Alcohols, Phenols and Ethers

Alcohols, Phenols and Ethers
DESIGNED
Alcohol:-They are indicated by presence of—OH group in a chain .This -OH is regarded
as hydroxyl group.
Functional group – OH
Suffix used: “ol”
Examples: Its homologous series is: Methanol (CH3OH), Ethanol(C2H5OH), Propanol (C3H7OH)
and so on.
Classification of alcohols: We can classify alcohols on the basis of different factors:

1) On the basis of number of -OH (hydroxyl) group attached:
• Monohydric alcohols: They have only one hydroxyl group attached.
Example: methanol (CH3OH), ethanol (C2H5OH)
• Dihydric alcohols: They have two hydroxyl groups attached.
Example: ethylene-glycol
• Polyhydric alcohol: That have three or more hydroxyl groups in it.
Example: glycerol
2) On the basis of primary secondary or tertiary carbon atom (alpha carbon):
Structure of Alcohol: The oxygen atom of alcohols is Sp3 hybridised and they have
tetrahedral position of hybrid atomic orbitals.
• The value of ROH bond angle depends upon the R group. For
methyl alcohol, it is (∠C – O – H) 108.9° due to repulsion of
lone pairs.
Preparation of alcohols: It can be prepared by following methods:
1) From Alkenes:
Mechanism:-
2) Aldehydes yield primary alcohols

whereas ketones give secondary alcohols, when subjected to reduction.
4) From Grignard reagents: The reaction produces a primary alcohol with methanal, a
secondary alcohol with aldehydes (except methanal) and tertiary alcohol with ketones.
5) Hydrolysis of alkyl halides:
6) Hydrolysis of ethers:
Physical Properties of Alcohols
a) Lower alcohols are colourless liquids, members from C5 – C11 are oily liquids and higher
members are waxy solids.
b) The hydroxyl groups in alcohols can form H-bonds with
water, so alcohols are miscible with water. The solubility
decreases with increase in molecular mass.
Chemical Reactions of Alcohols:-

1) Reactions involving cleavage of O–H Bond:
a) Acidity of alcohols: Reaction with metals
• Alcohols are weaker acids than water due to +1 group present in alcohols, which
decreases the polarity of -O-H bond.
• Acid strength of alcohols
Electron releasing group increases electron density on oxygen to decrease the

polarity of – OH bond.
• Order of acidity is
b) Esterification: Alcohols reacts with carboxylic acids, acid chloride and acid
anhydrides to form esters.
2) Reaction involving cleavage of C-O bond in alcohols
a) Reaction with halogen acids
• For a given alcohol order of reactivity of HX is

• For a given halogen acid order of reactivity of alcohols
Lucas test: The difference in reactivity of three classes of alcohols with HCl
distinguishes them from one another.
Primary alcohol → No Reaction OR No turbidity at room temp.
Secondary alcohol → Turbidity appears within about 5 minutes.
Tertiary alcohol → Turbidity appears immediately.
b) Reaction with phosphorus halides:-
c) Reaction with thionyl chloride:-
d) Dehydration of alcohols:-
• The relative ease of dehydration of alcohols follows the following order:-

Mechanism:-
e) Oxidation reactions: Oxidising reagents used for the oxidation of alcohols are
neutral, acidic or alkaline KMnO4 and acidified K2Cr2O7. CrO3 in anhydrous medium is
used as the Oxidising agent for the isolation of aldehydes. A better reagent for
oxidation of primary alcohols to aldehydes in good yield is pyridinium chlorochromate
(PCC).
f) Dehydrogenation:
Phenol:-
Classification of Phenols: We can classify phenols on the basis of number of -OH

(hydroxyl) group attached:
Structure of Phenols: In phenols, the –OH group is attached to

Sp2 hybridised carbon and thus, the C–O bond acquires a partial
double bond character.
Preparation of Phenols: It can be prepared by following methods-
1) From haloarenes:-
2) From benzenesulphonic acid:-
3) From diazonium salts:-

4) From cumene:-
Physical Properties of Phenols

a) These are colourless liquids or crystalline solids but become coloured due to slow
oxidation with air.
b) Phenol is also called carbolic acid.
c) Because of the presence of polar -OH bond, phenols form intermolecular H-bonding with
other phenol molecules and with water.
Chemical Reactions of Phenols:-

1) Reactions involving cleavage of O–H Bond:
a) Acidity of phenols: Reaction with metals
• Phenol is more acidic than alcohols due to stabilisation of phenoxide ion through
resonance. Presence of electron withdrawing group increases the acidity of phenol
by, stabilising phenoxide ion while presence of electron releasing group decreases
the acidity of phenol by destabilising phenoxide ion.
• Thus. increasing acidic strength is-
• Higher Ka and lower pKa value corresponds to the stronger acid.
b) Esterification: Phenols reacts with carboxylic acids, acid chloride and acid
anhydrides to form esters.
2) Reactions of Phenols: Following reactions are shown by phenols only,
1. Electrophilic substitution reactions: The -OH group attached to the benzene
ring activates it towards electrophilic substitution at ortho and para positions.
a) Nitration: With dilute nitric acid at low temperature (298 K), phenol yields a
mixture of ortho and para nitrophenols.
With concentrated nitric acid, phenol is converted to 2,4,6-trinitrophenol. The

