Krishnarjuna N(Department of chemistry VSPU BLR) Page |1

VIDYASOUDHA PU COLLEGE
II PUC CHEMISTRY NOTES
CHAPTER NAME: 11.ALCOHOLS, PHENOLS AND ETHERS

ALCOHOLS:
 Alcohols are the organic compound defined by replacing one or more hydrogen atoms of an aliphatic
hydrocarbon by hydroxyl groups.
 These are hydroxyl derivatives of alkanes.
Ex: Methyl alcohols, Ethyl alcohols etc.,
PHENOLS:
 Phenols are the hydroxyl derivatives of aromatic hydro carbons.
 The hydroxyl group should be directly attached to the aromatic ring.
Ex: Phenol, Cresol etc.,
ETHERS:
 Ethers are the organic compound obtained by replacing hydrogen atom of an alkane with alkoxy(RO-)
or aryloxy (ArO- ) group.
 These are alkoxy or aryloxy derivatives of hydrocarbon
Ex: Dimethylether CH3OCH3 , Anisole C6H5OCH3 etc.,
CLASSIFICATION OF ALCOHOLS AND PHENOLS:
Alcohols and phenols may be classified as monohydric, dihydric, trihydric, polyhydric based on the number
of hydroxyl groups present in the molecule.

 Monohydric alcohols are further classified in to primary alcohol, secondary alcohol and tertiary
alcohol based on the nature of carbon atom to which the hydroxyl group is attached as follows.
i) Compound containing (sp3 ) C-OH bond:
 In this type of alcohols the OH group is attached to an sp3 hybridised carbon atom of an alkyl group.
 They are further classified as Primary, secondary and tertiary alcohols.
 In these three types of alcohols, the –OH group is attached to primary secondary and tertiary carbon
atom.

Allylic alcohols:
If the hydroxyl group is attached to allylic carbon, then the alcohol is known as allyl alcohol.
Ex:
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Benzyl alcohol:
If the hydroxyl group is attached to benzylic carbon then the alcohol is known as benzyl alcohol.
(Benzylic carbon: sp3 carbon next to the benzene ring)

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

ii) Compounds containing (sp2)C -OH bond:
 These alcohols contain -OH group bonded to a carbon-carbon double bond i.e., to a vinylic carbon or
to an aryl carbon. These alcohols are also known as vinyl alcohols.
 Vinyl alcohol: CH2 = CH – OH

CLASSIFICATION OF ETHERS:
Ethers are classified into two types
1) Simple or symmetrical ethers
2) Mixed or unsymmetrical ethers

1) Simple or symmetrical ethers:

 If the alkyl or aryl groups attached to the oxygen atom are the same.
Ex: Diethyl ether C2H5OC2H5 Dimethyl ether CH3OCH3
2) Mixed or unsymmetrical ethers:
 If the alkyl or aryl groups attached to the oxygen atom are different.
Ex: Ethyl methyl ether C2H5OCH3 Ethyl phenyl ether C2H5OC6H5

NOMENCLATURE:
ALCOHOLS:
The common name of alcohols is "alkyl alcohols"
Ex: CH3OH=>Methyl alcohol
IUPAC name is derived by substituting 'e' of alkane with the suffix 'ol'.
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NOMENCLATURE OF PHENOLS:
The IUPAC name of phenol is benzenol. But the name phenol is accepted by the IUPAC system

NOMENCLATURE OF ETHER:
 In IUPAC system, ethers are named as alkoxy alkane, in which oxygen of ether is taken along with
smaller alkyl group.
 Bigger alkyl group is considered as part of the alkane.
 Alkoxy is the prefix used before alkane name.
 In common name, ethers are named by naming the two alkyl or aryl groups in an alphabetical order
and adding to the word ether.
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STRUCTURE OF FUNCTIONAL GROUPS:

1) In alcohols -OH group attached to carbon by sigma (σ) bond both C and oxygen are sp3 hybridized.
The bond angle in alcohols is slightly less than the tetrahedral angle (1090.281 ). It is due to repulsion
between the unshared electron pair of oxygen.

2) In phenols, -OH group attached to sp2 hybridised carbon of an aromatic ring. The C-O bond length is
slightly less (136pm) than that in methanol. This is due to
i) Partial double bond characteristic of –OH group with aromatic ring.
ii) sp2 hybridised state of carbon to which oxygen is attached.

