Since  1996  9414248318, 9468590309, 7791835250

Unit % 11 Alcohols, Phenols and Ethers Marks % 1

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
𝐬𝐩𝟑 hybridized carbon atoms while in phenols hydroxyl group is attached to 𝐬𝐩𝟐
hybridize carbon atom. The group of compounds obtained by displacing hydrogen by
alkoxy (−𝐎𝐑) 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 𝐇𝟐𝐧+𝟐 𝐎 or 𝐂𝐧 𝐇𝟐𝐧+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 name 𝐈. 𝐔. 𝐏. 𝐀. 𝐂. e
𝐂𝐇𝟑 𝐎𝐇 𝐂𝐇𝟑 − 𝐎𝐇 Methyl alcohol Carbinol Methanol 𝟏°
𝐂𝟐 𝐇𝟓 𝐎𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇 Ethyl alcohol Methylcarbinol Ethanol 𝟏°
𝐂𝟑 𝐇𝟕 𝐎𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐎𝐇 𝐧 − Propyl alcohol, Ethylcarbinol Propan−𝟏 −ol 𝟏°
𝟏° − Propyl alcohol
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟑 Isopropyl alcohol, Dimethyl Propan−𝟐 −ol 𝟐°

𝐎𝐇 𝟐° − Propyl alcohol carbinol

𝐂𝟒 𝐇𝟗 𝐎𝐇 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐎𝐇 𝐧 − Butyl alcohol, Propylcarbinol Butan−𝟏 −ol 𝟏°
𝟏° − Butyl alcohol
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝟐° − Butyl alcohol Ethyl Butan−𝟐 −ol 𝟐°

𝐎𝐇
methylcarbinol
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐎𝐇 Isobutyl alcohol Isopropyl 𝟐 − Methyl 𝟏°

𝐂𝐇𝟑 carbinol propan−𝟏 −ol

𝐂𝐇𝟑 𝟑° − Butyl alcohol Trimethyl 𝟐 − Methyl 𝟑°

𝐂𝐇𝟑 − 𝐂 − 𝐎𝐇
carbinol propan−𝟐 −ol

𝐂𝐇𝟑
𝐂𝟓 𝐇𝟏𝟏 𝐎𝐇 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐎𝐇 𝐧 − Pentyl alcohol, Butyl carbinol Pentan−𝟏 −ol 𝟏°
𝟏° − Pentyl alcohol
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 𝐂𝐇𝟑 Active 𝟐° − pentyl Methyl Pentan−𝟐 −ol 𝟐°

𝐎𝐇 alcohol propylcarbinol
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇 − 𝐂𝐇𝟐 𝐂𝐇𝟑 𝟐° − Pentyl alcohol Diethyl carbinol Pentan−𝟑 −ol 𝟐°

𝐎𝐇
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇 − 𝐂𝐇𝟐 𝐎𝐇 Activepentyl 𝟐° −Butyl 𝟐 − Methyl 𝟏°
 alcohol carbinol butan−𝟏 −ol 2
𝐂𝐇𝟑
𝐎𝐇 𝟑° − Pentyl alcohol Ethyl dimethyl 𝟐 − Methyl 𝟑°

𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂 − 𝐂𝐇𝟑 carbinol butan−𝟐 −ol

𝐂𝐇𝟑
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Activeisopentyl Isopropyl 𝟑 − Methyl 𝟐°

𝐎𝐇 𝐂𝐇𝟑 alcohol, 𝟐 − methyl carbinol butan−𝟐 −ol

°

isopentyl alcohol
𝐇𝐎𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇 − 𝐂𝐇𝟑 Isopentyl alcohol Isobutyl 𝟑 − Methyl 𝟏°

𝐂𝐇𝟑
carbinol butan−𝟏 −ol
𝐂𝐇𝟑 Neopentyl alcohol 𝟑° −Butyl 𝟐, 𝟐 − 𝟏°
carbinol Dimethyl
𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟐 − 𝐎𝐇
Propan−𝟏 −ol
𝐂𝐇𝟑
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 − 𝐂𝐇𝟐 − 𝐎𝐇. In these −𝐂𝐇𝟐 −
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 𝐑 𝟐 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 𝐑 𝟑𝐂 − 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 𝐂𝐬𝐩𝟑 − 𝐎𝐇 bond : In this class of alcohols, the −𝐎𝐇
group is attached to an 𝐬𝐩𝟑 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
𝐬𝐩𝟑 hybridised carbon next to the carbon-carbon double bond,
that is to an allylic carbon. For example,
𝐂𝐇𝟑
𝟐 𝟑
𝐬𝐩 𝐬𝐩
𝐂𝐇𝟐 = 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐎𝐇, 𝐂𝐇𝟐 = 𝐂𝐇 − 𝐂𝐇 − 𝐎𝐇, 𝐂𝐇𝟐 = 𝐂𝐇 − 𝐂 − 𝐎𝐇

𝐂𝐇𝟑 𝐂𝐇𝟑
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 𝐬𝐩𝟑 hybridised carbon atom next to an aromatic ring. For
example,
𝐂𝐇𝟐 − 𝐎𝐇 𝐂𝐇𝟑

& 𝐂𝐇 − 𝐎𝐇 − 𝐂 − 𝐎𝐇

𝐂𝐇𝟑 𝐂𝐇𝟑
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 𝐬𝐩𝟑 hybrid carbon are called alkylic alcohols.
For example,
𝐎𝐇 𝐎𝐇

𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐎𝐇, 𝐂𝐇𝟑

Butan−𝟏 −ol Cyclohexanol 𝟐 −cyclopentanol

b) Compounds containing 𝐂𝐬𝐩𝟐 − 𝐎𝐇 bond : In this class of alcohols, the −𝐎𝐇
group is attached to an 𝐬𝐩𝟑 hybridised carbon atom of an alkyl 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

