Alcohols, Phenols and Ethers

General Formula R-OH C6H5-OH R-O-R‫׀‬

Compound Alcohol Phenol Ether
Alcohols and Phenols:
Classification:
I Classification based on number of hydroxyl groups:
On the basis of number of –OH groups, alcohols are classified into monohydric,dihydric and
trihydric alcohols. Example,

CH3-CH2-OH CH2-CH2 CH2-CH-CH2

OH OH OH OH OH
Monohydric alcohol Dihydric alcohol Trihydric alcohol
Ethyl alcohol Ethylene glycol Glycerol or glycerine

OH OH

OH
Monohydric phenol Dihydric phenol
Phenol Catechol

Trihydric phenols OH OH
OH OH
OH
HO OH
OH OH
Pyrogallol Hydroxyquinol Phloroglucinol

II Classification based on the hybridization of carbon containing OH group:

1) Alcohols containing OH group connected to sp3 carbon:
(i) Alkyl alcohols: -OH is connected to alkyl carbon.
Eg., CH3-CH2-OH Ethyl alcohol
(ii) Allylic alcohols: -OH is connected to allylic carbon.
Eg., CH2=CH-CH2-OH Allyl alcohol
(iii) Benzylic alcohols: -OH is connected to benzylic carbon.
CH2-OH
Benzyl alcohol

Alkyl, allyl and benzyl alcohols are further classified into primary(10), secondary(20) and tertiary(30)
alcohols depending on whether –OH group is attached to primary(10), secondary(20) and tertiary(30)
carbon atoms.

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2) Alcohols containing OH group connected to sp2 carbon:
(i) Vinylic alcohols: -OH is connected to vinylic carbon.
CH2=CH-OH Vinyl alcohol OH
(ii) Aryl alcohols or phenols: -OH is connected to benzene ring. Phenol

Nomenclature
Compound Common name IUPAC name
CH3-CH2-CH2-CH2-OH n-butyl alcohol Butan-1-ol
CH3-CH-CH2-OH
isobutyl alcohol 2-Methylpropan-1-ol
CH3
CH3-CH-CH2-CH3
sec-butyl alcohol Butan-2-ol
OH
CH3
CH3-C-OH tert-butyl alcohol 2-Methylpropan-2-ol
CH3
CH3
CH3-C-CH2-OH neopentyl alcohol 2,2-Dimethylpropan-1-ol
CH3
OH
Cyclohexyl alcohol Cyclohexanol

OH
CH3 o-cresol 2-Methylphenol

OH

m-cresol 3-Methylphenol
CH3
OH

p-cresol 4-Methylphenol

CH3
OH
OH

Catechol Benzene-1,2-diol

2
 OH

Resorcinol Benzene-1,3-diol
OH
OH

Quinol or Hydroquinone Benzene-1,4-diol

OH
Ethers:
Classification:
(i) Simple or symmetrical ethers: Ethers with two similar alkyl groups attached to oxygen
Eg., CH3-O-CH3
(ii) Mixed or unsymmetrical ether: Ethers with two different alkyl groups attached to oxygen
Eg., CH3-CH2-O-CH3
Nomenclature:
Compound Common name IUPAC name
CH3OCH3 Dimethyl ether Methoxymethane
CH3CH2OCH3 Ethyl methyl ether Methoxyethane
CH3-CH-O-CH2-CH3
Ethyl isopropyl ether 2-Ethoxypropane
CH3
(CH3)2CHOCH(CH3)2 Diisopropyl ether 2-isopropoxypropane (or)
2-(1-Methylethoxy)propane
O
CH3 Cycohexyl methyl ether Methoxycyclohexane

Methyl phenyl ether (or) Methoxybenzene (or)

C6H5-O-CH3
Anisole Anisole
Ethyl phenyl ether (or) Ethoxybenzene (or)
C6H5-O-CH2CH3
Phenetole Phenetole
O
(CH2)7CH3 Octyl phenyl ether 1-Phenoxyoctane

O
Diphenyl ether Phenoxybenzene

Q. The ROH bond angle in alcohol is less than the tetrahedral bond angle. Why?
It is due to greater repulsion between the lone pairs of electrons on oxygen atom.

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Q. The ROR bond angle in ether is greater than the tetrahedral bond angle. Why?
It is due to greater steric repulsion between the two bulky alkyl groups.
Q. The C-O bond length in phenol is less than that of methanol (or aliphatic alcohols). Why?
It is because (i) The C-O bond in phenol has partial double bond character due to resonance effect,
and (ii) The carbon connected to -OH group is sp2 hybridized hence it forms shorter bond and stronger
bond.
Q. Phenol is less polar than methanol. (or) Dipole moment of phenol is less than that of methanol.
Why?
In methanol the –OH group is connected to sp3 hybridised carbon whereas in phenol the -OH group
is connected to sp2 hybridized carbon which forms shorter bond. Dipole moment is the product of
charge and distance between the atoms. Hence the dipole moment of phenol is less.
Q. Lower alcohols are miscible (soluble) in water. Why?
Lower alcohols form hydrogen bond with water.
Q. Solubility of alcohols decrease with increase in size of alkyl group or increase in number of carbon
atoms. Why?
Alkyl group is non-polar and hydrophobic hence as the size of the alkyl group increases
hydrophobic nature increases and the ability to form hydrogen bonding decreases.
Q. Solubility of alcohols increases with branching. Why?
Branching reduces the surface area of alkyl group hence reduces the hydrophobic effect.
Q. Boiling points of alcohols are much higher than that of alkanes, ethers, aldehydes and ketones of
similar molar mass. Why?
There is strong intermolecular hydrogen bonding in alcohols.
Q. Boiling points of alcohols and phenols increase with increase in number of carbons but decrease
with increase of branching. Why?
With increase in number of carbon atoms, molar mass and surface area increases hence there is
increase in Van der waal’s force of attraction. Whereas branching decreases the surface area hence
decreases the Van der waal’s forces of attraction.
Preparation of alcohols:
1) By acid catalysed hydration of alkenes (or) Catalytic hydration of alkenes:

Alkenes react with water in the presence of acid to form alcohols:

H2SO4
CH2 = CH2 + H2O CH3-CH2-OH Ethanol
Addition of H2O to unsymmetrical alkene follows Markovnikov’s rule.
OH
H+
CH3-CH= CH2 + H2O CH3-CH-CH3 Propan-2-ol

4
Mechanism of acid catalysed hydration of alkene to form alcohol
The reaction involves three steps
First step is protonation of alkene to form a carbocation by electrophilic attack of H3O+
Second step is nucleophilic attack of water on carbocation to form protonated alcohol.
Third step is deprotonation to form alcohol.