3) In ethers, Oxygen attached to two carbon four pair of electron (2 bond pair + 2 lone pair) will arranged in
tetrahedral arrangement. The bond angle slightly greater than tetrahedral angle due to repulsive interaction
between two bulky (-R) groups.

PREPARATION OF ALCOHOLS :
1) FROM ALKAENES:
i) By acid catalysed hydration(hydrolysis):
 Alkenes react with water in the presence of acid as catalyst to form alcohols.
 In case of unsymmetrical alkenes the reaction follows Markownikoff's rule.
Ex: When propene is reacted with water in the presence of acid catalyst, it form 2-propanol as the
major product.

Mechanism The mechanism of the reaction involves the following three steps:
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O+ .

Step 2: Nucleophilic attack of water on carbocation.

Step 3: Deprotonation to form an alcohol.

Note: Since the mechanism involves carbocation intermediate rearrangements can take place before forming
the final product.
ii) By hydroboration – Oxidation reaction:
 Alkenes are reacted with diborane (B2H6) to form trialkyl boranes, which on oxidation using
hydrogen peroxide in pressure of basic medium, give respective alcohol.
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 The overall reaction is the addition of water to alkene according to anti Markownikoff's rule.
Ex: When propene is reacted with diborane, it forms tripropylborane, this on oxidation gives propan-
1-ol.

2) FROM CARBONYL COMPOUND:

i) By reduction of aldehydes and ketones: Aldehydes or ketones on reduction gives respective alcohols.
Aldehydes give primary alcohols and ketones give secondary alcohols.

ii) From carboxylic acids and esters: Carboxylic acids and ester are reduced to respective alcohols by using
Lithium aluminium hydride.

3) FROM GRIGNARD REAGENTS:

 Grignard reagents reacts with carboxyl compounds (aldehydes and ketones) followed by hydrolysis to
give alcohols.
Step-1: Nucleophilic addition of Grignard reagent to the carboxyl group to form adduct.
Step-2: Hydrolysis of the adduct yields an alcohol.

 Formaldehydes forms primary alcohol, any other aldehyde forms secondary alcohols and ketones
forms tertiary alcohols. The over all reactions can be written as

PREPARATION OF PHENOLS:
Phenol, also known as carbolic acid, isolated from coal tar.
1) FROM HALOARENES:
Chlorobenzene is fused heated with NaOH or KOH at 623K and 320 atmospheric pressure to give
sodium phenoxide, which upon acidification gives phenol.
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2) FROM BENZENE SULPHONIC ACID:

Benzene is sulphonated with oleum (H2S2O7) to give benzene sulphonic acid which converted to
sodium phenoxide on heating with molten sodium. This on acidification gives phenol.

3) FROM DIAZONIUM SALTS:

Aniline treated with nitrous acid (NaNO2 + HCl) at 273 – 278K to give benzene diazonium salt.
Which upon hydrolysed to give phenols.

4) FROM CUMENE:
Cumene (isopropylbenzene) is oxidized in the presence of air to cumene hydroperoxide. It is
converted to phenol and acetone by treating it with dilute acid.

PHYSICAL PROPERTIES OF ALCOHOLS AND PHENOLS BOILING POINTS:

1. The boiling points of alcohols and phenols increase with increase in the number of carbon atoms.
2. In alcohols boiling points decreases with increase in branching in carbon chain (due to decrease in
van der Waals force).
3. The hydroxyl group in alcohols and phenols can form intermolecular hydrogen bonds. As a result
boiling point of alcohols and phenols are higher than that of hydrocarbons, alkyl halides and ether of
comparable molecular mass.

Solubility:
1) Alcohols and phenols have higher solubility in water due to the formation of intermolecular hydrogen
bonds with water molecules.
2) Solubility decreases with increase in the size of alkyl or aryl groups.
3) Lower member of alcohols like methanol or ethanol are completely miscible with water in all proportions.
CHEMICAL PROPERTIES OF ALCOHOLS AND PHENOLS:
 Alcohols can behave both as electrophiles and nucleophile during a chemical reaction. The reaction in
which the O-H bond breaks represents its nucleophilic nature.
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 Alcohols behave as electrophiles when the C-OH bond breaks during a chemical reaction.