𝐂𝐇𝟑 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,
𝐬𝐩𝟐 𝐬𝐩𝟐
𝐂𝐇𝟐 = 𝐂𝐇 − 𝐎𝐇, 𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇 − 𝐎𝐇
Ethenol (Vinyl alcohol) Prop−𝟏 −en−𝟏 −ol
These alcohols are less stable; they are rearranged in Keto form.
For example,
𝐂𝐇𝟐 = 𝐂𝐇 − 𝐎𝐇 ⇌ 𝐂𝐇𝟑 − 𝐂𝐇 = 𝐎
enol form (unstable) keto form (stable)
2) 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 𝐇𝟐𝐧+𝟐𝐎𝟐 . 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 −𝐂𝐇𝟐 − groups. For example,
𝐂𝐇𝟐 − 𝐂𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐

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 𝐇𝟐 𝐎 molecule to become stable carbonyl
compounds.
3) 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 𝐇𝟐𝐧+𝟐𝐎𝟑. They are named in 𝐈. 𝐔. 𝐏. 𝐀. 𝐂. like monohydric alcohols. Unlike
monohydric alcohols, three – 𝐎𝐇 groups are also numbered. For example,
𝐂𝐇𝟐 − 𝐂𝐇 − 𝐂𝐇𝟐

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 𝐂𝐇𝟑 −
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 𝐬𝐩𝟑 hybridisation. 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 and
oxygen is attached to hydrogen by a sigma (𝛔) bond
formed by the overlap of a 𝐬 −orbital of hydrogen with a
second 𝐬𝐩𝟑 hybridised orbital of oxygen.
Other two 𝐬𝐩𝟑 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 phenol is angular(𝐕). The bond angle in phenol is 𝟏𝟎𝟖. 𝟗° . This bond angle
is slightly less than the tetrahedral angle (𝟏𝟎𝟗° − 𝟐𝟖′ ). It is due to the maximum
repulsion between the unshared electron pairs(𝓵𝐩) 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 < + 𝐇𝟐 𝐎 >𝐂−𝐂<

𝐇 𝐎𝐇
Mechanism:
The mechanism of the reaction involves the following three steps:
Step𝟏 : Protonation of alkene to form stable carbocation by electrophilic
attack of 𝐇𝟑 𝐎+.
𝐇𝟐 𝐎 + 𝐇 + 𝐇𝟑 𝐎+
𝐇 𝐇
> 𝐂 = 𝐂 < + 𝐇 − 𝐎+ − 𝐇 > 𝐶 − 𝐂 + < + 𝐇𝟐 𝐎
Step𝟐 : Nucleophilic attack of water on carbocation.
𝐇 𝐇
 > 𝐶 − 𝐂+ < + 𝐇 − 𝐎 − 𝐇 >𝐶−𝐂<

𝐇 − 𝐎+ − 𝐇
Step𝟑 : Deprotonation to form an alcohol by the presence of water.
𝐇 𝐇

>𝐶−𝐂< + 𝐇−𝐎−𝐇 > 𝐶 − 𝐂 < + 𝐇 − 𝐎+ − 𝐇

𝐇 − 𝐎+ − 𝐇 𝐎𝐇 𝐇
 Since 1996 9414248318, 9468590309, 0141-2719117

Propene reacts with water in the presence of acid like dil 𝐇𝟐 𝐒𝐎𝟒 or dil
𝐇𝐂𝓵 to form 𝟐 −propanol.
𝐝𝐢𝐥. 𝐇𝟐 𝐒𝐎𝟒
𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇𝟐 + 𝐇 − 𝐎 − 𝐇 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 5
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.
𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇𝟐
𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇𝟐 + 𝐇 − 𝐁𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐

𝐇 𝐁𝐇𝟐
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐
𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇𝟐
𝐇 𝐁 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐇 𝐁𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑

𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑

Or
𝟏
3CH3—CH=CH2 + 𝟐 𝐁𝟐 𝐇𝟔 (CH3—CH2—CH2)3B
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 + 𝐇𝟐 𝐎 = 2AgOH) give alcohol of same carbon.
R—X + aqueous KOH R—OH + KX
𝐂𝐇𝟑 —𝐂𝐇𝟐 —Br + KOH (aq.) 𝐂𝐇𝟑 —𝐂𝐇𝟐 —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 𝐇𝟐 𝐒𝐎𝟒 or dil 𝐇𝐂𝓵. 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 𝐇𝟐 𝐎 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 𝐇𝟐 𝐎 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 𝐇𝟐 𝐎 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 (𝐍𝐚𝐁𝐇𝟒) or lithium aluminium hydride
(𝐋𝐢𝐀𝓵𝐇𝟒 ). Formaldehyde yield methanol, Alkyl aldehydes yield primary
alcohols whereas ketones give secondary alcohols. From this method
tertiary alcohols can not be obtained.
𝐋𝐢𝐀𝓵𝐇𝟒
𝐇 − 𝐂𝐇𝐎 + 𝟐𝐇 𝐂𝐇𝟑 − 𝐎𝐇
Formaldehyde Methanol
𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂𝐇𝐎 + 𝟐𝐇 𝐑 − 𝐂𝐇𝟐 − 𝐎𝐇
𝐋𝐢𝐀𝓵𝐇𝟒
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 − 𝐂𝐇𝟐 − 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
−𝐂𝐇𝟐 − 𝐎𝐇 in this reaction.
(𝐢) 𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂𝐎𝐎𝐇 + 𝟒𝐇 𝐑 − 𝐂𝐇𝟐 − 𝐎𝐇
(𝐢𝐢) 𝐇𝟐 𝐎
(𝐢) 𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂𝐎𝐎𝐑 + 𝟒𝐇 𝐑 − 𝐂𝐇𝟐 − 𝐎𝐇 + 𝐑 − 𝐎𝐇
(𝐢𝐢) 𝐇𝟐 𝐎
However, 𝐋𝐢𝐀𝓵𝐇𝟒 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.
𝐇𝟐 𝐒𝐎𝟒
𝐑 − 𝐂𝐎𝐎𝐇 + 𝐑′ − 𝐎𝐇 𝐑 − 𝐂𝐎𝐎𝐑′ + 𝐇𝟐 𝐎
𝐏𝐝
𝐑 − 𝐂𝐎𝐎𝐑′ + 𝐇𝟐 𝐑 − 𝐂𝐇𝟐 − 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:
 group of alcohol is attached with
−𝐎𝐇
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, it
prevents the formation of hydrogen bonding with water molecule, and hence
7
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
2) 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.
..
𝐑— 𝐎— 𝐇 + 𝐂+ — 𝐑— 𝐎+ — 𝐂 — 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.
..
: 𝐁𝐫 − : + 𝐂𝐇𝟐 — 𝐎+ − 𝐇 — 𝐁𝐫— 𝐂𝐇𝟐 + 𝐇𝟐 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
Reactions involving cleavage of 𝐎 − 𝐇 bond 8
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 + H2
Sodium alkoxide
6CH2—CH2—OH + 2A𝓁 2(CH3CH2O)3A𝓁 + H2
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 𝐇𝐂𝓵 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 (𝐂𝐇𝟑 𝐂𝐎) group in alcohols or phenols is known as
acetylation.
𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞
R — OH + R’ — COC𝓁 R — COOR’ + 𝐇𝐂𝓵
 𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞
𝐂𝟐 𝐇𝟓 𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐎𝐂𝓵 𝐂𝐇𝟑 𝐂𝐎𝐂𝟐 𝐇𝟓 + 𝐇𝐂𝓵
Acetylation of salicylic acid produces aspirin. This is used as analgesics and
antipyretic medicine.
COOH COOH
OH CH3—C—O—C— CH3 𝐇+ OCO CH3
+ + CH3COOH
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

