) Bromination in presence of nonpolar medium : when the reaction is
carried out in solvents of low polarity such as CHC l3 or CS 2 and at
low temperature, monobromophenols are formed.
OH OH OH
CS2 ,273 K Br
+ Br 2 +
−HBr
Phenol O−¿ Bromophenol Br
¿ Minor ¿ p−¿ Bromophenol ¿ Major
¿ ¿
¿
 9414248318, 0141-2719117 
Since 1996 9414248318
 ii) Bromination in presence of polar medium : when phenol is treated with
bromine water, 2,4,6−¿ tribromophenol is formed as white precipitate.
OH OH
Br Br 17
+ 3 Br 2
−3 HBr
Phenol Br
2) Nitration :
i) By dil nitric acid : with dilute nitric acid at low temperature, phenol yields
a mixture of ortho and para nitrophenols.
OH OH OH
dil HNO3 , 298 K NO2
+
−H 2 O
Phenol O−¿ Nitrophenol NO2
¿ Minor ¿ p−¿ Nitrophenol ¿
¿ ¿
Major ¿
The ortho and para isomers can be separated by steam distillation.
Because, O−¿ Nitrophenol is steam volatile due to weak intramolecular
hydrogen bonding while p-nitrophenol is less volatile due to strong
intermolecular hydrogen bonding, so it is obtained first.
O— H
−¿¿
O
−¿ … … HO — −¿ … …
+¿ … HO — ¿ ¿
¿ +¿ — O +¿ — O
N
— N¿ —N¿
O
O O
ii) By concentrate nitric acid : with concentrated nitric acid, phenol is
converted to 2,4,6−¿ trinitrophenol.
OH OH
Con. HNO 3 NO2 NO2

−3 H 2 O
Phenol NO2
2,4,6−¿ Trinitrophenol ¿¿ picric acid ¿
The yield of the reaction product is poor. So, nowadays picric acid is
prepared by treating phenol first with concentrated sulphuric acid which
converts it to phenol −2,4−¿ disulphonic acid, and then with
concentrated nitric acid to get 2,4,6−¿ trinitrophenol.
OH OH
Con. H 2 SO 4 SO 3 H

−2 H 2 O
Phenol SO 3 H
Phenol −2,4−¿ disulphonic acid
OH OH OH
SO 3 H NO2 SO 3 H HNO 3
NO2 NO2
+ HNO3
−H 2 O −2 H 2 SO 4
SO 3 H SO 3 H
NO2
3) Friedel-Crafts reaction :
 Friedel-Crafts alkylation or Friedel-Crafts acylation can be carried out with the
reaction of alkyl halide or acyl halide respectively in the presence of anhydrous
A lC l 3 .
OH OH OH
anhyd . A lC l 3 CH 3
+ CH 3 C l + +
−HC l
Phenol O−¿ Cresol CH 3
¿ Minor ¿ p−¿ Cresol ¿ Major
¿ ¿
¿
Since 1996 9414248318
 OH OH OH
anhyd . A lC l 3 COCH 3 18
+ CH 3 COC l +
−HC l
Phenol 2−¿ hydroxyacetophenone COCH 3
¿ Minor ¿ 4−¿ hydroxyacetophenone ¿
¿ ¿
Major ¿
4) Reimer-Tiemann reaction :
When phenol is heated with chloroform and alcoholic potassium hydroxide,
then salicylaldehyde is obtained. In this reaction, hydrogen of benzene ring is
replaced by formyl ( — CHO) group.
OH OH
CHO
+ CHC l 3 + 3 NaOH + 3 NaC l + 2 H 2O

It is an electrophile substitution reaction, here dichlorocarbene used as an

electrophile reagent.
CHC l 3 + −¿ −¿ Ć C l 3 −¿
OH ¿ ¿ Ć C l 2 + C l¿
❑
−H 2 O
+¿ +¿
OH −¿ . Na¿ −¿ . Na ¿
O¿ O¿
+¿
−¿ . Na¿ OH
O¿
CHC l 2 −¿
NaOH Ć C l 2 2OH ¿
CH
OH
−H 2 O
+¿ +¿
−¿ . Na¿ OH −¿ . Na¿ OH
O¿ O¿
CH CHO CHO
−H 2 O +¿¿
OH H

