CHAPTER X

PHENOLS
1) Introduction
2) Nomenclature
4) Physical properties
a) Boiling point (volatility)
b) Solubility in water
5) Preparations
6) Acidity
7) Reactions

INTRODUCTION
Phenols are those aromatic organic compounds which possess an -OH group directly
bonded to an aromatic group. C6H5OH is phenol itself but one can also have
substituted phenols.

The OH group directly bonded to an aromatic system can also be found in some
naturally occurring compounds such as the neurotransmitter serotonin, the vanilla
bean extract vanillin and the hormone adrenalin shown below:

Phenols are also used as disinfectants in house cleaning products and in industry as
intermediates in synthesis. Certain plastics, explosives such as picric acid and the drug
aspirin use phenol as a starting material. In the past, phenol itself was used as an
antiseptic during and following surgery. Phenol is toxic and causes severe burns in
concentrated form.

NOMENCLATURE
The simplest compound in this group is C6H5OH which is called phenol. Molecules
that have an OH and another group bonded to the aromatic ring are named in the
usual way i.e. if the group is usually used as a prefix it is named in this manner whilst
if the group is represented by a suffix, then the OH becomes a ‘hydroxy’.

The ring can also have more than one OH group or multiple groups together with the
OH group.

PHYSICAL PROPERTIES

INSERT BALL STICK MODEL?

Phenol is a toxic, white crystalline solid with a disinfectant smell. It quickly causes
white blistering to the skin, which goes away after a short period.

a) BOILING POINT (VOLATILITY)

The boiling point of phenol is determined by the intermolecular forces. Permanent

dipole-dipole attractions due to the electronegative oxygen are present. More
significant is the hydrogen bonding between the lone pair on the oxygen in one
molecule and the H of an OH group on a neighbouring molecule. These interactions
give phenol higher melting and boiling points compared to some other molecules. For
example, comparing the properties of phenol having hydrogen bonding with
methylbenzene with no hydrogen bonding clearly shows the role of the intermolecular
forces in determining melting and boiling points. Both molecules have an aromatic
ring with the same shape and number of electrons. The difference lies in that one has
the non-polar methyl group whilst the other has the polar OH group.

mpt ⁰C bpt ⁰C
C6H5OH 40-43 182
C6H5CH3 -95.0 111

b) SOLUBILITY IN WATER

Hydrogen bonding between the OH group in phenol molecules and water also
influences solubility in water. Phenol is moderately soluble in water with a solubility
of about 8g in 100g of water (20⁰C). For amounts greater than 8g, two layers form, an
upper layer consisting of a phenol solution in water and a lower water in phenol
solution.

PREPARATION

LABORATORY PREPARATION

1. Phenol can be prepared from benzenesulfonic acid by heating with solid

sodium hydroxide to fusion. Sodium phenoxide is obtained which is then acidified to
obtain phenol.

‘fuse’
C6H5SO3H + 3NaOH C6H5ONa + Na2SO3 + 2H2O
Benzenesulfonic
sodium phenoxide
acid

C6H5ONa + H+ C6H5OH + Na+

Sodium
phenol
phenoxide

2. Phenol can also be prepared from diazonium salts. These are compounds
formed by the reaction of phenylamine with nitric (III) acid which in turn can be
formed in situ from the reaction of NaNO2 and HCl.

C6H5NH2 + NaNO2 + 2HCl C6H5N2+Cl- + 2H2O + NaCl

phenylamine <5 oC phenyldiazonium chloride

The diazonium compound is then hydrolysed to phenol by reacting with a dilute acid.
 H+
C6H5N2+
+H2O C6H5OH + N2 + H+
phenyldiazonium ion Phenol

ACIDITY OF PHENOLS
Phenols have an OH group which can dissociate in water making them weak acids
(pKa approximately 10). Since they are weakly acidic, the equilibrium is shifted to the
left.

+ H2O + H3O+

phenol phenoxide

Phenols are more acidic than alcohols (ethanol has a pKa of 16) because the phenoxide
ion formed is more stable than the alkoxide in alcohols. In alkoxides (R-O-), the
negative charge is enhanced by the inductive effect of the neighbouring alkyl group
making it a strong conjugate base so likely to pick up H+ and reform the alcohol. Hence
alcohols are very weakly acidic (low dissociation and the equilibrium strongly shifted
to the left). The phenoxide ion can delocalise its negative charge around the ring. One
of the lone pairs on the oxygen is in a p orbital which is aligned with the p orbitals of
the benzene ring. This lone pair can be delocalised to form an extended delocalised
system involving the benzene ring but also extending over the oxygen.

DIAGRAM OF EXTENDED DELOCALISED SYSTEM ?