1) Synthesis of Alkyl halide : 9
i) Reaction with halogen acids :
HC𝓁 reactivity is lowest in all the halogen acids, then alcohol reacts with
HC𝓁 in presence of dry ZnC𝓁2. Mixture of HC𝓁 and dry ZnC𝓁2 is called Lucas
reagent.
dry ZnC𝓁2
CH3—CH2—OH + HC𝓁 CH3—CH2—C𝓁 + H2O
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. H2SO4. Here, HBr prepared by the
reaction of con. H2SO4 and KBr or NaBr.
con. H2SO4
CH3—CH2—OH + HBr CH3—CH2—Br + H2O
Iodoalkanes are also be prepared by heating of alcohol and hydroiodic
acid (HI) in presence of catylist con. H3PO4 . Like HBr, HI also be prepared by
the reaction of con. H3PO4 and KI or NaI during the reaction.
con. H3PO4
CH3—CH2—OH + HI CH3—CH2—I + H2O
ii) Reaction with phosphorus halides :
CH3—CH2—O— H + PC𝓁5 CH3—CH2—C𝓁 + POC𝓁3 + HC𝓁
C𝓁—PC𝓁3—C𝓁 Ethyl chloride Phosphorus
Ethyl alcohol oxy chloride
R—OH C𝓁
R—OH + P C𝓁 3R—C𝓁 + H3PO3
R—OH C𝓁 Orthophosphorus acid
iii) Reaction with thionyl chloride :
pyredene
CH3—CH2—O— H + SOC𝓁2 CH3—CH2—C𝓁 + SO2 + HC𝓁
C𝓁— SO —C𝓁 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 𝐇𝟐 𝐒𝐎𝟒 or 𝐇𝟑 𝐏𝐎𝟒 . 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 𝐇𝟐 𝐒𝐎𝟒 at
𝟒𝟒𝟑 𝐊. For example,
 𝐂𝐨𝐧. 𝐇𝟐 𝐒𝐎𝟒
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇 𝐂𝐇𝟐 = 𝐂𝐇𝟐 + 𝐇𝟐 𝐎
𝟒𝟒𝟑 𝐊
The mechanism of dehydration of ethanol involves the following steps:
Mechanism
Step𝟏 : Formation of protonated alcohol.
𝐅𝐚𝐬𝐭
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐇 + 𝐇 + 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎+ − 𝐇

𝐇
Protonated ethanol
 Since 1996 9414248318, 9468590309, 7791835250

Step𝟐 : Formation of stable carbocation from protonated alcohol. It is the

slowest step and hence, the rate determining steps of the reaction.
𝐒𝐥𝐨𝐰
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎+ − 𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝟐+ + 𝐇 − 𝐎 − 𝐇