Mechanism of acid catalysed hydration of ethene to form ethanol:

The mechanism involves three steps
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O+
H2O + H+ → H3O+
CH2=CH2 + H3O+ → CH3-CH2+ + H2O
Step2: Nucleophilic attack of water on carbocation
CH3-CH2+ + H2O → CH3-CH2-OH2+
Step3: Deprotonation to form alcohol
CH3-CH2-OH2+ + H2O → CH3-CH2-OH + H3O+
2) Hydroboration-Oxidation:
Alkenes react with diborane to give trialkylboranes which on oxidation with alkaline hydrogen
peroxide solution give alcohols.
CH2=CH2 CH2=CH2
CH2=CH2 + B2H6 → CH3-CH2BH2 (CH3-CH2)2BH (CH3-CH2)3B
Triethyl borane
H2O2/OH—
(CH3-CH2)3B 3 CH3-CH2-OH + B(OH)3
In this reaction, water is added indirectly to alkene to give alcohol.
In case of unsymmetrical alkenes, the addition of water is according to anti-Markovnikov’s rule. Eg.,
Propene on hydroboration and oxidation gives propan-1-ol
(BH3)2 H2O2/OH—
CH3-CH=CH2 (CH3-CH2-CH2)3B 3CH3-CH2-CH2-OH + B(OH)3

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 (OR)
(i) (BH3)2
CH3-CH=CH2 (ii) H2O2/OH— CH3-CH2-CH2-OH

3) By catalytic reduction (or) catalytic hydrogenation of carbonyl compounds:

(i) Reduction of aldehydes and ketones:
Aldehydes and ketones can be reduced by lithium aluminium hydride (LiAlH4),
sodium borohydride (NaBH4), Ni/H2, Pt/H2 or Pd/H2
Aldehydes on reduction give primary alcohols and ketones on reduction give secondary alcohols.
Pd
CH3CHO + H2 CH3CH2OH
NaBH4
CH3COCH3 CH3CH(OH)CH3
(ii) Reduction of carboxylic acids:
Carboxylic acids are reduced to primary alcohols only by strong reducing agent LiAlH4
LiAlH4
CH3COOH CH3CH2OH
LiAlH4 is an expensive reagent, hence commercially, acids are converted esters and the esters are
reduced to alcohols by cheaper reducing agent like Ni/H2
H+
CH3CH2COOH + CH3CH2OH CH3CH2COOCH2CH3 + H2O

Ni/H2
CH3CH2COOCH2CH3 CH3CH2CH2OH + CH3CH2OH
Sodium borohydride (NaBH4) can reduce only carbonyl group but cannot reduce acid, ester and
amide functional groups. Eg.,
CH3COCH2COOCH2CH3 NaBH4 CH3CHCH2COOCH2CH3
OH
4) From Grignard reagents:
Grignard reagent reacts with carbonyl compound to form an adduct which on hydrolysis give alcohols
(i) With methanal or formaldehyde (HCHO), GR gives a primary alcohol.
(ii) With any other aldehyde (RCHO), GR gives secondary alcohol.
(iii) With any ketone (RCOR), GR gives tertiary alcohol.
Example;
(i) Methyl magnesium chloride on treatment with methanal (formaldehyde) followed by hydrolysis
gives ethanol (primary alcohol)
H H3O+
CH3MgCl + C O CH3-CH2-OMgCl CH3-CH2-OH + Mg(OH)Cl
H

6
(ii) Methyl magnesium chloride on treatment with ethanal (acetaldehyde) followed by hydrolysis
gives isopropyl alcohol (secondary alcohol)
CH3 H3O+
CH3MgCl + C O CH3- CH-OMgCl CH3- CH- OH + Mg(OH)Cl
H
CH3 CH3

(iii) Methyl magnesium chloride on treatment with propanone (acetone) followed by hydrolysis gives
tert-butyl alcohol (tertiary alcohol)
CH3 CH3
CH3 H3O+
CH3MgCl + C O CH3- C-OMgCl CH3- C- OH + Mg(OH)Cl
CH3
CH3 CH3
Q. Write the mechanism for addition of Grignard reagent to carbonyl group:
The reaction occurs in two steps. In the first step Grignard reagent adds to carbonyl group to form
an adduct. In the second step, adduct is hydrolysed to give alcohol.

H3O+
RMgX + C O R-C-OMgX R-C-OH + Mg(OH)X

Laboratory preparation of phenol (or) carbolic acid:

(i) From haloarenes:
Chloro benzene is converted to phenol by heating in aqueous NaOH solution at 623 K and at 300 atm
pressure followed by acidification.
Cl ONa OH
(i) NaOH, 623 K, 300 atm H+

Chlorobenzene Sodium phenoxide Phenol

(ii) From benzene sulphonic acid:
Benzene is treated with oleum (or) concentrated sulphuric acid to give benzene sulphonic acid which
on heating with NaOH followed by acidification gives phenol.