REACTION INVOLVING CLEAVAGE OF OXYGEN-HYDROGEN (O-H) BOND IN ALCOHOLS:

1. ACIDIC NATURE OF ALCOHOLS AND PHENOLS:
Reaction with active metals:
 Alcohols and phenols reacts with active metals like sodium, potassium and aluminium to yield
corresponding alkoxides/phenoxides and hydrogen.

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

 The above reactions show that alcohols and phenols are acidic in nature. Alcohols and phenols are
Bronsted acids i.e., they can donate a proton to a stronger base.

Acidic strength of alcohols:

 Alcohols undergo dissociation as

 The acidic strength of alcohols depends on the stability of alkoxide ion, the alkoxide ion is
destabilized by the +I – effect of alkyl group. More the +I effect of alkyl groups, lesser will be the
acidic strength. So the order of acidic strength of alcohols is

 Acidic strength of alcohols compared with water.When water is reacted with alkoxide, it forms
alcohols and hydroxide ion, this shows water is a better proton donor than alcohols.
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Hence alkoxides are better proton acceptors than hydroxide ion.

Acidic strength of phenols:
 The ionisation of an alcohol and a phenol takes place as follows:

 In phenoxide ion, the negative charge on oxygen atom is delocalized into benzene ring due to
resonance.

Due to this charge distribution, phenoxide ion is stabilized. Hence dissociation of phenol is
favourable so phenol is more acidic than alcohol and water.
EFFECT OF SUBSTITUENTS ON ACIDIC STRENGTH OF PHENOL:
 The presence of an electron with drawing group (EWG) stabilize the phenoxide ion and hence
increases the acidic strength of phenols.
 The effect will be more when such group is present at ortho and para position than at Meta.
 The presence of an electron donating group (EDG) decreases the stability of phenoxide ion.
-NO2 – group is E.W.G
CH3 – group is E.D.G
Acidic strength in cresols:

Acidic strength in nitrophenols:

2. ESTERIFICATION REACTION:
 Alcohols and phenols react with carboxylic acids acid chlorides and acid anhydrides to form esters.
 When alcohol phenols react with carboxylic acids or acid anhydrides in presence of concentrated
sulphuric acid to for respective esters.
 The reaction is reversible, reaction. Sulphuric acid acts as dehydrating agent.

Ex: Methanol treated with acetic acid in the presence of conc. H2SO4 to give methyl ethanoate.
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 The reaction with acid chloride is carried out in the presence of a base pyridine. This will neutralize
HCl produced during the reaction and shift equilibrium to the right side.

The above reaction is also known as acylation reaction.

PREPARATION OF ASPIRIN:
Salicylic acid on acetylation gives acetyl salicylic acid which is known as aspirin.

REACTION INVOLVING CLEAVAGE OF CARBON – OXYGEN (C-O) BOND IN ALCOHOLS:

Cleavage of C-O bond takes place only in alcohols and in phenol observed when reacts with Zinc.
1) REACTION WITH HYDROGEN HALIDES:
Alcohols react with HX to form alkyl halides
𝐴𝑛ℎ𝑦.𝑍𝑛𝐶𝑙2
R – OH + HX → R – X + H2O
𝐴𝑛ℎ𝑦.𝑍𝑛𝐶𝑙2
Ex: CH3 – OH + HCl → CH3 – Cl + H2O
2) REACTION WITH PHOSPHOROUS HALIDES:
Alcohols reacts with PCl5 or PCl3 to form respective alkyl chlorides.

Lucas Test: [Conc HCl + Anhydrous ZnCl2]

 When an alcohol is treated with lucas reagent, it forms respective alkyl chloride, the formed alkyl
chloride is insoluble in aqueous medium and forms turbidity.
 Formation of turbidity indicates the formation of alkyl chloride.
 The order of reactivity of alcohols towards this reaction is 30 >20 >10 .
 If turbidity appear immediately, then the alcohol is a tertiary alcohol.
 If the turbidity appear after 5-10 minutes, then the alcohol is secondary alcohol.
 If the turbidity does not appear at room temperature, then the alcohol is a primary alcohols.
3) DEHYDRATION OF ALCOHOLS:
 Alcohols undergo dehydration in the pressure of concentrated H2SO4 or H3PO4 or anhydrous Al2O3
etc., to form alkenes.
 Ethanol undergo dehydration in the presence of concentrated H2SO4 at 443K, to form ethane.