𝐇
Ehyl carbonium ion
Step𝟑 : 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% 𝐇𝟑 𝐏𝐎𝟒
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐎𝐇 𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇𝟐 + 𝐇 − 𝐎 − 𝐇
𝟒𝟒𝟎 𝐊
𝐂𝐇𝟑
𝐂𝐇𝟑
𝟐𝟎% 𝐇𝟑 𝐏𝐎𝟒
𝐂𝐇𝟑 − 𝐂 − 𝐎𝐇 𝐂𝐇𝟑 − 𝐂 = 𝐂𝐇𝟐 + 𝐇 − 𝐎 − 𝐇
𝟑𝟓𝟖 𝐊
𝐂𝐇𝟑 𝐂𝐇𝟑
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 KMn𝐎𝟒 [O]
R—C—O + [O] R—C=O R—C=O
−H2O
H H
Secondary alcohols are oxidised to ketones of same number of carbon atoms as
the secondary alcohol.
R R
𝐀𝐜𝐢𝐝𝐢𝐜 KMn𝐎𝟒
R—C—O + [O] R—C=O
−H2O
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 𝐊𝐌𝐧𝐎𝟒 [𝐎]
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐎𝐇 𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐎𝐎𝐇 + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎
[𝐎]
𝐂𝐇𝟑 𝐎
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& 60, Shiv Colony, Near Arjun Nagar Phatak, Kisaan Marg
11
XII, XI (CBSE & RBSE) Alcohols, Phenols and 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.
𝐂𝐇𝟑 𝐂𝐇𝟑 𝐂𝐇𝟑
𝐀𝐜𝐢𝐝𝐢𝐜 KMn𝐎𝟒 [O]
𝐂𝐇𝟑 —C—OH 𝐂𝐇𝟑 —C= 𝐂𝐇𝟐 𝐂𝐇𝟑—C=O + HCHO
−H2O
𝐂𝐇𝟐 H
𝐂𝐇𝟑
𝐀𝐜𝐢𝐝𝐢𝐜 KMn𝐎𝟒
𝐂𝐇𝟑 —C=O 𝐂𝐇𝟑 —C𝐎𝐎𝐇 + HCOOH
[O]
𝐇—C—OH 𝐀𝐜𝐢𝐝𝐢𝐜 KMn𝐎𝟒 𝐇𝐎—C—OH
𝐂𝐎𝟐 + 𝐇𝟐 𝐎
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, 𝐂𝐫𝐎𝟑 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.
𝐂𝐫𝐎𝟑
R—𝐂𝐇𝟐 —OH + [O] R—C𝐇𝐎
−H2O
R R
𝐂𝐫𝐎𝟑
R—CH—OH + [O] R—C=O
−H2O
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 𝐇𝐂𝓵.
𝐏𝐂𝐂
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝐎
𝐏𝐂𝐂
𝐂𝐇𝟐 = 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐎𝐇 𝐂𝐇𝟐 = 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, 𝟓𝟕𝟑𝐊
R—𝐂𝐇𝟐 —OH R—C𝐇𝐎
−H2
R R
𝐂𝐮, 𝟓𝟕𝟑𝐊
R—CH—OH R—C=O
−H2
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐂𝐮, 𝟓𝟕𝟑𝐊
𝐂𝐇𝟑 —C—OH 𝐂𝐇𝟑 —C= 𝐂𝐇𝟐
−H2O
 𝐂𝐇𝟐 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.
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& 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 𝐂𝐇𝟑 —CH(OH) — or
𝐂𝐇𝟑 —CO— groups gives yellow ppt. of iodoform. It is known as iodoform test.
𝐂𝐇𝟑 𝐂𝐇𝟐—OH + 𝟒𝐈𝟐 + 6NaOH 𝐂𝐇𝐈𝟑 + 𝐇𝐂𝐎𝐎𝐍𝐚 + 5NaI + 5𝐇𝟐 𝐎
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 + 𝟐𝐇𝟐 𝐂𝐇𝟑 − 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 𝐇𝟐𝟐 𝐎𝟏𝟏 + 𝐇𝟐 𝐎 𝐂𝟔 𝐇𝟏𝟐 𝐎𝟔 + 𝐂𝟔 𝐇𝟏𝟐 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 𝐇𝟏𝟐 𝐎𝟔 𝟐𝐂𝟐 𝐇𝟓 𝐎𝐇 + 𝟐𝐂𝐎𝟐
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
13
member of phenol family. This is also known as the carbolic acid. The 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
𝐂𝐇𝟑
𝐂𝐇𝟑
Carbolic acid 𝐎 −Cresol 𝐦 −Cresol 𝐂𝐇𝟑 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 𝐬𝐩𝟑 hybridisation. The oxygen of the −𝐎𝐇 group is
attached to carbon by a sigma (𝛔) bond formed by the overlap of a 𝐬𝐩𝟐 hybridised
orbital of benzene ring carbon with a 𝐬𝐩𝟑 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 𝐬𝐩𝟑 hybridised orbital of oxygen.
Other two 𝐬𝐩𝟑 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) 𝐬𝐩𝟐 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 𝐚𝐧𝐝 𝟑𝟎𝟎 𝐚𝐭𝐦 𝐝𝐢𝐥. 𝐇𝐂𝓵
𝐂𝟔 𝐇𝟓 —𝐂𝓵 + 𝐍𝐚𝐎𝐇 𝐂𝟔 𝐇𝟓 —𝐎𝐍𝐚 𝐂𝟔 𝐇𝟓 —𝐎𝐇
−𝐇𝐂𝓵 −𝐍𝐚𝐂𝓵
2) From Benzene diazonium salt :
Phenol is obtained by reacting benzene diazonium salt with hot water.
𝐂𝟔 𝐇𝟓 —𝐍 + ≡ 𝐍.𝐂𝓵− + H—OH 𝐂𝟔 𝐇𝟓 —𝐎𝐇 + 𝐍𝟐 + H𝐂𝓵
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.
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐂𝐇 𝐂 — 𝐎— 𝐎𝐇 𝐎𝐇
𝐂𝐇𝟑 𝐂𝐇𝟑 𝐇+
+ 𝐎𝟐 𝐇𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐎𝐂𝐇𝟑
Cumene Cumene hydroperoxide Phenol Acetone14
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.
𝐒𝐎𝟑
𝐂𝟔 𝐇𝟓 —𝐇 + 𝐇𝟐 𝐒𝐎𝟒 𝐂𝟔 𝐇𝟓 —𝐒𝐎𝟑 𝐇 + 𝐇𝟐 𝐎
Benzene Benzene sulphonic acid
𝐂𝟔 𝐇𝟓 —𝐒𝐎𝟑 𝐇 + NaOH 𝐂𝟔 𝐇𝟓 —𝐒𝐎𝟑 𝐍𝐚 + 𝐇𝟐 𝐎
Sodium benzene sulphonate
𝐂𝟔 𝐇𝟓 —𝐒𝐎𝟑 𝐍𝐚 + NaOH 𝐂𝟔 𝐇𝟓 —𝐎𝐍𝐚 + 𝐍𝐚𝐇𝐒𝐎𝟑
𝐝𝐢𝐥. 𝐇𝐂𝓵
𝐂𝟔 𝐇𝟓 —𝐎𝐍𝐚 𝐂𝟔 𝐇𝟓 —𝐎𝐇 + 𝐍𝐚𝐂𝓵
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 𝐇𝟓 𝐂𝟔 𝐇𝟓 𝐂𝟔 𝐇𝟓 𝐂𝟔 𝐇𝟓