SO3H OH
Oleum (i) NaOH
(ii) H+
Benzene Benzene sulphonic acid Phenol
(iii) From diazonium salts:

Aniline is treated with a mixture of NaNO2 and HCl (or HNO2) to give benzene diazonium salt which
on treating with warm water or dilute acids gives phenol.

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 NH2 N2Cl OH
NaNO2 / HCl H2O
Heat
Aniline Benzene diazonium chloride Phenol
Industrial manufacture (or) Commercial synthesis of phenol from cumene (isopropyl benzene):
Cumene is oxidised by air to give cumene hydroperoxide which on hydrolysis gives phenol and
acetone.
CH3 CH3
CH3 C-H CH3 C-O-O-H OH

O2 H3O+
+ CH3COCH3

Cumene Cumene hydroperoxide Phenol Acetone

Chemical reactions of alcohols:
Alcohols react both as nucleophiles and electrophiles. When alcohols react as nucleophiles the O-H
bond is broken but when they react as electrophiles the C-O bond is broken.
Example for alcohols reacting as nucleophiles:
H
•• +
+
R-O-H + C → R O C → R O C + H+
•• ••

Example for alcohols reacting as elecrophiles:

+
R-OH + H+ → R-OH2 + Br— → R-Br + H2O
Reactions involving cleavage of O-H bond:
1) Acidity of alcohols and phenols:
Alcohols are weak acids and liberate H2 gas when reacted with active metals like Na, K, Al etc
2 CH3-CH2-OH + 2 Na → 2 CH3-CH2-ONa + H2
Sodium ethoxide
2 C6H5-OH + 2 Na → 2 C6H5-ONa + H2
Sodium phenoxide
6 (CH3)3C-OH + 2 Al → 2 (CH3)3C-O 3Al + 3 H2
Aluminium tert-butoxide
Acidity of alcohols:
o Alcohols are amphoteric
o The acidic nature of alcohols is due to the presence of polar O-H bond.
o Alcohols are Bronsted acids (or) Arrhenius acids because they give out H+ ions.
Ka
R-OH + B B-H + R-O— (alkoxide ion)
Alcohol Base Conjugate acid Conjugate base
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 Greater the Ka value (or lower the pKa value) greater is the acidic strength.
o The basic nature of alcohols is due to the presence of lone pairs on oxygen. Hence they are lewis
bases.
Acidity of phenols:
The acidic strength of phenol is much greater than aliphatic alcohols. Explain.
(i) Benzene ring withdraws electron from oxygen by resonance effect and thus increases the polarity
of O-H bond in phenols.
(ii) Eventhough both phenol and phenoxide are resonance stabilised, phenoxide ion is more stable
than phenol because there is no charge separation in the resonance structures of phenoxide. Therefore
the equilibrium moves to the right. Whereas alkoxide is less stable than alcohol and hence the
equilibrium moves to the left.
OH O—

+ H+
•
Phenol Phenoxide
R-OH R-O— + H+
Alcohol Alkoxide •
Resonance stabilisation of phenol:
••••
OH
•• +
OH
•• + •• ••
•• OH
OH OH+
•• ••
•
••
Resonance stabilisation of phenoxide:
••••
O ••
••• •• •• • ••
O• O •• O• •• O ••

•• ••

••

Effect of substituent on acidic strength of phenols:

(i) The presence of electron withdrawing groups (-NO2, -CN, X etc) increases the acidic strength of
phenol.
Reason: By electron withdrawing resonance effect. they (i) increase the stability of phenoxide by
dispersal of negative charge. (ii) increase the polarity of O-H bond.
(ii) The presence of electron releasing groups (-CH3, C2H5, OCH3 etc) decreases the acidic strength of
phenol.

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Reason: By electron releasing resonance effect. they (i) decrease the stability of phenoxide by
concentrating the negative charge on oxygen (ii) decrease the polarity of O-H bond.
Q. Alcohols are less acidic than water. Why?
The alkyl group is electron releasing hence it decreases the polarity of O-H bond and also
decreases the stability of alkoxide.
Q. Alkoxide (OR—) is stronger base/stronger nucleophile than hydroxide (OH—) . Why?
The alkyl group is electron releasing effect hence it increases the electron density on oxygen.
Therefore alkoxide is a stronger base/stronger nucleophile than hydroxide.
Q. Acidic nature of alcohols decrease with increase in branching at alpha carbon. (or)
Acidic nature of alcohols decrease in the order; Primary > secondary > tertiary. Why?
As the number of alkyl groups increases at alpha carbon the electron releasing inductive effect also
increases which decreases the polarity of O-H bond and also decreases the stability of alkoxide ion.
Q. p-nitrophenol is more acidic than phenol. Why?
Nitro group at para position withdraw electron by resonance hence it (i) increases the stability of
phenoxide by dispersal of negative charge. (ii) increases the polarity of O-H bond.
Q. m-nitrophenol is more acidic than phenol. Why?
Nitro group at meta position withdraw electron by inductive effect hence it (i) increases the stability
of phenoxide (ii) increases the polarity of O-H bond.
Q. m-nitrophenol is less acidic than o-nitrophenol and p-nitrophenol. Why?
This is because resonance is not possible at meta position hence nitro group at meta position can
withdraw electron only by inductive effect which is less effective than resonance. Whereas nitro group
at ortho and para position withdraw electron by resonance effect hence it can increase the stability of
phenoxide to greater extent.
Q. o-nitro phenol is less acidic than p-nitrophenol. Why?
The intramolecular hydrogen bonding in ortho nitro phenol reduces the extent of ionisation.
Q. p-cresol (4-methylphenol) is less acidic than phenol. Why?
Methyl group is electron releasing hence it decreases acidic strength by (i) decreasing the stability of
phenoxide by concentrating the negative charge on oxygen (ii) decreasing the polarity of O-H bond.
2) Esterification (or) Acylation:
The introduction of acyl (RCO) group in alcohols and phenols to form ester is known as acylation
reaction or esterification reaction. Carboxylic acids, acid chlorides and acid anhydrides are used as
acylating agents. Eg.,
H+
R-OH + R‫׀‬-COOH R-OCOR‫ ׀‬+ H2O
(i) Acetylation:
The introduction of acetyl (CH3CO) group in alcohols and phenols is known as acetylation
reaction. H+
CH3CH2OH + CH3COOH CH3COOC2H5 + H2O