product is commonly known as picric acid. The yield of the reaction product is poor.
b) Halogenation: With calculated amount of Br2 in CS2 or CHCl3 it gives ortho and
para product.
When phenol is treated with bromine water, 2,4,6-tribromophenol is formed as

white precipitate.
c) Sulphonation:
p-hydroxybenzene
o-hydroxybenzene Sulphonic acid
Sulphonic acid
2. Kolbe’s reaction:-
3. Reimer-Tiemann reaction: On treating phenol with chloroform in the presence of

sodium hydroxide, a –CHO group is introduced at ortho position of benzene ring. This
reaction is known as Reimer - Tiemann reaction.
4. Reaction with zinc dust: Phenol is converted to benzene on heating with zinc dust.
5. Oxidation: Oxidation of phenol with chromic acid produces a conjugated diketone

known as benzoquinone.
Test to distinguish between alcohol and phenol

a) Litmus test: Phenol turns blue litmus red, whereas alcohols have no effect.
b) Coupling reaction–(azo dye test): Phenol give orange colour while alcohol do not give any
reaction.
c) Bromine water test: When Phenol is added to Br2 water they give white ppt, But alcohol
do not give any such test.
Ethers:- Ethers are the organic compounds in which two alkyl or aryl groups are
attached to a divalent oxygen. These are represented by the general formula R–O-R.
Nomenclature of Ethers: In the IUPAC system, ethers are regarded as ‘alkoxy alkanes’
in which the ethereal oxygen is taken along with smaller alkyl group while the bigger alkyl
group is regarded as a part of the alkane.
Preparation of Ethers:-
The formation of ether is a nucleophilic bimolecular reaction (SN2) involving the attack
of alcohol molecule on a protonated alcohol
2) Williamson’s synthesis: Only primary alkyl halides when react with sodium alkoxide
give ether while tertiary alkyl halides give alkene due to steric hindrance.
Ethers containing substituted alkyl groups (secondary or tertiary) may also be prepared
by this method.
Physical Properties of Ethers: Lower members are gases and higher members may be
liquids or solid due to increase in the Vander wall force.
• Ethers have higher dipole moments because of electro negativity difference and
structure is bent.
• They have larger bond angles than alcohol.
• More the bulky group’s, lower is the value of dipole moments.
• But as number of Carbon atoms increase, solubility decrease because non polar part
increase.
Chemical Reactions of Ether:

1) Reaction with HX:
The order of reactivity of hydrogen halides is as follows: HI > HBr > HCl
2) Halogenation:
3) Friedel-Crafts reaction:
4) Nitration:
Uses of ethers: Ethers are used as a refrigerant.

• They are used as industrial solvent for fat and oils.
• When mixed with alcohol they make alcohol denatured.

Alcohols, Phenols and Ethers

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Alcohols, Phenols and Ethers

Suffix used: “ol”

Classification of alcohols: We can classify alcohols on the basis of different factors:

• Monohydric alcohols: They have only one hydroxyl group attached.

Example: methanol (CH3OH), ethanol (C2H5OH)

• Dihydric alcohols: They have two hydroxyl groups attached.

• Polyhydric alcohol: That have three or more hydroxyl groups in it.

2) On the basis of primary secondary or tertiary carbon atom (alpha carbon):

2) Aldehydes yield primary alcohols

5) Hydrolysis of alkyl halides:

Chemical Reactions of Alcohols:-

Electron releasing group increases electron density on oxygen to decrease the

• For a given alcohol order of reactivity of HX is

Primary alcohol → No Reaction OR No turbidity at room temp.

Secondary alcohol → Turbidity appears within about 5 minutes.

Tertiary alcohol → Turbidity appears immediately.

b) Reaction with phosphorus halides:-

c) Reaction with thionyl chloride:-

• The relative ease of dehydration of alcohols follows the following order:-

Classification of Phenols: We can classify phenols on the basis of number of -OH

Structure of Phenols: In phenols, the –OH group is attached to

Preparation of Phenols: It can be prepared by following methods-

2) From benzenesulphonic acid:-

3) From diazonium salts:-

Physical Properties of Phenols

Chemical Reactions of Phenols:-

• Higher Ka and lower pKa value corresponds to the stronger acid.

With concentrated nitric acid, phenol is converted to 2,4,6-trinitrophenol. The

When phenol is treated with bromine water, 2,4,6-tribromophenol is formed as

3. Reimer-Tiemann reaction: On treating phenol with chloroform in the presence of

5. Oxidation: Oxidation of phenol with chromic acid produces a conjugated diketone

Test to distinguish between alcohol and phenol

• They have larger bond angles than alcohol.

• More the bulky group’s, lower is the value of dipole moments.

Chemical Reactions of Ether:

Uses of ethers: Ethers are used as a refrigerant.

• When mixed with alcohol they make alcohol denatured.

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