5) Kolbe’s reaction :
Phenoxide ion generated by treating phenol with sodium hydroxide is even
more reactive than phenol towards electrophilic aromatic substitution. Hence, it
undergoes electrophilic substitution with CO2 , a weak electrophile. Ortho
hydroxybenzoic acid ¿¿ Salicylic acid ¿ is formed as the main reaction product.
+¿
OH −¿ . Na¿
O¿

+ NaOH
−H 2 O
+¿
−¿ . Na¿ OCOONa OH
O¿
OH
CO2 Rearrangement COONa COOH

dil HC l
Sod. phenyl carbonate Sod. salicylate Salicylic acid
6) 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.
OH O
Na 2 Cr 2 O 7

H 2 SO 4

O
Benzoquinone
Classification and Nomenclature of Ether ⇨
The compounds in which an oxygen atom is present and both the valences of
oxygen are attached with two alkyl groups, two phenyl groups or an alkyl and a
phenyl group are called Ethers. The ethers are also called anhydride of alcohols
since they are formed by removing a water molecule from the alcohol. The
functional group of ether is – O−¿ . Ethers are also called dialkyl derivatives of
water as they are by displacing both hydrogen of water by alkyl group. There are
two types of ethers:
19
1) Simple or Symmetrical Ethers :
The ethers in which two similar alkyl groups or phenyl groups are attached to
oxygen atom are called symmetrical ethers. They are generally represented as
R−O−R or Ar −O− Ar . In the common naming system, they are named as
dialkyl ether or diphenyl ether respectively.
2) Mixed or Unsymmetrical Ethers :
The ethers in which two different alkyl groups or phenyl groups or an alkyl and a
phenyl group are attached to oxygen atom are called asymmetrical ethers. They
are generally represented as R−O−R' or R−O−Ar or Ar −O− Ar ' . In the
common naming system, they are named as alkyl alkyl ether, alkyl phenyl ether or
phenyl phenyl ether respectively.
In I . U . P . A .C . , they are named as follows:
 Largest carbon chain containing ether functional group is selected. But, in this
name system ether is used as substitute and it is written as alkoxy. Those carbon
atoms of that side are counted in alkoxy where the carbon atoms are less in
number.
 Numbering is done in this way that the ether functional group gets the least
number.
 The name is written as:
Ether and other substitute ¿¿ if exists ¿ +¿ alk +¿ ane
Common and I . U . P . A .C . names of some ether are illustrated bellow in the table:
Gen. Structural formula Common Name I . U . P . A .C .
formula
C2 H 6 O CH 3 −O−CH 3 Dimethyl ether Methoxy methane
C3 H 8 O CH 3 −CH 2−O−CH 3 Ethyl methyl ether Methoxy ethane
C 4 H 10 O CH 3 −CH 2−CH 2 −O−CH 3 Methyl propyl ether 1−¿ Methoxy
propane
CH 3 −CH −CH 3 Isopropyl methyl ether, 2−¿ Methoxy
2 −¿ Propyl methyl propane
°
OCH 3
ether
CH 3 −CH 2−O−CH 2−CH 3 Diethyl ether Ethoxy ethane
 C5 H 12 O CH 3 −CH 2−CH 2 −CH 2−OCH 3 n−¿ Butyl methyl 1−¿ Methoxy
ether, butane
1 −¿ Butyl methyl
°

ether
CH 3 −CH −CH 2−CH 3 2 −¿ Butyl
°
methyl 2−¿ Methoxy
ether butane
OCH 3
CH 3 −CH −CH 2−O−CH 3 Isobutyl methyl ether 1−¿ Methoxy
−2−¿ methyl
CH 3
propane
CH 3 3 −¿ Butyl
°
methyl 2−¿ Methoxy
ether −2−¿ methyl
CH 3 −C−O−CH 3
propane
CH 3
CH 3 −CH 2−CH 2 −O−CH 2 CH 3 Ethyl propyl ether 1−¿ Ethoxy
propane
CH 3 −CH −CH 3 Ethyl Isopropyl ether, 2−¿ Ethoxy
Ethyl 2 −¿ Propyl propane
°
OCH 2−CH 3
ether
C6 H 5−O−CH 3 Methyl phenyl ether, Methoxy benzene
Anisole
C6 H 5−O−CH 2 −C H 3 Ethyl phenyl ether, Ethoxy benzene
Phenetole
C6 H 5−O−CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Heptyl phenyl ether 1−¿ Phenoxy
heptane
CH 3 −CH −CH 2−CH 2 −O−C 6 H 5 Isopentyl phenyl ether 20
3−¿ Methylbutoxy
benzene
CH 3
C H 3−O−CH 2 −C H 2−O−CH 3 1,2−¿ Dimethoxy
ethane
C H3 C H3 1−¿ Methoxy
OC H 3 −2,2−¿ dimethyl
benzene
Ethers show functional isomerism with isomer alcohols and show only
metamerism with other isomer ethers.
Structure of Ether Functional Group ⇨
In ether, oxygen atom exhibited sp 3 hybridisation. Both
sp hybrid orbitals are attached to cabon of alkyl group
3