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 H+
CH3CH2OH + (CH3CO)2O CH3COOC2H5 + CH3COOH
Acetic anhydride Ethyl acetate

C6H5OH + CH3COCl Pyridine CH3COOC6H5 + HCl

Acetyl chloride Phenyl acetate
Aspirin is produced by acetylation of salicylic acid. Aspirin is an analgesic (reduces pain), anti-
inflammatory and antipyretic (reduces fever). IUPAC name of aspirin is 2-acetoxybenzoic acid.
COOH COOH
OH OCOCH3
H+
+ (CH3CO)2O + CH3COOH

Salicylic acid Acetyl salicylic acid (Aspirin)

(ii) Benzoylation:
The introduction of benzoyl (C6H5CO) group in alcohols and phenols is known as benzoylation
reaction. H+
C2H5OH + C6H5COOH C6H5COOC2H5 + H2O
Benzoic acid Ethylbenzoate
Q. Acylation with carboxylic acid and anhydride is carried out in the presence of H+ (or) small amount
of concentrated sulphuric acid. Why?
The reaction is reversible. The acid is used to remove the side product water and to shift the
equilibrium in forward direction.
Q. Acylation with acid chloride is carried out in the presence of a strong base like pyridine. Why?
The reaction is highly reversible. The base pyridine is used to neutralise the side product HCl and
thus to shift the equilibrium to the right.
Reactions involving cleavage of C-O bond:
1) Reaction with HX:
Alcohols react with HX to form alkyl halides.
R-OH + HX → R-X + H2O
Lucas test:
This test is used to distinguish primary, secondary and tertiary alcohols and it is based on their
difference in reactivity.
The alcohol is treated with Lucas reagent which is a mixture of con. HCl and anhydrous ZnCl2.
Alcohol is soluble in Lucas reagent whereas the product chloroalkane in insoluble and produce
turbidity.
If the turbidity appears immediately, it is tertiary alcohol. If the turbidity appears after 5-10
minutes, it is secondary alcohol. If turbidity is not produced at room temperatue but produced only on
heating, it is primary alcohol.

11
2) Dehydration:
Alcohols on heating with concentrated H2SO4 or H3PO4 or catalyst like anhydrous ZnCl2 or
alumina undergo dehydration to form alkene.
Ethanol undergoes dehydration at 443 K in the presence of conc. H2SO4 to form ethene. Secondary
and tertiary alcohols undergo dehydration under mild conditions because they are more reactive.
H2SO4
CH3CH2OH CH2=CH2 + H2O
443 K

85% H3PO4
CH3CH(OH)CH3 CH3-CH=CH2 + H2O
440 K
CH3
20% H3PO4
CH3-C-OH CH3-C=CH2 + H2O
358 K
CH3 CH3
The rate of dehydration follows the order; tertiary > secondary > primary. This is due to decreasing
order of stabilities of the respective carbocation intermediates.
Q. Tertiary alcohol is the most reactive to dehydration. Why?
Tertiary carbocation is the most stable hence it is readily formed from tertiary alcohol.
Mechanism of dehydration of ethanol at 443 K to form ethene:
The mechanism involves three steps
Step 1: Formation of protonated alcohol.
CH3-CH2-OH + H+ → CH3-CH2-OH2+
Step2: Formation of carbocation. It is the slow step and hence the rate determining step.
CH3-CH2-OH2+ → CH3-CH2+ + H2O
Step3: Deprotonation to form alkene
CH3-CH2+ → CH2=CH2 + H+
3) Oxidation of alcohols:
(i) Primary alcohols are oxidised to aldehydes and then to carboxylic acids by stronger oxidising
agents like acidified potassium permanganate (KMnO4/H+), acidified potassium dichromate
(K2Cr2O7/H+) and chromic acid (H2CrO4)
(O) (O)
CH3CH2OH CH3CHO CH3COOH
(ii) Controlled oxidation:
In order to stop the oxidation at aldehyde, the following mild oxidising reagents are used.
(1) Pyridinium chloro chromate (PCC) in dichloromethane as solvent. PCC is a complex of pyridine
with chromium trioxide and HCl. PCC does not affect double bond. It oxidises primary alcohols to
aldehydes and secondary alcohols to ketones.

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(2) Anhydrous CrO3. It also oxidises primary alcohols to aldehydes and secondary alcohols to
ketones.
PCC
CH3-CH=CH-CH2-OH CH2Cl2 CH3-CH=CH-CHO

CH3CH(OH)CH3 Anhyd.CrO3 CH3COCH3

Propan-2-ol Propanone
(iii) Ketones are not easily oxidised. But under vigorous conditions, ketones are oxidised to a mixture
of carboxylic acids.
KMnO4/H+
CH3COCH2CH2CH3 CH3COOH + CH3CH2COOH
High temperature
(iii) Tertiary alcohols do not undergo oxidation under normal condition but under vigorous condition
they get oxidised to a mixture of carboxylic acids with less number of carbon atoms.
4) Dehydrogenation:
When the vapours of primary and secondary alcohols are passed through copper tube at
573 K, they undergo dehydrogenation. Primary alcohol gives aldehyde and secondary alcohol gives
ketone.
Cu
CH3-CH2-OH CH3-CHO
573 K
CH3CH(OH)CH3 Cu CH3COCH3
Propan-2-ol 573 K Propanone
Tertiary alcohols do not undergo dehydrogenation due to absence of alpha hydrogen but undergo
dehydration to form alkenes.
CH3
Cu
CH3-C-OH CH3-C=CH2 + H2O
573 K
CH3 CH3
Reactions of phenol:
1) Electrophilic aromatic substitution:
OH group in phenol is strongly activating and ortho/para directing.
(i) Nitration:
(a) Mononitration: Phenol when treated with dilute nitric acid gives a mixture of ortho and para nitro
phenols.
OH OH OH
NO2
Dilute HNO3
+
NO2
Phenol o-Nitrophenol p-Nitrophenol