… 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:̈ − : 𝐎̈ : 𝐎̈ : 𝐎̈ : 𝐎:̈ −
 ⊖ ⊖

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 𝐇𝟓 𝐎𝐇 + 𝐍𝐚 𝐂𝟔 𝐇𝟓 𝐎𝐍𝐚 + 𝐇𝟐
𝟐
𝐂𝟔 𝐇𝟓 𝐎𝐇 + 𝐍𝐚𝐎𝐇 𝐂𝟔 𝐇𝟓 𝐎𝐍𝐚 + 𝐇𝟐 𝐎 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 𝐇𝟓 𝐎𝐇 𝐂𝟐 𝐇𝟓 𝐎− + 𝐇 +
Stable Less stable
𝐂𝟔 𝐇𝟓 𝐎𝐇 𝐂𝟔 𝐇𝟓 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 𝐇𝟓 𝐎𝐇 + 𝐍𝐚𝟐 𝐂𝐎𝟑 𝐂𝟔 𝐇𝟓 𝐎𝐍𝐚 + 𝐍𝐚𝐇𝐂𝐎𝟑
𝐂𝟔 𝐇𝟓 𝐎𝐇 + 𝐍𝐚𝐇𝐂𝐎𝟑 No reaction.
𝐑𝐂𝐎𝐎𝐇 + 𝐍𝐚𝟐 𝐂𝐎𝟑 𝐑𝐂𝐎𝐎𝐍𝐚 + 𝐍𝐚𝐇𝐂𝐎𝟑
𝐑𝐂𝐎𝐎𝐇 + 𝐍𝐚𝐇𝐂𝐎𝟑 𝐑𝐂𝐎𝐎𝐍𝐚 + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎
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:
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 > 𝐂𝟔 𝐇𝟓 𝐎𝐇 > 𝐂𝟐 𝐇𝟓 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 −𝐍𝐎𝟐, −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 𝐂𝐎𝟑 or 𝐍𝐚𝐇𝐂𝐎𝟑 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 𝐇𝟓 𝐎𝐇 + 𝐑 − 𝐂𝐎𝐎𝐇 𝐑 − 𝐂𝐎𝐎𝐂𝟔 𝐇𝟓 + 𝐇𝟐 𝐎
𝐇+
𝐂𝟔 𝐇𝟓 𝐎𝐇 + 𝐑 − C — O — C — 𝐑 𝐑 − 𝐂𝐎𝐎𝐂𝟔 𝐇𝟓 + 𝐑 − 𝐂𝐎𝐎𝐇

O O
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. This reaction is known as acylation and the
introduction of acetyl (𝐂𝐇𝟑 𝐂𝐎) group in alcohols or phenols is known as
acetylation.
𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞
𝐂𝟔 𝐇𝟓 𝐎𝐇 + 𝐑 − 𝐂𝐎𝐂𝓵 𝐑 − 𝐂𝐎𝐎𝐂𝟔 𝐇𝟓 + 𝐇𝐂𝓵
𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞
𝐂𝟔 𝐇𝟓 𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐎𝐂𝓵 𝐂𝐇𝟑 𝐂𝐎𝐂𝟔 𝐇𝟓 + 𝐇𝐂𝓵
Phenol Acetyl chloride Aceto phenone
2) Reaction with phosphorus halides :
C6H5—O H + PC𝓁5 C6H5—C𝓁 + POC𝓁3 + HC𝓁
C𝓁—PC𝓁3—C𝓁 Choloro benzene Phosphorous oxychloride
C6H5—OH C𝓁
C6H5—OH + P C𝓁 3C6H5—C𝓁 + H3PO3
C6H5—OH C𝓁 Ortho phosphorous acid
3) Reduction %
Phenol is converted to benzene on heating with zinc dust.
C6H5—OH + Zn C6H5—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 𝐂𝐇𝐂𝓵𝟑 or 𝐂𝐒𝟐 and at low
temperature, monobromophenols are formed.
𝐎𝐇 𝐎𝐇 𝐎𝐇
𝐂𝐒𝟐 , 𝟐𝟕𝟑𝐊 Br
+ 𝐁𝐫𝟐 +
−𝐇𝐁𝐫
Phenol 𝐎 −Bromophenol Br
(Minor) 𝐩 −Bromophenol (Major)
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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
+ 𝟑𝐁𝐫𝟐 17
−𝟑𝐇𝐁𝐫
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
+
−𝐇𝟐 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−
+
𝐍 … 𝐇𝐎— — 𝐍 + — 𝐎− … … 𝐇𝐎— — 𝐍 + — 𝐎− … …
𝐎
𝐎 𝐎
ii) By concentrate nitric acid : with concentrated nitric acid, phenol is
converted to 𝟐, 𝟒, 𝟔 −trinitrophenol.
𝐎𝐇 𝐎𝐇
𝐂𝐨𝐧. 𝐇𝐍𝐎𝟑 𝐍𝐎𝟐 𝐍𝐎𝟐