 Secondary and tertiary alcohols undergo dehydration quite easily The reaction follow saytzeff's rule
and involve carbocation intermediate and order is 30 >20 >10
Mechanism:
Step 1: Formation of protonated alcohol
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Step 2: Formation of carbocation: It is the slowest step and hence, the rate determining step of the
reaction

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

Note: Carbocations undergo rearrangement before forming alkene.

4) OXIDATION:
 Alcohols on oxidation gives aldehydes and ketones.
 Primary alcohols give aldehydes, secondary alcohols give ketones.
 These reactions are also known as dehydrogenation reaction as these involves loss of two hydrogen.
 The reagent for oxidation of primary alcohols to aldehydes are
1) PCC (pyridinium chloro chromate)
2) PDC (pyridinium dichromate)

 Secondary alcohols oxidized to ketones by chromic anhydride (CrO3)

5) DEHYDROGENATION OF ALCOHOLS:
 Vapours of alcohols is passed over red hot copper at 573K dehydrogenation takes place forming
carbonyl compounds.
 Primary alcohols gives aldehydes, secondary alcohols gives and ketones and tertiary alcohols
gives alkenes.

 Strong oxidation: Alcohols on strong oxidation with acidified or alkaline potassium permanganate
give carboxylic acids.

REACTIONS OF PHENOL:
1) ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS:
In phenol, the hydroxyl group is an activating group and an ortho and para directing group. This activating
nature is due to + R effect of –OH group
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A) HALOGENATION:
i) When phenol is reacted with bromine in CCl4 or CHCl3 or CS2 (low polarity solvents) it form a mixture of
ortho bromo phenol and para bromo phenol

ii) When phenol is reacted with bromine water, a white precipitate of 2, 4, 6-tribromophenol is obtained.

B) NITRATION:
i) Phenol reacts with with dilute HNO3 dilute nitric acid at room temperature to form a mixture of ortho and
para nitrophenols.

 The ortho and para isomers are separated by steam distillation. o-nitro phenol is steam volatile due
to intra molecular hydrogen bonding. The para isomer is less volatile as it forms intermolecular
hydrogen bonding.

ii) With Conc.HNO3 Phenol is heated with concentrated nitric acid to give 2, 4, 6-trinitrophenol which is
known as picric acid.

 Picric acid is a strong acid due to the presence of three electron with drawing –NO2 group.
2) REIMER-TIEMANN REACTION:
When phenol is reacted with chloroform and sodium hydroxide to give a intermediate which on
acidification gives salicylaldehyde In this reaction –CHO group is introduced at ortho position with
respect to phenol group.
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3) KOLBE'S REACTION:
Phenol is treated with sodium hydroxide to form sodium phenoxide, which is reacted with carbon
dioxide to get salicylic acid. The reaction is known as Kolbe's reaction.

4) REACTION WITH ZINC DUST:

When phenol is heated with zinc dust it is reduced to benzene.

5) OXIDATION:
Phenol is oxidized to benzoquinone in presence of acidified sodium or potassium dichromate.

 Phenol slowly oxidized in air to give a dark coloured solution which is a mixture of quinines.
 So phenols are always stored in brown bottles to avoid oxidation.
COMMERCIALLY IMPORTANT ALCOHOLS:
1) METHANOL:
 Methanol or methyl alcohol (CH3OH) also known as "wood spirit".
 It is manufactured by the reduction of carbon monoxide in the presence of ZnO – Cr2O3 catalyst

 Methanol is colourless liquid.

 It is poisonous in nature.
 Small quantities of methanol consumed may cause blindness and large quantities cause even death.
 It is mainly used as a solvent in paints, varnishes and also in the manufacture of formaldehyde.
2) ETHANOL:
 Ethanol, C2H5OH, is commonly known as alcohol.
 A mixture of 95.5% ethanol and 4.5% water is known as rectified spirit.
 It is manufactured by fermentation process.
 Sugar in molasses, sugar cane or grape fruit juice is converted to glucose and fructose in the presence
of enzyme invertase.

 The activity of zymase is reduced when the concentration of formed alcohol is more than 14%.
 Ethanol is a colourless liquid.
 It is mainly used as a solvent in paint industry and in preparation of alcoholic beverages.
 The alcohol is made unfit for drinking by adding little copper sulphate and pyridine this alcohol is
known as denatured alcohol.
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ETHERS:
GENERAL METHODS OF PREPARATION:
1. DEHYDRATION OF ALCOHOLS:
Alcohols on dehydration using concentrated H2SO4 or H3PO4 at 413K to give ethers as major
product.
Ex: When ethanol is heated with concentrated sulphuric acid at 413K, it gives ethoxy ethane as the
major product.