13
 (b) Trinitration:
Phenol when treated with concentrated nitric acid gives 2,4,6-trinitrophenol also known as picric
acid. OH
OH ON NO2
2
Conc. HNO3
Picric acid
NO2

Q. Ortho and para nitro phenols can be separated by steam distillation. Why?
In o-nitrophenol there is intramolecular hydrogen bonding hence force of attraction between the
molecules is weak Van der waal’s force of attraction. Hence it is volatile in steam.
Whereas p – nitrophenol is associated by intermolecular hydrogen bonding hence large amount of
energy is required to break the hydrogen bonds. Therefore it is non-volatile in steam. Also it has
higher boiling point than o-nitrophenol.
(ii) Halogenation:
(a) Monosubstitution (or) monobromination:
Phenol when treated with Br2 in a solvent of low polarity i.e. organic solvent like CS2 or CCl4
gives a mixture of ortho and para bromo phenols.
OH OH OH
Br
Br2
CHCl3/CS2
Br
Phenol o-Bromophenol p-Bromophenol
(b) Trisubstitution (or) tribromination: Phenol when treated with aqueous bromine gives 2,4,6-
tribromophenol. OH
OH Br Br
Br2/H2O

Br
2) Kolbe’s reaction:
Sodium phenoxide when treated with CO2 followed by acidification gives salicylic acid.
OH ONa OH
COOH
NaOH (i) CO2
Salicylic acid (or)
(ii) H+ 2-Hydroxy benzoic acid

14
3) Reimer-Tiemann reaction:
Phenol when when treated with chloroform and alkali followed by acidification gives
salicylaldehyde.
OH ONa ONa OH
CHCl2 CHO CHO
CHCl3 + NaOH NaOH H+

Salicylaldehyde (or)
Intermediate 2-Hydroxy benzaldehyde
4) Reaction with zinc dust:
Phenol when heated with zinc dust gives benzene.
OH

Zn

Oxidation of phenol:
Phenol is oxidised to benzoquinone by chromic acid (or) acidified potassium permanganate (or)
acidified potassium dichromate.
OH O

Na2Cr2O7
H2SO4 Benzoquinone

O
Phenols are oxidised by air to give a dark coloured mixture containing quinones.
Commercially important alcohols:
Methanol and ethanol are the two commercially important alcohols:
Methanol is also known as wood spirit because it was produced by destructive distillation of wood.
(i) Commercial synthesis of methanol from water gas:
Methanol is produced by catalytic hydrogenation of carbon monoxide at 573 – 673 K and at 200 –
300 atm pressure and in the presence of ZnO – Cr2O3 catalyst.
ZnO – Cr2O3
CO + 2H2 CH3OH
573 – 673 K
200 – 300 atm

Methanol is highly poisonous. Even when taken in small quantities it causes blindness and and in
large quntities causes death. It is used as a solvent in paints, varnishes and for making formaldehyde.
(ii) Commercial synthesis of ethanol:

15
 Ethanol is manufactured by fermentation of sugar in molasses, sugarcane or in grapes using yeast.
Grapes are the source of sugar for making wine. Fermentation is anaerobic process because yeast
converts sugar to ethanol in the absence of oxygen.
The enzyme invertase present in yeast converts sugar into glucose and fructose.
Invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
Another enzyme zymase present in yeast converts glucose and fructose into ethanol and CO2.

Zymase
C6H12O6 2C2H5OH + 2CO2
Ethanol produced by fermentation is very dilute. It is purified by fractional distillation until
95% (v/v) of ethanol is produced. Remaining water is removed by using conc. H2SO4.
95% (v/v) of ethanol in water is known as rectified spirit or rectified alcohol.
100 % pure alcohol is known as absolute alcohol or absolute spirit.
Commercial ethanol is mixed with pyridine (which is foul smelling and poisonous) and copper
sulphate (which gives blue colour) to make it unfit for drinking. This is known as denatured spirit and
the process is known as denaturation of alcohol.
If ethanol is mixed with methanol (which is a poison), it is known as methylated spirit.
Ethanol is used in alcoholic beverages, as solvent in paint industry, as fuel etc
Q. Fermentation must be done only in anaerobic condition. Why?
In the presence of air ethanol is oxidised to ethanoic acid which spoils the taste of alcoholic drinks.
Preparation of ethers:
1) By dehydration of alcohols:
Ethanol is dehydrated in the presence of sulphuric acid at 413 K to give diethyl ether.
H2SO4
2 CH3CH2OH CH3CH2OCH2CH3 + H2O
413 K
Mechanism of dehydration of ethanol at 413 K to form diethyl ether:
The mechanism involves three steps
Step 1: Formation of protonated alcohol:
CH3-CH2-OH + H+ → CH3-CH2-OH2+
Step2: Nucleophilic attack on protonated alcohol:
+
CH3CH2OH + CH3-CH2-OH2+ → CH3-CH2-O-CH2-CH3 + H2O
Nucleophile Electrophile H
Step3: Deprotonation to form ether:
+
CH3-CH2-O-CH2-CH3 → CH3-CH2-O-CH2-CH3 + H+
H

16
Limitations of bimolecular dehydration of alcohols to form ethers.:
(i) Secondary and tertiary alcohols cannot be used to get ethers because they dehydrate to give alkenes
as major product.
(ii) This method is not suitable to prepare unsymmetrical ethers because when two alcohols are used,
the reaction gives mixture of many products which are difficult to be separated.
Q. Bimolecular dehydration is not appropriate for the preparation of ethyl methyl ether. Explain?
The reaction gives mixture of many products which are difficult to be separated.
2) Williamson synthesis:
Alkyl halides react with sodium alkoxide to produce ethers.
R-X + RꞋ - ONa → R-O-RꞋ + NaX
CH3CH2Br + CH3ONa → CH3CH2-O-CH3 + NaX

Limitations of Williamson synthesis:

(i) In order to prepare unsymmetrical ethers containing a secondary or tertiary alkyl group, a primary
halide must be used with a secondary or tertiary alkoxide.
Example, in order to prepare tert-butyl ethyl ether, ethyl halide must be treated with sodium
tert-butoxide.

