Phenol (Hydroxybenzene)

Phenols are compounds in which the hydroxyl group is attached to an aromatic ring.
Their general formula is:
OH

phenol

Preparation of phenols
Laboratory preparation
i. Sulphonation of benzene and subsequent alkali fusion
SO 2 OH OH
conc H2SO4 i. NaOH
ii. H+

ii. Hydrolysis of benzene Diazonium Salts

+
NH2 N N OH
HCl+NaNO2 H2O
273 - 278 K Warm

benzenediazonium ion phenol

iii. From cumene

This starts with benzene and propene, which are both produced in oil refineries by the
cracking of petroleum.
CH3
H3C CH3
CH H3C C O O H OH

H3PO4 O2 (Air) dil. H2SO4

+ CH3CH CH2 250 C

prop-1-ene
benzene (propan-2-yl)benzene 2-phenylpropane-2-peroxol phenol

iv. From haloarene

- + OH
Cl O Na

+ NaOH 623K
300atm
HCl

Chemical properties of phenols

Phenols undergoes two types of reaction.
- Reactions involving the hydroxyl group
- Electrophilic substitution of the aromatic ring.
-
1. Reaction involving the hydroxyl group
i. Acidity
Phenols are stronger acids than the alcohols. This is due to
+M effect of the hydroxyl group which facilitates the release of a proton from the
hydroxyl group by delocalizing the negative charge which is produced on the oxygen
atom.
Mechanism

ii. Williamsons Ether synthesis

Phenol in an alkaline solution reacts with haloalkanes to give ether.
The presence of an alkali leads to the formation of the phenoxide ion, which then
acts as a nucleophile, attacking the haloalkane.

- + CH2 R
O Na O
NaOH(aq)
+ R CH2 X + Na X

Example
- + CH2 CH3
O Na O
NaOH(aq)
+ CH3 CH2 Cl + NaCl

ethoxybenzene

Sometimes in this reaction side-reaction may occur due to the +M activating effects
of the oxide anion in the phenoxide ion thus, alkylation.

iii. Esterification
Phenol form esters with acid chlorides and acid anhydride under alkaline condition.
O
O
-
OH O O C R
R C
+ Cl
+ NaOH(aq) Na + NaCl

phenyalkanoate
(Ester)

Note
Phenol does not reacts with carboxylic acids under those condition which favour
esterification of the alcohols.

iv. Displacement of hydroxyl group

Phenols do not react with hydrogen halides.
They react only very slowly with PCl5 giving a very poor yield.
Hence, the reaction is of no practical use.
OH Cl

+ PCl5 + POCl3 + HCl

chlorobenzene
(Very poor yield)

v. Complex formation with FeCl3 solution

Phenols reacts with neutral 3 solution to give coloured complexes which can be
used as identification test.
 OH -
O

+ FeCl3 Fe + 3HCl
3

In this case the complex has purple colour, green then brown colour or brown-red colour.

vi. Reduction
Phenols is reduced by zinc dust to form benzene.
OH
distil
+ Zn (dust) + ZnO

vii. Formation of phenylamine

Phenols reacts with ammonia under high pressure to yield phenylamine.
OH NH2
NH3 high pressure
+ + ZnO

2. Electrophilic substitution into the ring

Due to +M effect, the hydroxyl group activates the ring towards electrophilic substitution at
the 2 ,4 ,6 .
i. Halogenation
Phenols reacts readily with aqueous solutions of the halogens like bromine water.
A catalyst is not required due to strongly activating +M effect of the hydroxyl
substituent.

OH OH
Br Br

+ 3Br2 (aq) + 3HBr

Br
2,4,6-tribromophenol
(white precipitste)

- Monohalogenation can be achieved if a carefully calculated amount of the halogen is

dissolved in glacial ethanoic acid.
Example

OH OH OH
Br
Ethanoic acid
+ Br2 and + HBr

2-bromophenol
(Minor product) Br
4-bromophenol
(Major product)

ii. Alkylation
 a) Friedel-Crafts alkylation ( , 3 ) under normal process cannot be carried
out on phenols, because of the two nucleophilic sites in a phenol, the oxygen
atom and the aromatic ring.
Instead nucleophilic substitution by the phenoxide ion on the haloalkane results
into an aromatic ether (Williamsons ether synthesis reaction).

