Alcohel Phenol

Introduction
In this unit, we shall discuss the chemistry of three classes of

compounds, namely — alcohols, phenols and ethers. Alcohols
and phenols are formed when a hydrogen atom in a
hydrocarbon, aliphatic and aromatic respectively, is replaced
by –OH group. The subsitution of a hydrogen atom in a
hydrocarbon by an alkoxy group (R–O/Ar–O) yields another
class of compounds known as ‘ethers’.
Alcohols and Phenols : Classification
Alcohols and phenols may be classified as mono, di, tri-or

polyhydric compounds depending upon number of hydroxyl
groups respectively in their structures as given below:
1
(i)Compounds Containing Csp3 -OH bond
a) Primary, secondary and tertiary alcohols: In these
three types of alcohols, the –OH group is attached to 1ºC,
2ºC and 3ºC atom respectively.
b) Allylic alcohols: In these alcohols, the –OH group is

attached to a sp3 hybridized carbon next to the carbon-
carbon double bond.
2
(c) Benzylic alcohols: In these alcohols, the –OH group is
attached to a benzylic carbon atom.
(ii) Compounds Containing Csp2 -OH bond
These alcohols contain –OH group bonded to a carbon-carbon

double bond i.e., vinylic carbon or to an aryl
carbon. Ex. Vinylic alcohol : CH2=CH–OH
3
Nomenclature
(a) Alcohols
The common name of an alcohol is derived from the common

name of the alkyl group and adding the word alcohol to it.
Cyclic alcohols are named using the prefix cyclo and

considering the –OH group attached to C–1.
4
(b) Phenols
Alcohols and Phenols
1. Preparation of Alcohols
5
(i). From Alkenes
(A) By acid reflux followed by hydrolysis: Alkenes react

with water in the presence of acid as catalyst. The addition
reaction takes place in accordance of Markovnikov’s rule.
RCH=CH2 + H2O ⟶ RCH(OH)-CH3 + RCH2CH2OH
(B) By hydroboration-oxidation: Diborane reacts with

alkenes to give trialkyl boranes, which is oxidised to alcohol
by H2O2 in alkaline medium to give alcohol.
RCH=CH2 ⟶ RCH2-CH2-OH
(ii). From hydrolysis of alkyl halides
Alkyl halides upon hydrolysis yields alcohol.
RCH2-X ⟶ HO-CH2R
(iii). From carbonyl compounds
(A) By reduction of aldehyde and ketones: Aldehydes and

ketones can be reduced to the corresponding alcohols by using
reducing agents Pd/H2, LiAIH4, NaBH4.
6
R-CO-H ⟶ RCH2OH
R-CO-R ⟶ R2CH-OH
(B) By Grignard reagent: Addition of Grignard reagent to

carbonyl group is the nucleophilic addition reaction. The
adduct formed upon hydrolysis yields an alcohol.
R2C=O + RMgX ⟶ R2C(OH)-R
(C) From carboxylic acids: Carboxylic acids are reduced to

primary alcohol in excellent yield by lithium aluminium
hydride.
R-COOH + H2O ⟶ RCH2-OH
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2. Preparation of Phenols
Phenols can be prepared from benzene derivatives by any of

the following methods:
(i). From Haloarenes
Chlorobenzene is fused with NaOH at 623 K and 320

atmospheric pressure, phenol is obtained by acidification of
sodium phenoxide.
(ii). From diazonium salt
Diazonium salts are hydrolysed to phenols by warming with

water or by treating with dil.acids.
8
(iii). From benzene sulphonic acid
Benzene sulphonic acid is fused with NaOH. Acidification of

the sodium salt gives phenol.
(iv). From cumene
Cumene is oxidised in air to form cumene hydroperoxide. It is

converted to phenol and acetone by treating with dilute acid.
9
Physical Properties
Alcohols and phenols both are water soluble due to their

ability to form H-bond with water. The solubility decreases
with increase in size of hydrophobic group. Due to the same
reason their boiling points are also greater than corresponding
compounds of similar molecular mass except carboxylic
acids. They are polar and protic in nature.
Chemical Properties
(i) Reaction with metals: Alcohol and phenol reacts with

active metals such as sodium, potassium and aluminium to
yield corresponding alkoxide/phenoxide and hydrogen.
CH3–CH2–OH + Na ⟶ CH3CH3–ONa + 1/2H2
(ii) Acidity of alcohols: The acidic character of alcohols is

due to the polar nature of O–H bond. An electron releasing
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group increases electron density on oxygen tending to
decrease the polarity of –OH bond. This decreases the acid
strength. Hence acidic strength follows the order
(iii) Acidity of phenols: The hydroxyl group of phenol is

directly attached to the sp2 hybridised carbon of benzene ring
which acts as an electron withdrawing group.
(iii) Esterification: Alcohols and phenols both react with