CH3 CH3
CH3-C-ONa + CH3CH2Br → CH3-C-O-CH2CH3 + NaBr
CH3 CH3
Sodium tert-butoxide tert-butyl ethyl ether
Secondary and tertiary halides cannot be used because in the presence of alkoxide which is a stronger
base, secondary and tertiary halides undergo elimination to give alkenes as major product. Example,

CH3 CH3
CH3-C-Br + CH3CH2ONa CH3-C=CH2 + CH3CH2OH + NaBr
CH3

tert-butyl alcohol sodium ethoxide 2-methylpropene

(ii) In order to prepare aryl alkyl ethers, alkyl halides must be treated with sodium phenoxide. Eg.,
ONa OCH3
+ CH3Br → + NaBr

Sodium phenoxide Methoxy benzene (Anisole)

While preparing aryl alkyl ethers, aryl halides should not be used because aryl halides do not
undergo nucleophilic substitution reaction.

17
Reactions of ethers:
1) Cleavage of C-O bond in ethers: Reaction with HX
(i) When ethers are treated with HX in equal mole ratio, an alkyl halide and an alcohol are produced.
R-O-R + HX → RX + ROH
(ii) When ethers are treated with excess of HX, two moles of alkyl halides are produced.
R-O-R + 2 HX → 2 RX + H2O
Product formation in case of unsymmetrical ethers:
(i) If there is no tertiary alkyl group, then the halogen goes with smaller alkyl group. Example,
CH3-O-CH2-CH3 + HI → CH3-I + CH3-CH2-OH
Reason: The reaction follows SN2 mechanism. Hence the halide attacks the carbon with lesser steric
hindrance.

(ii) If there is a tertiary carbon, then halogen goes to tertiary carbon producing a tertiary halide.
Example,
CH3 CH3
CH3-C-O-CH3 + HI → CH3-C – I + CH3-OH
CH3 CH3

Reason: The reaction follows SN1 mechanism if there is a tertiary alkyl group. In the first step a
tertiary carbocation is formed and halide attacks the tertiary carbon in the second step leading to the
formation of tertiary halide.

(iii) In alkyl aryl ethers, the halogen combines with alkyl group forming alkyl halides. Example,

OCH3 OH
+ HI → + CH3-I

Reason: The phenyl carbon-oxygen bond has partial double bond character due to resonance hence its
cleavage is difficult. Moreover the halide ion is sterically hindered by benzene ring therefore it attacks
the alkyl group.
The order of reactivity of hydrogen halides: HI >HBr>HCl> HF
This is due to increase in bond enthalpy.
HI is the most reactive due to low bond enthalpy.
Electrophilic aromatic substitution:
Alkoxy group in aromatic ethers is activating and ortho/para directing. Para isomer is the major
product due to lesser steric hindrance.
(i) Nitration:

18
 Anisole when treated with a mixture of concentrated nitric acid and concentrated sulphuric acid
(Nitrating mixture) gives a mixture of o-nitroanisole and p-nitroanisole.
OCH3
OCH3 OCH3
NO2
Con. H2SO4
+ Con. HNO3 +
NO2
Major product
(ii) Halogenation:
Anisole when treated with bromine in acetic acid gives a mixture of o-bromoanisole and
p-bromoanisole.
OCH3 OCH3 OCH3
Br
CH3COOH
+ Br2 +

Br
Major product
(iii) Sulphonation:
Anisole when treated with concentrated sulphuric acid gives a mixture of o-methoxy
benzenesulphonic acid and p-methoxy benzenesulphonic acid. OCH3
OCH3 OCH3
SO3H
Con. H2SO4
SO3H
Major product
(iv) Friedel – Crafts alkylation of anisole:
Anisole when treated with chloromethane in the presence of anhydrous AlCl3 gives a mixture of
o-methoxy toluene and p-methoxy toluene.
OCH3
OCH3 OCH3
CH3
Anhyd. AlCl3
+ CH3Cl +
CH3
Major product

19
(iv) Friedel – Crafts acylation of anisole:
Anisole when treated with acetyl chloride in the presence of anhydrous AlCl3 gives a mixture of
2-methoxy acetophenone and 4-methoxy acetophenone. OCH3
OCH3 OCH3
COCH3
Anhyd. AlCl3
+ CH3COCl +
COCH3
Major product
Q. Commercially, acids are converted to esters and then reduced to alcohols. Why?
Carboxylic acids are reduced by LiAlH4 which is an expensive reagent. But esters can be reduced
by cheaper reducing agent like Ni/H2. Hence to make the process economical, acids are converted to
esters and then reduced to alcohols.
Q. Boiling points of ethers are much lower than the isomeric alcohols. Why?
Ethers have only weak dipole-dipole forces whereas alcohols have stronger intermolecular
hydrogen bonds.
Q. Lower ethers are soluble in water. Why?
Lower ethers can form hydrogen bonds with water hence they are soluble.
Q. -OH group in phenol is ortho and para directing towards electrophilic aromatic substitution. Why?
Hydroxy group is electron releasing by resonance effect and by releasing electrons it increases the
electron density at ortho and para positions.
Q. -OH group in phenol is strongly activating towards electrophilic aromatic substitution. Why?
Hydroxy group is electron releasing by resonance effect and by releasing electrons it increases the
overall electron density in benzene. Hence it increases the reactivity.
Q. Alkoxy group (-OR) in aromatic ethers is ortho and para directing towards electrophilic
substitution. Why?
Alkoxy group is electron releasing by resonance effect and by releasing electrons it increases the
electron density at ortho and para positions.
Q. Alkoxy group (-OR) in aromatic ethers is strongly activating towards electrophilic substitution.
Why?
Alkoxy group is electron releasing by resonance effect and by releasing electrons it increases the
overall electron density in benzene. Hence it increases the reactivity.
Q. Phenol undergoes bromination even in the absence of catalyst FeBr3. Why?
Because the -OH group in phenol is electron releasing by resonance and strongly activating.
Q. Anisole undergoes bromination even in the absence of catalyst FeBr3. Why?
Because the methoxy group in anisole is electron releasing by resonance and strongly activating.
Q. What are the harmful effects of ethanol?
Ethanol acts on the central nervous system hence it reduces the ability to thing and causes brain
damage. At higher concentration, it causes nausea, loss of consciousness and even death.