by sigma ( σ ) bond formed by the overlap of a sp 3

hybridised orbital of carbon with a sp 3 hybridised
orbital
of oxygen. Other two sp hybridised orbital of oxygen do not participate in bonding,
3

because two lone pair electons are present there. Therefore, according to VSPER
theory, the geometry of ether is angular (V ) . The repulsion towards the bond pair
electrons increases due to + I effect of both alkyl groups together due to which the
bond angle increases and becomes 111.7° .
Preparation of Ethers ⇨
1) Williamson’s ether Synthesis :
Primary haloalkanes when treated with sodium or potassium alkoxide form
ethers. This reaction is known as Williamson’s ether Synthesis. In this reaction
when secondary and tertiary alkyl halide is taken, alkene is formed as a main
product by the elimination reaction. Since alkoxide are not only nucleophilic but
also strong alkaline. Thus we can say that Williamson’s ether synthesis is a good
example of SN 2 reaction.
CH 3 −CH 2−Br +NaO CH 2 C H 3 CH 3 −CH 2−O−CH 2−C H 3 + NaBr
Ethyl bromide Sodium ethoxide Diehyl ether
CH 3 CH 3

CH 3 — CH 2 —X+NaO—C— CH 3 CH 3 — CH 2 —O—C— CH 3 + NaX

CH 3 CH 3
Ethyl halide Sodium tertiary butoxide Tertiary butyl ethyl ether
The reaction of sodium ethoxide with tertiary butyl bromide gives 2−¿
methylpropene only and no ether is formed.
CH 3 CH 2

CH 3 —C—Br + NaO— CH 2 — CH 3 CH 3 —C + CH 3 — CH 2 —
OH + NaX
 CH 3 CH 3
Ter. butyl bromide Sodium ethoxide Isobutylene Ethyl alcohol
This process is also used to change phenols into ethers. The phenol is first
converted into sodium phenoxide.
CH 3 −CH 2−Br + NaO C 6 H 5 C6 H 5−O−CH 2 −C H 3 + NaBr
Phenetole
CH 3 −Br + NaO C 6 H 5 C6 H 5−O−C H 3 + NaBr
Anisole
2) By dehydration of alcohols :
The product of the reaction involving primary alcohols is 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.
Con. H 2 SO 4
CH 3 −C H 2−OH CH 2=C H 2 + H 2 O
443 K
Diethyl ether is obtained by heating mixture of excess of ethyl alcohol and conc.
H 2 SO 4 at 413 K temperature.
413 K 21
CH 3 −CH 2−OH + HO SO 3 H CH 3 −CH 2−O SO 3 H + H −OH
413 K
CH 3 −CH 2−O SO 3 H + HO−CH 2−C H 3 CH 3 −CH 2−O−CH 2−C H 3 + H 2 SO 4
Or
Con. H 2 SO 4
CH 3 −CH 2−OH + HO−CH 2−C H 3
CH 3 −CH 2−O−CH 2−C H 3 + H−OH
413 K
This method is suitable only for the ethers containing primary alcohol group.
Therefore the formation of ether is a SN 2 reaction. The mechanism of
dehydration of ethanol involves the following steps:
Mechanism
Step 1 : Attack of protic acids like, H 2 SO4 , H 3 PO 4 etc. gives protonated
alcohol.

+¿¿ +¿−H
CH 3 −C H 2−O−H +¿ ¿
H CH 3 −C H 2−O

H
Step 2 : In this step, another alcohol molecule attacks on a protonated alcohol.