acids, acid chlorides and acid anhydrides to form esters. With
carboxylic acids esterification is carried with little amounts of
conc. H2SO4;
R-OH + R'COOH ⇌ R'COOR + H2O
11
(vi) Reaction with HX: Alcohols reacts with HX to form
alkyl halides
CH3OH + HCl ⟶ CH3Cl + H2O
(vii) Reaction with PCl3 and PCl5
3R—OH + PCl3 ⟶ 3R—Cl + H3PO3
ROH + PCl5 ⟶ R — Cl + POCl3 + HCl
(viii) Reaction with SOCl2
R—OH + SOCl2 ⟶ R—Cl + SO2 + HCl
(ix) Dehydration: Alcohols undergoes dehydration to form

alkene on treating with a protic acid e.g., conc. H 2SO4 and
H3PO4 or Al2O3.
CH3-CH(OH)-CH3 ⟶ CH3-CH=CH2 + H2O
(x) Oxidation: Oxidation state of carbon bearing – OH group

is (–2) so it can be oxidised to aldehydes (Oxidation state = 0)
and carboxylic acids (Oxidation state = +2) by use of suitable
reagents.
RCH2–OH ⟶ RCHO ⟶ R–C(OH)=O

12
(xi) Nitration: With dil. HNO3 acid at low temperature
phenol yields a mixture of –o and p– nitrophenols.
(xii) Halogenation: When phenol is treated with Br2 in

solvents of low polarity such as CHCl3 or CS2 and at low
temperature monosubstituted phenols are formed.
(xiii) Kolbe’s Reaction: Phenol when treated with NaOH it

gives phenoxide ion which is more reactive than phenol,
hence it undergoes electrophilic substitution reaction with
CO2, a weak electrophile. Orthohydroxy benzoic acid is
formed as the main product.
13
(xiv) Reimer-Tiemann Reaction: On treating phenol with
CHCl3 in the presence of NaOH a –CHO group is introduced
at o-position of benzene ring.
(xv) Reaction of phenol with zinc dust: Phenol is converted

to benzene on heating with zinc dust.
(xvi) Oxidation: By application of strong oxidising agents

phenol converts into benzoquinone. In the presence of air
phenols are slowly oxidised to dark coloured mixtures
containing quinones.
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Some Commercially Important Alcohols
1. Methanol
Methanol, CH3OH, 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 – Cr2O3 catalyst.
CO + 2H2 ⟶ CH3-OH
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.
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1. Ethanol
It is obtained commercially by fermentation of sugars. The

sugar is molasses.
C12H22O11 + H2O ⟶ C6H12O6 + C6H12O6
Glucose and fructose undergoes fermentation in the presence

of zymase, which is found in yeast.
C6H12O6 ⟶ C2H5OH + 2CO2
Ethers
Classification
Ethers are classified as simple or symmetrical, if the alkyl or

aryl groups attached to the oxygen atom are the same, and
mixed or unsymmetrical, if the two groups are different.
Diethyl ether, C2H5OC2H5, is a symmetrical ether whereas
C2H5-O-CH3 and C2H5-O-C6H5 are unsymmetrical ethers.
16
Naming of Ethers:
Common names of ethers are derived from the names of

alkyl/aryl groups written as separate words in alphabetical
order and adding the word ether at the end.
C2H5-O-CH3 - Ethylmethyl ether

C2H5-O-C2H5 - Diethyl ether
According to IUPAC system of nomenclature, ethers are

regarded as hydrocarbon derivatives in which a hydrogen
atom is replaced by an –OR or –OAr groups. The larger (R)
group is chosen as the parent hydrocarbon.
C2H5-O-CH3 - Methoxyethane
C2H5-O-C2H5 - Ethoxyethane
Preparation of Ethers
1. By inter-molecular dehydration of alcohols
Alcohols undergo dehydration in presence of protic acid.
RCH2OH + HOCH2R ⟶ RCH2-O-CH2R
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2. Williamson’s synthesis
It is an important method to prepare all types of ether. Alkyl

halide is allowed to react with sodium alkoxide.
RO-Na + X-R ⟶ R-O-R'
Physical Properties
Due to large size of alkyl groups R–O–R bond angle in ethers

is large (>110°) therefore net dipole-moment becomes less
and therefore ethers show:
 (i) Low boiling points

 (ii) Low solubility in water
Solubility in water further decreases with increasing molar

mass of ethers as etheral oxygen becomes more hindered and
become less available to inter-molecular H-bonding with
water.
18
Chemical Properties
(i) Cleavage of C–O bond in ethers: Ethers due to low

polarity are least reactive among other functional groups.
With strong acids they form alkyl halide and alcohols by “C
— O” bond cleavage:
RCH2—O—CH2R + RCH2OH + RCH2—X
(ii) Electrophilic substitution: Aryl ethers show the reactions

like phenols as –OR is also an activating group. The
electrophilic substitution shown by aryl ethers are:
 (a) Halogenation
 (b) Friedel-Crafts Reaction
 (c) Nitration
19
20
Sammury
1. Alcohols and phenols are classified (i) on the basis of