This delocalisation makes the phenoxide ion less negative, more stable and so less
likely to pick up H+ than the alkoxide. For phenol, the above equilibrium is shifted to
the left to a lower extent than for alcohols and hence phenols are stronger acids though
still weak.

Being acidic, phenol will react with a base and readily dissolve in it (though almost
insoluble in water) to form a colourless solution.

+ NaOH + H2O

phenol sodium phenoxide

Unlike aliphatic alcohols, phenol is acidic enough to react with sodium carbonate
where the carbonate accepts H+ from phenol to form a hydrogencarbonate and the
phenoxide. The hydrogencarbonate however cannot accept another hydrogen ion to
form carbon dioxide and water since the phenol is a weak acid. Phenol therefore does
not react with hydrogencarbonate but does react with a carbonate WITHOUT the
evolution of CO2. This property can be used to distinguish between phenols and
carboxylic acids which although both acidic, do not give the same result with a
carbonate. Only the carboxylic acids give off CO2 which turns lime water milky.

C6H5OH + Na2CO3 C6H5ONa + NaHCO3

phenol
2CH3COOH + Na2CO3 2CH3COONa + H2O + CO2
ethanoic acid

Substituted phenols will have a lower or higher acidity compared to phenol depending
on the groups directly bonded to the benzene ring.

Electron withdrawing groups like halogens and NO2 will reduce the electron density
in the ring favouring the delocalisation of the negative charge around the ring.

4- chlorophenoxide ion

The substituted phenoxide will be more stable and so more likely to form. 4-
chlorophenol (pKa about 9.18) will be more acidic than phenol and 2,4,6-trinitrophenol
(pKa about 0.40) even more acidic.

Electron pushing/donating groups will enhance the electron density in the ring and
so the delocalisation of the lone pair on the oxygen occurs to a lower extent making the
substituted phenoxide ion less likely to form and hence the compound less acidic (pKa
about 10.26).

4-methylphenoxide ion

REACTIONS OF PHENOLS

Phenols can have two different types of reactions

REACTIONS OF THE OH GROUP

1. Ester formation can take place for phenols but this reaction occurs less readily in
phenols than in alcohols. The reaction with carboxylic acids is very slow and is not
normally used. Esters of phenol are formed by reacting with an acid chloride at room
temperature or an acid anhydride whilst warming.
 + CH3COCl + HCl

phenol ethanoyl chloride phenyl ethanoate

+ (CH3 CO)2O + CH3COOH

phenol ethanoic anhydride phenyl ethanoate ethanoic acid

The esterifications with acid chlorides and anhydrides are still slower than the
corresponding reactions with alcohols. Sometimes, the phenoxide is used instead of
phenol as this gives a better reaction since the phenoxide is more reactive (a better
nucleophile due to the negative charge. These reactions are nucleophilic substitutions).
This is especially used when reacting aromatic acid chlorides and anhydrides that are
less reactive than their aliphatic forms. The phenoxide is prepared by reacting phenol
with a solution of NaOH in which it dissolves. Then it is reacted with the aromatic acid
chloride to form a solid product.

+ + NaCl

sodium phenoxide benzoyl chloride phenyl benzoate

The anhydride is also more reactive with the phenoxide.

+ (CH3 CO)2O + CH3COOH

sodium phenoxide ethanoic anhydride phenyl ethanoate ethanoic acid

2. Phenols can also form ethers in a reaction similar to that of aliphatic alcohols. The
phenol is first converted to the alkoxide and then reacted with a halogenoalkane.

RX
+ NaOH

reflux
+ CH3CH2Br + NaBr

sodium phenoxide bromoethane ethoxybenzene

REACTIONS OF THE RING

The presence of the OH group directly bonded to the ring activates the ring making it
more reactive towards electrophiles. This is due to the fact that one of the lone pairs on
the oxygen is in a p orbital which is aligned with the p orbitals of the benzene ring.
This lone pair can be delocalised to form an extended delocalised system involving the
benzene ring but also extending over the oxygen. The lone pair is now delocalised into
the ring system which is therefore richer in electrons and hence more reactive towards
electrophiles, the latter being a positive species. Phenol will therefore undergo
electrophilic substitution with greater ease and so needs milder conditions for its
reactions. Dilute acids are used instead of concentrated ones and heating or in some
cases the use of catalysts is not required.

DIAGRAM OF EXTENDED DELOCALISED SYSTEM ?

The OH group and the delocalisation of the lone pair has another effect on the reactions
of the ring. The OH group is 2,4- directing.

Delocalisation of the lone pair in the ring makes positions 2 and 4 negatively charged
and so more prone to attack by electrophiles than the other ring carbons. Substitution
in the ring in phenol is therefore likely to occur in these positions.