+¿−H +¿−CH 2−C H 3+ H−O

CH 3 −C H 2−O ¿
+CH 3−C H 2−O CH 3 −C H 2−O¿

H H H
H
Step 3 : Formation of ether by elimination of a proton.
+¿−CH 2−C H 3 +¿
CH 3−C H 2−O¿ CH 3 −C H 2−O−CH 2−C H 3+ H ¿

H
This method is suitable for the preparation of ethers having primary alkyl groups
only. In secondary and tertiary alcohols, the alcohol will preferably undergo
dehydration to yield alkene. Because, the dehydration of secondary and tertiary
alcohols to give corresponding ethers is unsuccessful as elimination competes
over substitution.
CH 3 CH 3
Con. H 2 SO4
 CH 3 −C−O H CH 3 −C+ H −OH

CH 2−H CH 2
2−¿ Methylpropan −2−¿ ol 2−¿ Methylpropene
This reaction is not suitable for the formation of unsymmetrical ethers like ethyl
methyl ethers because here we obtain the mixture of different ethers.
Con. H 2 SO 4
'
R−OH + R '−OH R−O−R+ R −O−R ' + R−O−R '
413 K
Physical Properties of Ethers ⇨
1) Solubility in water :
The solubility of ethers is comparable to those of corresponding alcohols. For
example, dimethyl ether and n−¿ butyl alcohol are both equally soluble.
H R O
H Lower ethers are formed hydrogen bonds with water like
RO
alcohols. As the molecular mass of ethers increase, the
O
hydrophobic part or hydrocarbon part of ethers is also
H increase due to which the ability of formation of
H
hydrogen bond decreases. As a result, the solubility in water decreases.
2) Boiling and Melting point :
The C−O bonds in ethers are polar and thus, ethers have a net dipole
moment. But due to +I effect of both alkyl groups ethers are slightly polar in
nature. 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. The large difference in
boiling points of alcohols and ethers is due to the presence of hydrogen bonding
in alcohols. 22
Chemical Properties of Ethers ⇨
Cleavage of C−O bond in ethers
Ethers are the least reactive and most stable of the functional groups. This is because
in ethers the functional group −O−¿ does not have any active centre whereas in
alcohols and phenols the functional group −OH have a active functional group.
They are less reactive like alkanes. Therefore, the cleavage of C−O bond in ethers
takes place under drastic conditions with excess of hydrogen bromides or hydrogen
iodides. The reaction takes place with HBr or HI because these reagents are
sufficiently acidic. The reaction of dialkyl ether gives two molecules of alkyl bromide or
alkyl iodide.
R−O−R+ H−Br R−OH + R−Br
R−OH + H−Br R−Br + H 2 O
This reaction is a nucleophilic substitution reaction. Therefore, if at least one of the
groups of −O−¿ functional group of ether is SN 1 group ¿¿ the formation of more
stable benzyl or allyl or tertiary carbonium ion due to cleavage of C−O bond ¿ ,
the reaction is SN 1 else SN 2 . For example,
SN 2
CH 3 −O−CH 2−CH 3+ H−I CH 3 −I +CH 3−CH 2−OH
CH 3 −CH 2−OH + H −I CH 3 −CH 2−I + H 2 O
The SN 2 mechanism of these reactions involves the following steps:
Mechanism
Step 1 : The SN 2 reaction of an ether with HI starts with protonation of ether
molecule.
+¿−C H 2−C H 3 −¿¿
CH 3 −O−C H 2 −C H 3 +¿ H−I
CH 3−O ¿ +I
 H
Step 2 : Due to low steric hinderence iodide attacks the least substituted carbon of
the oxonium ion formed in step 1 and displaces an alcohol molecule by SN 2
mechanism.
−¿
+¿−C H 2−C H 3
+¿−CH 2−C H 3
−¿+CH 3−O¿ CH 3 −I +CH 3 CH 2−OH
I … .. C H 3 … …O¿
I¿
H H
When HI is in excess and the reaction is carried out at high temperature, ethanol
reacts with another molecule of HI and is converted to ethyl iodide.
Step 3 : The SN 2 reaction of an alcohol with HI starts with protonation of
alcohol.
+¿−H −¿¿
CH 3 −C H 2−O−H +¿ H−I ¿
CH 3 −C H 2−O +I

H
Step 4 : Iodide attacks the least substituted carbon of the oxonium ion formed in
step 3 and displaces an ethyl iodide.
−¿
+¿−H
¿ +¿−H
−¿ +C H 2−O ¿ CH 3 −CH 2−I + H 2 O
¿ I … .. C H 2 … …O
I
CH 3 H CH 3 H
For example,
CH 3 CH 3
SN 1
CH 3 −C−O−CH 3 + H−I CH 3 −C−I +CH 3−OH

CH 3 CH 3
The SN 1 mechanism of this reaction involves the following steps:
Mechanism
Step 1 : The SN 1 reaction of an ether with HI starts with protonation of ether
molecule.
CH 3 CH 3