−𝟑𝐇𝟐 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. 𝐇𝟐 𝐒𝐎𝟒 𝐒𝐎𝟑 𝐇

−𝟐𝐇𝟐 𝐎
 Phenol 𝐒𝐎𝟑 𝐇
Phenol−𝟐, 𝟒 −disulphonic acid
𝐎𝐇 𝐎𝐇 𝐎𝐇
𝐒𝐎𝟑 𝐇 𝐍𝐎𝟐 𝐒𝐎𝟑 𝐇 𝐇𝐍𝐎𝟑 𝐍𝐎𝟐 𝐍𝐎𝟐
+ 𝐇𝐍𝐎𝟑
−𝐇𝟐 𝐎 − 𝟐 𝐇𝟐 𝐒𝐎𝟒
𝐒𝐎𝟑 𝐇 𝐒𝐎𝟑 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 𝐀𝓵𝐂𝓵𝟑 .
𝐎𝐇 𝐎𝐇 𝐎𝐇
𝐚𝐧𝐡𝐲𝐝. 𝐀𝓵𝐂𝓵𝟑 𝐂𝐇𝟑
+ 𝐂𝐇𝟑 𝐂𝓵 + +
−𝐇𝐂𝓵
Phenol 𝐎 −Cresol 𝐂𝐇𝟑
(Minor) 𝐩 −Cresol (Major)
Since 1996 9414248318

𝐎𝐇 𝐎𝐇 𝐎𝐇
𝐚𝐧𝐡𝐲𝐝. 𝐀𝓵𝐂𝓵𝟑 𝐂𝐎𝐂𝐇𝟑
+ 𝐂𝐇𝟑 𝐂𝐎𝐂𝓵 + 18
−𝐇𝐂𝓵
Phenol 𝟐 −hydroxyacetophenone 𝐂𝐎𝐂𝐇𝟑
(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
+ 𝐂𝐇𝐂𝓵𝟑 + 𝟑𝐍𝐚𝐎𝐇 + 𝟑𝐍𝐚𝐂𝓵 + 𝟐𝐇𝟐 𝐎

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

electrophile reagent.
𝐂𝐇𝐂𝓵𝟑 + 𝐎𝐇 − −
𝐂̈𝐂𝓵𝟑 𝐂̈𝐂𝓵𝟐 + 𝐂𝓵−
−𝐇𝟐 𝐎
𝐎𝐇 𝐎− . 𝐍𝐚+ 𝐎− . 𝐍𝐚+ 𝐎− . 𝐍𝐚+ 𝐎𝐇
𝐍𝐚𝐎𝐇 𝐂̈𝐂𝓵𝟐 𝐂𝐇𝐂𝓵𝟐 𝟐𝐎𝐇 − 𝐂𝐇
𝐎𝐇
−𝐇𝟐 𝐎
𝐎− . 𝐍𝐚+ 𝐎𝐇 𝐎− . 𝐍𝐚+ 𝐎𝐇
𝐂𝐇 𝐂𝐇𝐎 𝐂𝐇𝐎
𝐎𝐇 −𝐇𝟐 𝐎 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 𝐎− . 𝐍𝐚+

+ 𝐍𝐚𝐎𝐇
−𝐇𝟐 𝐎
𝐎− . 𝐍𝐚+ 𝐎𝐂𝐎𝐎𝐍𝐚 𝐎𝐇 𝐎𝐇
𝐂𝐎𝟐 𝐑𝐞𝐚𝐫𝐫𝐚𝐧𝐠𝐞𝐦𝐞𝐧𝐭 𝐂𝐎𝐎𝐍𝐚 𝐂𝐎𝐎𝐇

𝐝𝐢𝐥 𝐇𝐂𝓵
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
𝐍𝐚𝟐 𝐂𝐫𝟐 𝐎𝟕

𝐇𝟐 𝐒𝐎𝟒

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 𝐇𝟔 𝐎 𝐂𝐇𝟑 − 𝐎 − 𝐂𝐇𝟑 Dimethyl ether Methoxy methane
𝐂𝟑 𝐇𝟖 𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟑 Ethyl methyl ether Methoxy ethane
𝐂𝟒 𝐇𝟏𝟎 𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟑 Methyl propyl ether 𝟏 −Methoxy propane
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟑 Isopropyl methyl ether, 𝟐 −Methoxy propane
𝐎𝐂𝐇 𝟐° −Propyl methyl ether
𝟑
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Diethyl ether Ethoxy ethane
𝐂𝟓 𝐇𝟏𝟐 𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐎𝐂𝐇𝟑 𝐧 −Butyl methyl ether, 𝟏 −Methoxy butane
𝟏° −Butyl methyl ether
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝟐° −Butyl methyl ether 𝟐 −Methoxy butane

𝐎𝐂𝐇𝟑
 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟑 Isobutyl methyl ether 𝟏− Methoxy − 𝟐 −
𝐂𝐇𝟑 methyl propane
𝐂𝐇𝟑 𝟑° −Butyl methyl ether 𝟐− Methoxy − 𝟐 −
𝐂𝐇𝟑 − 𝐂 − 𝐎 − 𝐂𝐇𝟑
methyl propane

𝐂𝐇𝟑
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟐 𝐂𝐇𝟑 Ethyl propyl ether 𝟏 −Ethoxy propane
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟑 Ethyl Isopropyl ether, 𝟐 −Ethoxy propane

𝐎𝐂𝐇𝟐 − 𝐂𝐇𝟑
Ethyl 𝟐° −Propyl ether
𝐂𝟔 𝐇𝟓 − 𝐎 − 𝐂𝐇𝟑 Methyl phenyl ether, Methoxy benzene
Anisole
𝐂𝟔 𝐇𝟓 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Ethyl phenyl ether, Ethoxy benzene
Phenetole
𝐂𝟔 𝐇𝟓 − 𝐎 − 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟑 Heptyl phenyl ether 𝟏 −Phenoxy heptane
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝟔 𝐇𝟓 Isopentyl phenyl ether 𝟑− 20
Methylbutoxy
𝐂𝐇𝟑
benzene
𝐂𝐇𝟑 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟑 𝟏, 𝟐 − Dimethoxy
ethane
𝐂𝐇𝟑 𝐂𝐇𝟑 𝟏 − Methoxy − 𝟐, 𝟐 −
𝐎𝐂𝐇𝟑
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 𝐬𝐩𝟑 hybridisation. Both
𝐬𝐩𝟑 hybrid orbitals are attached to cabon of alkyl group
by sigma (𝛔) bond formed by the overlap of a 𝐬𝐩𝟑
hybridised orbital of carbon with a 𝐬𝐩𝟑 hybridised orbital
of oxygen. Other two 𝐬𝐩𝟑 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 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 𝐒𝐍𝟐 reaction.
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐁𝐫 + 𝐍𝐚𝐎𝐂𝐇𝟐 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐍𝐚𝐁𝐫
Ethyl bromide Sodium ethoxide Diehyl ether
𝐂𝐇𝟑 𝐂𝐇𝟑