Mechanism:
Step-1: The alcohol gets protonated to form protonated alcohols

Step-2: Attack of another alcohol on protonated alcohol to form protonated ether and water this is SN2
reaction.

Step-3: The protonated ether loses proton to form the ether.

 The above method is suitable for ether having primary alkyl groups.
 If the alkyl groups are secondary or tertiary, the elimination predominates over substitution form
alkene as the major product.
2. WILLIAMSON'S ETHER SYNTHESIS:
 This is a method of preparing both symmetrical and unsymmetrical ethers.
 An alkyl halide reacts with sodium or potassium alkoxide to form respective ethers.
 It is an example for SN2 reaction.

Alkyl halide Sodium alkoxide ether

Ex: CH3Cl + CH3ONa → H3C-O-CH3
methyl chloride Sodium methoxide methoxy methane
Important features of Williamson’s reaction:
1) Mixed ethers can be prepared by this method.
2) Ethers containing primary, secondary and tertiary alkyl groups can be prepared.
3) The alkyl halide must be primary to get the better yield of ether.
4) Secondary and tertiary alkyl halides will undergo elimination to form alkenes.
5) Aryl and vinyl halide do not answer the reaction as they are less reactive towards nucleophilic
substitution.
Note: In order to prepared tertiary alkyl ether, the tertiary alkyl group should be present in alkoxide but not
in alkyl halide [because alkoxide also acts as bases to lead to form elimination reactions].

 Aryl alkyl ether are prepared by reacting sodium or potassium phenoxide with alkyl halides
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PHYSICAL PROPERTIES:
1) Ethers have slight polarity due to the presence of C-O bond. But this polarity does not increase the
boiling point appreciably.
2) The boiling point of alkanes and ether with comparable molecular mass are almost equal. But
alcohols have higher boiling point due to H-bonding between molecules. Ethers are miscible with
water as they can form hydrogen bonds with water molecules

3) As the molecular mass increases, the miscibility or solubility in water decreases.

CHEMICAL PROPERTIES OF ETHER:
1) Cleavage of ethers [ethers are the least reactive of the functional group] :
 Ether undergo cleavage of C-O bond in presence of hydrogen halides under strong acidic conditions
to form alkyl halides and an alcohol

 If excess of HX is used another alkyl halide

 In arylalkyl ethers the cleavage takes place only at alkyl oxygen bond. The aryl-oxygen bond does not
break as it has partial double bond character due to resonance.

 Phenols do not reacts with excess of HX.

 Aryl-Aryl ether do not undergo cleavage even at high temperature.
Mechanism of ether cleavage:
 The ether cleavage can follow either SN1 or SN2 mechanism depending on the type of alkyl groups
attached to oxygen atom.
SN1 mechanism:
 The mechanism is followed if one of the alkyl group is tertiary.
 It has three step
Step-1: The ether reacts with HI to form protonates ether molecule

Step-2: The protonated ether molecule loses alcohol to form tertiary carbon

Step-3: The tertiary carbocation reacts with iodide ion to form tertiary alkyl halide.

 Thus cleavage of ethers having tertiary alkyl group, the alkyl iodide is formed with tertiary alkyl
group and alcohol is formed with the other alkyl group.
SN2 mechanisms:
 This mechanism is followed if the alkyl groups are either primary or secondary.
 The mechanism has two steps
Step-1: The ether reacts with HI to form protonated ether
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Step-2: The iodide ion being a good nucleophile attacks the less stearically hindered carbon to form
alkylhalide with displacement of alcohol.

 Thus, alkyl halide is formed with a less bulky group and the alcohol is formed with a more bulky
group

2) ELECTROPHILIC SUBSTITUTION REACTIONS OF ARYL ETHERS:

The alkoxy group attached to benzene ring is an activating group and an ortho and para director. This
is due to +R effect of alkoxy group.

a) Halogenation:
Anisole when reacted with bromine in acetic acid to form a mixture of ortho and para bromoanisole
para isomer will be the major produced

b) 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 aluminium
chloride (a Lewis acid) as catalyst.
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c) Nitration:
Anisole reacts with a mixture of concentrated sulphuric and nitric acids to yield a mixture of ortho
and para nitro anisole.

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