20
Q. Give one use of diethyl ether.
Diethyl ether was widely used as general anaesthetic but because of its slow effect and unpleasant
recovery period it is replaced by better anaesthetics.
Q. Give a chemical test to distinguish phenol from ethanol.
Phenol gives violet colour with neutral FeCl3 solution whereas ethanol doesn’t.
Q. Explain the mechanism of the following reaction
CH3-CH2OH + HBr → CH3-CH2Br + H2O
Step1: Protonation of alcohol
CH3-CH2-OH + H+ → CH3-CH2-OH2+
Step2: Formation of carbocation
CH3-CH2-OH2+ → CH3-CH2+ + H2O
Step3: Attack of Br—
CH3-CH2+ + Br-- → CH3-CH2Br
Q. Write the mechanism of the reaction of HI with methoxy methane.
Step 1: Protonation of methoxymethane
CH3-O-CH3 + H-I → CH3-OH+-CH3 + I—
Step 2: Nucleophilic attack of I— (SN2 reaction)
I— + CH3-OH+-CH3 → CH3I + CH3-OH

21
 Questions:

1 Write all possible isomers of C4H10O and give their common and IUPAC names.
2 Draw the structures of all isomeric alcohols of molecular formula C5H12O and give their IUPAC
names. Also classify them as primary, secondary and tertiary alcohols.
3 Give the IUPAC names of the following:
(i) CH3CH(Cl)CH(CH3)CH2CH2CH2OH (ii) CH3-CH=CH-CH(C2H5)-CH2OH
(iii) CH3CH2OC(CH3)3 (iv) CH3CH(CH3)-O-CH2CH2C(CH3)2CH(OH)CH3
(v) CH3CH2OCH(CH3)CH(OH)CH(C2H5)CH2CH2Cl (vi) C6H5-O-C8H17(iso)
(vii) Ethyl sec-butyl ether (viii) CH3-C = C –CH2-OH (ix) CH2=CH-CH-(CH2)3-CH3
Br CH3 OH
CH2-OH NO2
(x) CH3-CH2-CH-CH-CH-CH3 (xi) CH3OCH2CH2CH2CH2OCH2CH3 (xii)
CH2Cl CH3 OC2H5

CH3 CH3 OH CH3 CH3

CH3 CH3
(xiii) OC2H5 (xiv) (xv) C2H5O- -OH (xvi)
OH
CH3
CH3
(xvii) CH3-O-CH2-CH-CH-O-CH3 (xviii) (CH3)3C-O-C-CH2-CH2-CH2-CH-O-CH3
CH3 CH3 CH3 CH3

(xix) HO-CH2-CH-CH2-OH (xx) CH3-CH= CH-CH-CH2-CH-CH2-CH3

OH OH CH2OH

4 Write the structure of the following:

(i) 2-Methylbutan-2-ol (ii) 1-Phenylpropan-2-ol (iii) 3,5-Dimethylhexane-1,3,5-triol
(iv) 1-Ethoxypropane (v) 2-Ethoxy-3-methylpentane (vi) Cyclohexylmethanol
(vii) 3-Cyclohexylpentan-3-ol (viii) Cyclopent-3-en-1-ol (ix) 1-phenoxyheptane
(x) 2-Chloromethylcyclopentanol (xi) 2-(3-Chlorophenyl)pent-2-en-1-ol (xii) diisopropyl ether.
5 Predict the products expected from the following reactions:
(i) Catalytic reduction of butanal.
(ii) Catalytic reduction of butanone
(iii) Catalytic hydration of cyclohexene.
(iv) Hydration of but-1-ene in the presence of dil. H2SO4
(v) Reaction of propanal with methyl magnesium bromide followed by hydrolysis.
(vi) Reaction of butanone with methyl magnesium bromide followed by hydrolysis.
(vii) Reaction of but-1-ene with diborane followed by oxidation with alkaline H2O2.
22
6 Using a suitable Grignard reagent show how will you prepare the following alcohols.
(i) n-butyl alcohol (ii) isobutyl alcohol (iii) sec-butyl alcohol (iv) tert-butyl alcohol
(v) tert-pentyl alcohol (vi) Benzyl alcohol (vii) Cyclohexyl methanol
(viii) 1-phenylethanol (ix) Pentan-1-ol (x) Diphenyl methanol
7 Write the structure of the major product of the following reactions:
(i) B2H6
(i) CH3-CH=CH2 H2O/H+ (ii) CH3-CH=CH2 (ii) H O /OH—
2 2
O
CH2 C OCH3 NH2
NaBH4 (i) HNO2
(iii) O (iv)
(ii) Warm H2O