- + CH2 R
O Na O
NaOH(aq)
+ R CH2 X + Na X

Example
- + CH2 CH3
O Na O
NaOH(aq)
+ CH3 CH2 Cl + NaCl

ethoxybenzene

b) Alkylation under warmed alcohol or alkene.

This reaction prevent the oxygen atom form acting as a nucleophile.
Phenol gently warmed with an alcohol or alkene in the presence of sulphuric
acid to form alkylated phenols.
OH OH

and + H2O
R R
OH
OH R-
H2SO 4
R
-1C
H=
CH OH OH
2
and
CH CH3 CH CH3
1 1
R R

Note
The presence of an acid catalyst prevents the phenol from dissociating. The high concentration of
hydrogen ions from the acid does not favour the release of a proton from the phenolic hydroxyl
group, thus the phenoxide ion is not formed and so it cannot act as a nucleophile.
iii. Acylation
This reaction experience similar difficulties to alkylation involving nucleophilic
attack by a phenoxide ion on the acid chloride to form phenylalkanoate esters.
However, under large excess of aluminium trichloride is used, a reasonable yield can
be achieved.
OH
O
OH OH
(excess AlCl 3) and
and HCl
+ R C
Cl C O O C
R R
2-and 4-hydroxyphenylalkanone
- A phenolic ketones (Acylation of phenol) can be prepared by Fries reaction which involves
two step and complicated mechanism.
First is the reaction of phenol with an acid anhydride under alkaline conditions
Second stage involves aluminium trichloride as a catalyst and is carried out in carbon
disulphide.

OH OH OH
I. (R -CO)2O, II.(excess AlCl3)
and
+ aq NaOH CS2, 35 C
C O O C
R R
2-and 4-hydroxyphenylalkanone

iv. Nitration
Phenols reacts with dilute nitric acid under room temperature to form mono-
nitration.
This strongly activating effect of the phenolic hydroxyl group means no catalyst is
required.

OH OH OH
NO2
25 C
+ 2HNO3(aq) + + H2 O

2-Nitrophenol
(Minor product) NO2
4-nitrophenol

Also
Phenols reacts with concentrated nitric acid under room temperature to form tri-
nitration, giving 2,4,6 .
OH OH
NO2 NO2
25 C
+ 3HNO3(Conc) + 3H2O

NO2
2,4,6-trinitrophenol

v. Sulphonation
Phenol reacts with ordinary concentrated sulphuric acid without any catalyst like
fuming sulphuric acid for sulphonation like in benzene, since it phenol is more
reactive than benzene.
At room temperature
The 2 will be the major product due to the formation of the hydrogen bond
between the sulphonyl and hydroxyl groups.
 OH OH
conc H2SO4
+ 25 C
+ H2O
SO 3 H
At high temperature
The 4 will be formed as the major product.

OH OH
conc H2SO4
+ 100 C
+ H2 O

SO 3 H

vi. Aldehyde and acid formation

Phenols boiled with trichloromethane (chloroform) in a 40% solution of sodium
hydroxide and then acidified with dilute acid to form
.

OH OH OH
i) NaOH(aq), CHCl3, boil
ii) Dilute HCl and

C O O C
H H
2-hydroxybenzaldehyde

Phenols boiled with tetrachloromethane in a 40% solution of sodium hydroxide and

then acidified with dilute acid to form 2 hydroxybenzoic acid.
OH OH
i) NaOH(aq), CCl4, boil
ii) Dilute HCl

C O

OH
2-hydroxybenzoic acid

vii. Coupling with Diazonium cation

i) NaOH, < 25 C
ii) HCl
Na O
+ -
+ N N
+
HO N N + NaCl

4-Hydroxyphenylazobenzene

viii. Carboxylation
Sodium phenoxide reacts with carbon dioxide under 130 and 5atm to form
sodium 2 hydroxybenzenecarboxylate which yield the parent acid on acid
hydrolysis.
Example

O Na OH OH
130 C, 5 atm HCl (aq)
+ O C O + NaCl
O O
C C
O OH
Na 2-hydroxybenzoic acid
sodium 2-hydroxybenzoate