𝐂𝐇𝟑 —𝐂𝐇𝟐 —X+NaO—C—𝐂𝐇𝟑 𝐂𝐇𝟑 —𝐂𝐇𝟐 —O—C—𝐂𝐇𝟑 + NaX

𝐂𝐇𝟑 𝐂𝐇𝟑
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.
 𝐂𝐇𝟑 𝐂𝐇𝟐

𝐂𝐇𝟑 —C—Br + NaO—𝐂𝐇𝟐 —𝐂𝐇𝟑 𝐂𝐇𝟑 —C + 𝐂𝐇𝟑 —𝐂𝐇𝟐 —OH + NaX

𝐂𝐇𝟑 𝐂𝐇𝟑
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.
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐁𝐫 + 𝐍𝐚𝐎𝐂𝟔 𝐇𝟓 𝐂𝟔 𝐇𝟓 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐍𝐚𝐁𝐫
Phenetole
𝐂𝐇𝟑 − 𝐁𝐫 + 𝐍𝐚𝐎𝐂𝟔 𝐇𝟓 𝐂𝟔 𝐇𝟓 − 𝐎 − 𝐂𝐇𝟑 + 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. 𝐇𝟐 𝐒𝐎𝟒
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇 𝐂𝐇𝟐 = 𝐂𝐇𝟐 + 𝐇𝟐 𝐎
𝟒𝟒𝟑 𝐊
Diethyl ether is obtained by heating mixture of excess of ethyl alcohol and conc.
𝐇𝟐 𝐒𝐎𝟒 at 𝟒𝟏𝟑 𝐊 temperature.
𝟒𝟏𝟑 𝐊
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇 + 𝐇𝐎𝐒𝐎𝟑 𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐒𝐎𝟑 𝐇 + 𝐇 − 𝐎𝐇 21
𝟒𝟏𝟑 𝐊
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐒𝐎𝟑 𝐇 + 𝐇𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐇𝟐 𝐒𝐎𝟒
Or
𝐂𝐨𝐧. 𝐇𝟐 𝐒𝐎𝟒
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇 + 𝐇𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐇 − 𝐎𝐇
𝟒𝟏𝟑 𝐊
This method is suitable only for the ethers containing primary alcohol group.
Therefore the formation of ether is a 𝐒𝐍𝟐 reaction. The mechanism of
dehydration of ethanol involves the following steps:
Mechanism
Step𝟏 : Attack of protic acids like, 𝐇𝟐 𝐒𝐎𝟒, 𝐇𝟑 𝐏𝐎𝟒 etc. gives protonated alcohol.
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐇 + 𝐇 + 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎+ − 𝐇

𝐇
Step𝟐 : In this step, another alcohol molecule attacks on a protonated alcohol.
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 + 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎+ − 𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎+ − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐇 − 𝐎

𝐇 𝐇 𝐇 𝐇
Step𝟑 : Formation of ether by elimination of a proton.
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎+ − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 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.
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐂𝐨𝐧. 𝐇𝟐 𝐒𝐎𝟒
𝐂𝐇𝟑 − 𝐂 − 𝐎𝐇 𝐂𝐇𝟑 − 𝐂 + 𝐇 − 𝐎𝐇

𝐂𝐇𝟐 − 𝐇 𝐂𝐇𝟐
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. 𝐇𝟐 𝐒𝐎𝟒
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 𝐇 Lower ethers are formed hydrogen bonds with water like
𝐑 𝐎
𝐎
alcohols. As the molecular mass of ethers increase, the
𝐑 𝐎 hydrophobic part or hydrocarbon part of ethers is also
𝐇 𝐇 increase due to which the ability of formation of
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.
Chemical Properties of Ethers ⇨ 22
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 + 𝐇𝟐 𝐎
This reaction is a nucleophilic substitution reaction. Therefore, if at least one of the
groups of − 𝐎 − functional group of ether is 𝐒𝐍𝟏 group (the formation of more stable
benzyl or allyl or tertiary carbonium ion due to cleavage of 𝐂 − 𝐎 bond), the reaction is
𝐒𝐍𝟏 else 𝐒𝐍𝟐 . For example,
𝐒𝐍𝟐
𝐂𝐇𝟑 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐈 + 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐈 + 𝐇𝟐 𝐎
The 𝐒𝐍𝟐 mechanism of these reactions involves the following steps:
Mechanism
Step𝟏 : The 𝐒𝐍𝟐 reaction of an ether with 𝐇𝐈 starts with protonation of ether molecule.
𝐂𝐇𝟑 − 𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐎+ − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 + 𝐈 −

𝐇
Step𝟐 : 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 𝐒𝐍𝟐 mechanism.
−
𝐈 − + 𝐂𝐇𝟑 − 𝐎+ − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐈 … . . 𝐂𝐇𝟑 … … 𝐎+ − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐈 + 𝐂𝐇𝟑 𝐂𝐇𝟐 − 𝐎𝐇

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.
Step𝟑 : The 𝐒𝐍𝟐 reaction of an alcohol with 𝐇𝐈 starts with protonation of alcohol.
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎 − 𝐇 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎+ − 𝐇 + 𝐈 −