the number of hydroxyl groups and (ii) according to the
hybridisation of the carbon atom, sp3 or sp2 to which the
–OH group is attached.
2. Ethers are classified on the basis of groups attached to
the oxygen atom.
3. Alcohols may be prepared (1) by hydration of
alkenes (i) in presence of an acid and (ii) by
hydroboration-oxidation reaction (2) from carbonyl
compounds by (i) catalytic reduction and (ii) the action
of Grignard reagents.
4. Phenols may be prepared by (1) substitution
of (i) halogen atom in haloarenes and (ii) sulphonic acid
group in aryl sulphonic acids, by –OH group (2) by
hydrolysis of diazonium salts and (3) industrially from
cumene.
5. Alcohols are higher boiling than other classes of
compounds, namely hydrocarbons, ethers and
haloalkanes of comparable molecular masses.
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6. The ability of alcohols, phenols and ethers to form
intermolecular hydrogen bonding with water makes them
soluble in it.
7. Alcohols and phenols are acidic in nature.
8. Electron withdrawing groups in phenol increase its acidic

strength and electron releasing groups decrease it.
9. Alcohols undergo nucleophilic substitution with

hydrogen halides to yield alkyl halides.
10. Dehydration of alcohols gives alkenes.
11. On oxidation, primary alcohols yield aldehydes with

mild oxidising agents and carboxylic acids with strong
oxidising agents while secondary alcohols yield ketones.
12. The presence of –OH group in phenols activates the

aromatic ring towards electrophilic substitution and
directs the incoming group to ortho and para positions
due to resonance effect.
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Alcohel Phenol

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Introduction

In this unit, we shall discuss the chemistry of three classes of

Alcohols and Phenols : Classification

Alcohols and phenols may be classified as mono, di, tri-or

b) Allylic alcohols: In these alcohols, the –OH group is

(ii) Compounds Containing Csp2 -OH bond

These alcohols contain –OH group bonded to a carbon-carbon

The common name of an alcohol is derived from the common

Cyclic alcohols are named using the prefix cyclo and

Alcohols and Phenols

(A) By acid reflux followed by hydrolysis: Alkenes react

RCH=CH2 + H2O ⟶ RCH(OH)-CH3 + RCH2CH2OH

(B) By hydroboration-oxidation: Diborane reacts with

(ii). From hydrolysis of alkyl halides

Alkyl halides upon hydrolysis yields alcohol.

(iii). From carbonyl compounds

(A) By reduction of aldehyde and ketones: Aldehydes and

(B) By Grignard reagent: Addition of Grignard reagent to

R2C=O + RMgX ⟶ R2C(OH)-R

(C) From carboxylic acids: Carboxylic acids are reduced to

R-COOH + H2O ⟶ RCH2-OH

Phenols can be prepared from benzene derivatives by any of

(i). From Haloarenes

Chlorobenzene is fused with NaOH at 623 K and 320

(ii). From diazonium salt

Diazonium salts are hydrolysed to phenols by warming with

Benzene sulphonic acid is fused with NaOH. Acidification of

(iv). From cumene

Cumene is oxidised in air to form cumene hydroperoxide. It is

Alcohols and phenols both are water soluble due to their

(i) Reaction with metals: Alcohol and phenol reacts with

CH3–CH2–OH + Na ⟶ CH3CH3–ONa + 1/2H2

(ii) Acidity of alcohols: The acidic character of alcohols is

(iii) Acidity of phenols: The hydroxyl group of phenol is

(iii) Esterification: Alcohols and phenols both react with

R-OH + R'COOH ⇌ R'COOR + H2O

CH3OH + HCl ⟶ CH3Cl + H2O

(vii) Reaction with PCl3 and PCl5

3R—OH + PCl3 ⟶ 3R—Cl + H3PO3

ROH + PCl5 ⟶ R — Cl + POCl3 + HCl

(viii) Reaction with SOCl2

R—OH + SOCl2 ⟶ R—Cl + SO2 + HCl

(ix) Dehydration: Alcohols undergoes dehydration to form

CH3-CH(OH)-CH3 ⟶ CH3-CH=CH2 + H2O

(x) Oxidation: Oxidation state of carbon bearing – OH group

RCH2–OH ⟶ RCHO ⟶ R–C(OH)=O

(xii) Halogenation: When phenol is treated with Br2 in

(xiii) Kolbe’s Reaction: Phenol when treated with NaOH it

(xv) Reaction of phenol with zinc dust: Phenol is converted

(xvi) Oxidation: By application of strong oxidising agents

Methanol, CH3OH, also known as ‘wood spirit’, was

Methanol is a colourless liquid and boils at 337 K. It is highly

It is obtained commercially by fermentation of sugars. The

C12H22O11 + H2O ⟶ C6H12O6 + C6H12O6

Glucose and fructose undergoes fermentation in the presence

C6H12O6 ⟶ C2H5OH + 2CO2

Ethers are classified as simple or symmetrical, if the alkyl or

Common names of ethers are derived from the names of

C2H5-O-CH3 - Ethylmethyl ether