NaBH4 NaBH4
(v) CH3-CH2-COOCH2-CHO (vi) CH3-CH2-CH-CHO
CH3
(vii) CH3-CH-MgBr + CH3-CHO ? H2O/H+ ?
CH3
8 Arrange the following in increasing order of their boiling points:
(i) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol and methanol
(ii) Butan-1-ol, n-butane, butanal, ethoxyethane, butan-2-one
9 Arrange the following in the increasing order of their acidic strength
Ethanol, propan-1-ol, isopropyl alcohol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol,
2,4-dinitrophenol, tert-butyl alcohol, 4-methylphenol and phenol
10 Write the structure of the major product expected from the following reactions:
(i) Mononitration of 3-methylphenol (ii) Dinitration of 3-methylphenol
(iii) Mononitration of phenyl methanoate (iv) Monobromination of phenyl ethanoate
(v) Mononitration of methyl benzoate
11 Using suitable reactant write equations for the preparation of the following ethers by
Williamson synthesis:
(i) 1-Propoxypropane (ii) Ethoxy benzene (iii) Methoxyethane (iv) 2-methoxypropane
(v) 2-Methoxy-2-methylpropane
12 Give a chemical test to distinguish the following pairs of compounds:
(i) tert-butyl alcohol and isopropyl alcohol (ii) Propan-1-ol and propan-2-ol
(iii) Phenol and cyclohexanol (iv) phenol and ethanol

23
13 Write the major products formed by heating the following ethers with HI
(i) 1-Ethoxypropane (ii) Methoxyethane (iii) Anisole (iv) Phenetole
(v) 1-Propoxypropane (vi) 2-Ethoxypropane (vii) tert-butyl ethyl ether
(viii) Benzyl phenyl ether (ix) Allyl vinyl ether (x) Cyclohexyl methyl ether

CH3
(xi) CH3-CH2-CH-CH2-O-CH2-CH3 (xii) CH3-CH2-CH2-O-C-CH3
CH3 CH3

(xiii) C6H5-CH2-CH-O-C6H5 (xiv) O

CH3

14 Predict the products in the following:

(i) CH3-CH2-CH2-O-CH3 + HBr
OC2H5 OC2H5
CH3COOH
(ii) + HBr (iii) + Br2

OC2H5
(iv) Con.HNO3 (v) (CH3)3C-OC2H5 + HBr
Con. H2SO4

Con. H2SO4
(vi) CH3-CH2-CH(OH)-CH3

(vii) CH3-CH2-CH(Br)-CH3 + CH3-CH2ONa

15 How is 1-propoxypropane synthesised from propan-1-ol? Write the mechanism for this reaction.
16 Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol
And 3-methylpentan-2-ol
17 Which of the following is an appropriate set of reactants for the preparation of 1-methoxy-4-
nitrobenzene and why?
Br ONa

(i) + CH3ONa (ii) + CH3Br

NO2 NO2

24
18 The following is not an appropriate reaction for the preparation of t-butyl ethyl ether.
CH3 CH3
CH3-C-Cl + CH3CH2ONa → CH3-C-O-CH2CH3 + NaCl
CH3 CH3

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

(ii) Write a suitable reaction for the preparation of t-butyl ethyl ether.
19 Predict the major product of acid catalysed dehydration of the following
(i) 1-Methylcyclohexanol (ii) Propan-1-ol (iii) Butan-2-ol
20 Give the structures of the products when butan-1-ol reacts with
(i) HCl-ZnCl2 (ii) HBr (iii) SOCl2 (iv) PCl5 (v) Red P4-I2 (vi) Na (vii) Con.H2SO4
21 Show how would you synthesise
(i) 1-Phenylethanol from suitable alkene (ii) Cyclohexyl methanol using an alkyl halide by SN2
reaction. (iii) Pentan-1-ol using a suitable alkyl halide (iv) Pentan-1-ol using a suitable alkene
(v) Pentan-2-ol using a suitable alkene. (vi) Phenol from benzene (vii) Aspirin from Phenol
22 Show how would you synthesise the following from a suitable alkene:
OH OH OH
(i) CH3 (ii) (iii) OH (iv)

OH
OH
(v) (vi) (vii)
OH
23 Name the reagent used in the following reactions:
(i) Oxidation of primary alcohol to carboxylic acid
(ii) Oxidation of primary alcohol to aldehyde
(iii) Dehydration of propan-2-ol to propene
(iv) Bromination of phenol to 2,4,6-tribromophenol
(v) Benzyl alcohol to benzoic acid
(vi) Benzyl alcohol to benzaldehyde
(vii) Cyclohexanol to cyclohexanone
(viii) Cyclohexanol from cyclohexanone
(ix) Allyl alcohol to acrolein (propenal)
(x) Anisole to 4-methoxyacetophenone
24 Effect the following conversions:
(i) Propan-2-ol from Propene
(ii) Propan-1-ol from Propene
(iii) Propanal to propan-1-ol
(iv) Benzyl chloride to benzyl alcohol
(v) Methanol to ethanol

25
 (vi) Methanol to propan-2-ol
(vii) Methyl magnesium bromide to 2-methylpropan-2-ol
(viii) Ethyl magnesium chloride to propan-1-ol
(ix) Butanone to butan-2-ol
(x) Propanone to tert-butyl alcohol.
25 Write chemical equations for the following
(i) Friedel-Craft’s alkylation of anisole
(ii) Friedel-Craft’s acylation of phenetole
(iii) Cumene converted to phenol
(iv) Phenetole converted to 4-ethoxybenzenesulphonic acid
(v) Phenol converted to toluene
26 Now a days picric acid is prepared by converting phenol to phenol-2,4-disulphonic acid and
then with concentrated nitric acid to get 2,4,6-trinitrophenol. Write equations for the same.
27 When 3-methylbutan-2-ol is treated with HBr, 2-bromo-2-methylbutane is formed as major
product. Give a suitable mechanism for this reaction.

26