𝐇
Step𝟒 : Iodide attacks the least substituted carbon of the oxonium ion formed in step 𝟑
and displaces an ethyl iodide.
 −
𝐈 − + 𝐂𝐇𝟐 − 𝐎+ − 𝐇 𝐈 … . . 𝐂𝐇𝟐 … … 𝐎+ − 𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐈 + 𝐇𝟐 𝐎

𝐂𝐇𝟑 𝐇 𝐂𝐇𝟑 𝐇
For example,
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐒𝐍𝟏
𝐂𝐇𝟑 − 𝐂 − 𝐎 − 𝐂𝐇𝟑 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐂 − 𝐈 + 𝐂𝐇𝟑 − 𝐎𝐇

𝐂𝐇𝟑 𝐂𝐇𝟑
The 𝐒𝐍𝟏 mechanism of this reaction involves the following steps:
Mechanism
Step𝟏 : The 𝐒𝐍𝟏 reaction of an ether with 𝐇𝐈 starts with protonation of ether molecule.
𝐂𝐇𝟑 𝐂𝐇𝟑

𝐂𝐇𝟑 − 𝐂 − 𝐎 − 𝐂𝐇𝟑 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐂 − 𝐎+ − 𝐂𝐇𝟑 + 𝐈 −

𝐂𝐇𝟑 𝐂𝐇𝟑 𝐇
9414248318, 9468590309 Alcohols, Phenols and Ethers
Step 𝟐 : The departure of leaving group 𝐂𝐇𝟑 − 𝐎𝐇 creates a more stable 𝟑° − butyl
carbonium ion and the reaction follows 𝐒𝐍𝟏 mechanism.
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐒𝐥𝐨𝐰
𝐂𝐇𝟑 − 𝐂 − 𝐎+ − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂 + + 𝐂𝐇𝟑 − 𝐎𝐇 23
𝐂𝐇𝟑 𝐇 𝐂𝐇𝟑
Step𝟑 : Nucleophile iodide ion attacks on carbonium ion and forms product.
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐅𝐚𝐬𝐭
𝐂𝐇𝟑 − 𝐂 + + 𝐈 − 𝐂𝐇𝟑 − 𝐂 − 𝐈

𝐂𝐇𝟑 𝐂𝐇𝟑
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,
𝐒𝐍𝟐
𝐂𝐇𝟑 − 𝐎 − 𝐂𝟔 𝐇𝟓 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐈 + 𝐂𝟔 𝐇𝟓 − 𝐎𝐇
The 𝐒𝐍𝟐 mechanism of this reaction involves the following steps:
Mechanism
Step𝟏 : The 𝐒𝐍𝟐 reaction of an ether with 𝐇𝐈 starts with protonation of ether molecule.
𝐂𝐇𝟑 − 𝐎 − 𝐂𝟔 𝐇𝟓 + 𝐇 − 𝐈 𝐂𝐇𝟑 − 𝐎+ − 𝐂𝟔 𝐇𝟓 + 𝐈 −

𝐇
Step𝟐 : The bond between 𝐎 − 𝐂𝐇𝟑 is weaker than the bond between 𝐎 − 𝐂𝟔 𝐇𝟓 because
the carbon of phenyl group is 𝐬𝐩𝟐 hybridised and there is a partial double bond
character. Therefore the attack by 𝐈 − ion breaks 𝐎 − 𝐂𝐇𝟑 bond and displaces a phenol
by 𝐒𝐍𝟐 mechanism.
−
𝐈 − + 𝐂𝐇𝟑 − 𝐎+ − 𝐂𝟔 𝐇𝟓 𝐈 … . . 𝐂𝐇𝟑 … … 𝐎+ − 𝐂𝟔 𝐇𝟓 𝐂𝐇𝟑 − 𝐈 + 𝐂𝟔 𝐇𝟓 − 𝐎𝐇

𝐇 𝐇
Phenols do not react further to give halides because the 𝐬𝐩𝟐 hybridised carbon of
phenol cannot undergo nucleophilic substitution reaction needed for conversion to
the halide.
The carbon of phenyl group is 𝐬𝐩𝟐 hybridised and there is a partial double bond
character in the bond between 𝐎 − 𝐂𝟔 𝐇𝟓. Therefore, diphenyl ether does not react with
𝐇𝐁𝐫 or 𝐇𝐈.
𝐂𝟔 𝐇𝟓 − 𝐎 − 𝐂𝟔 𝐇𝟓 + 𝐇 − 𝐁𝐫 No reaction.
Electrophilic substitution reactions
̈
: 𝐎𝐑 ̈
+𝐎𝐑 ̈
+𝐎𝐑 ̈
+𝐎𝐑 ̈
: 𝐎𝐑
 ⊖ ⊖

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.
𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑
𝐄𝐭𝐡𝐚𝐧𝐨𝐢𝐜 𝐚𝐜𝐢𝐝 Br
+ 𝐁𝐫𝟐 +
−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.
𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑
𝐇𝟐 𝐒𝐎𝟒 𝐍𝐎𝟐
+ 𝐇𝐍𝐎𝟑 +
−𝐇𝟐 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 𝐀𝓵𝐂𝓵𝟑 as catalyst.
𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑
futZy 𝐀𝓵𝐂𝓵𝟑 𝐂𝐇𝟑
+ 𝐂𝐇𝟑 𝐂𝓵 + +
𝐂𝐒𝟐
Anisole 𝟐 −Methoxytoluene 𝐂𝐇𝟑
(Minor) 𝟒 −Methoxytoluene (Major)
𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑
futZy 𝐀𝓵𝐂𝓵𝟑 𝐂𝐎𝐂𝐇𝟑
+ 𝐂𝐇𝟑 𝐂𝐎𝐂𝓵 +
−𝐇𝐂𝓵
Anisole 𝟐 −Methoxyacetophenone 𝐂𝐎𝐂𝐇𝟑
(Minor) 𝟒 −Methoxyacetophenone (Major)
Since 1996 XI, XII – CBSE & RBSE
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