+¿−C H 3 −¿¿
CH 3 −C−O−C H 3 +¿ H−I
CH 3 −C−O ¿ +I

CH 3 CH 3 H
9414248318, 9468590309 Alcohols, Phenols and Ethers
Step 2 : The departure of leaving group CH 3 −OH creates a more stable °
3 −¿
butyl carbonium ion and the reaction follows SN 1 mechanism.
CH 3 CH 3
Slow
23
+¿−C H 3 +¿ ¿
CH +CH 3−OH
3 −C
¿
CH 3 −C−O

CH 3 H CH 3
Step 3 : Nucleophile iodide ion attacks on carbonium ion and forms product.
CH 3 CH 3
Fast
+¿ −¿¿
CH 3 −C¿ CH 3 −C−I
+I

CH 3 CH 3
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. For example,
 SN 2
CH 3 −O−C 6 H 5 + H −I CH 3 −I +C 6 H 5−OH
The SN 2 mechanism of this reaction involves the following steps:
Mechanism
Step 1 : The SN 2 reaction of an ether with HI starts with protonation of ether
molecule.
+¿−C6 H 5 −¿¿
CH 3 −O−C 6 H 5 +¿ H−I
CH 3 −O ¿ +I

H
Step 2 : The bond between is weaker than the bond between O−C 6 H 5
O−CH 3
because the carbon of phenyl group is sp 2 hybridised and there is a partial double
−¿
bond character. Therefore the attack by I ¿ ion breaks O−CH 3 bond and displaces
a phenol by SN 2 mechanism.
−¿
+¿−C6 H 5
+¿−C 6 H 5
−¿ +CH 3 −O ¿ CH 3 −I +C 6 H 5−OH
I … .. C H 3 … …O¿
I¿
H H
Phenols do not react further to give halides because the sp 2 hybridised carbon of
phenol cannot undergo nucleophilic substitution reaction needed for conversion to the
halide.
The carbon of phenyl group is sp 2 hybridised and there is a partial double bond
character in the bond between O−C 6 H 5 . Therefore, diphenyl ether does not react
with HBr or HI .
C6 H 5−O−C6 H 5 + H−Br No reaction.
Electrophilic substitution reactions
: ´¿ + ´¿ + ´¿ + ´¿ : ´¿

❑⊖ ❑⊖
⊖
❑
This is clear from the above resonance structures of aeromatic ether that the electron
density is more on the ortho and para positions. The alkoxy group is ortho, para
directing and activates the aromatic ring towards electrophilic substitution.
1) Halogenation :
Anisole undergoes bromination with bromine in ethanoic acid even in the
absence of FeBr3 catalyst. It is due to the activation of benzene ring by the
methoxy group.
OCH 3 OCH 3 OCH 3
Ethanoic acid Br
+ Br 2 +
−HBr
Anisole O−¿ Bromoanisole Br
¿ Minor ¿ p−¿ Bromoanisole ¿
¿ ¿
Major ¿
9414248318, 0141-2719117 Alcohols, Phenols and Ethers

Since 1996  9414248318, 0141-2719117

24

2) Nitration :
Anisole reacts with a mixture of concentrated sulphuric and nitric acids to yield
a mixture of ortho and para nitroanisole.
 OCH 3 OCH 3 OCH 3
H 2 SO 4 NO2
+ HNO 3 +
−H 2 O
Anisole O−¿ Nitroanisole NO2
¿ Minor ¿ p−¿ Nitroanisole ¿ Major ¿
¿ ¿
3) Friedel-Crafts reaction :
Anisole undergoes Friedel-Crafts reaction, i.e., the alkyl and acyl groups are
introduced at ortho and para positions by reaction with alkyl halide and acyl
halide in the presence of anhydrous A lC l3 as catalyst.
OCH 3 OCH 3 OCH 3
futZy A lC l 3 CH 3
+ CH 3 C l + +
CS 2
Anisole 2−¿ Methoxytoluene CH 3
¿ Minor ¿ 4−¿ Methoxytoluene ¿
¿ ¿
Major ¿
OCH 3 OCH 3 OCH 3
futZy A lC l 3 COCH 3
+ CH 3 COC l +
−HC l
Anisole 2−¿ Methoxyacetophenone COCH 3
¿ Minor ¿ 4−¿ Methoxyacetophenone
¿
¿ Major ¿
¿

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