Remember therefore that electrophilic substitutions in the ring need milder conditions
and will give 2-/4- substituted phenols.

1. The product obtained when phenol reacts with nitric acid depends on the conditions
used.

a. With dilute nitric acid at room temperature, phenol gives a mixture of the 2-
nitrophenol and the 4-nitrophenol.

+ HNO3 + H2O

phenol dil. nitric acid 2-nitrophenol

 + HNO3 + H2O

phenol dil. nitric acid 4-nitrophenol

Although the two products are both nitrophenols, their boiling points differ with the
2-nitrophenol showing a lower boiling point. Both nitrophenols have polar oxygens
and a polar hydrogen and so can form intermolecular hydrogen bonding. In the 2-
nitrophenol, the OH and NO2 groups are on neighbouring carbons and so can also
engage in intramolecular hydrogen bonding. This takes place at the expense of the
intermolecular hydrogen bonding and so, with fewer intermolecular H-bonds, 2-
nitrophenol will show a lower boiling point (215⁰C as opposed to 279⁰C for 4-
nitrophenol at which point it decomposes).

b. With concentrated nitric acid, phenol undergoes more substitutions to give 2,4,6-
trinitrophenol also known as picric acid which is an explosive substance and one of
the most acidic phenols.

+ 3HNO3 + 3H2O

phenol conc. nitric acid 2,4,6-trinitrophenol

2. Phenol can react at room temperature with halogens without the use of a catalyst
and in the absence of water to give the 2-halophenol and 4-halophenol.

CHCl3
+ Br2 + HBr

2-bromophenol

CHCl3
+ Br2 + HBr

4-bromophenol
If the reagent is bromine water, then the phenol in water will have the presence of
phenoxide ions due to the acidity of phenol as previously explained. The ring becomes
even richer in electrons due to delocalisation of the negative charge of the phenoxide
ion making the ring even more reactive towards electrophiles than phenol itself.
Phenol will therefore react with bromine water to give a trisubstituted product.

+ 3 Br2 (aq) + 3HBr

bromine water 2,4,6-tribromophenol

The product has 3 bromines directly attached to the ring and these are electron pulling
groups greatly reducing the negative charge on the tribromophenoxide ion hence
reducing its solubility in water. The product is a white solid with an antiseptic smell.
This visible change can be used as a test for phenol where the brown bromine water
will be decolourised giving a white precipitate with phenol. Alkenes also decolourise
bromine water but do not give the precipitate. Note that phenylamine reacts in the
same way as phenol with bromine water and so this reaction cannot be used as a test
to distinguish between phenol and phenylamine.

3. Phenol also undergoes sulfonation, alkylation and acylation with substitutions

always in positions 2- and 4-.

Sulfonation in the o and p positions takes place with concentrated sulfuric acid and
heating.

heat
+ H2SO4 + H2O

concentrated 4-hydroxybenzenesulfonic acid

Alkylation of phenol with halogenoalkanes tends to give the ether as already discussed
above. Alkylation in the ring can take place with the use of a Friedel-Crafts catalyst
and a halogenoalkane to give a low yield of the o/p product.

AlCl3
+ CH3Cl + HCl

chloromethane 4-methylphenol

A more effective alkylation can take place with alkenes and acid.

H2SO4

+ CH2 =CH2

ethene 4-ethylphenol
The reaction of phenol with an acid chloride or an acid anhydride depends a lot on the
conditions. If no catalyst is used, the product will be the ester due to the reaction of the
OH group in phenol (this reaction was discussed previously in this chapter).

If excess Friedel-Crafts catalyst is used, then the acylation of the ring will take place
exclusively. Even if esterification takes place first, the excess catalyst will result in a
rearrangement reaction which will give the hydroxyarylketone.

excessAlCl3
+ CH3COCl + HCl

chloromethane 1-(4-hydroxyphenyl)ethanone

4. Phenol can react with methanal to give a condensation polymer. The reaction
involves methanal, with its slightly positive carbonyl carbon, attacking positions 2-
and 4- in phenol that are more negative as previously explained. Phenol is substituted
in all 3 positions. The reaction then continues with a condensation reaction with other
phenol molecules and more substitutions to give an extensive structure.

+ nHCHO + n H2 O
n

Phenol methanal repeating unit of the phenolic resin

The product is a phenolic resin found in a number of different forms with different
tradenames. The most common name is perhaps bakelite which was one of the first
plastics made from components that were synthetic. It was used in kitchenware, radio
and telephone casings and many other uses.

5. Phenol undergoes a coupling reaction with diazonium ions to form coloured

products called azo dyes.

+ + H+

phenyldiazonium ion 4-phenylazophenol

OTHER REACTIONS OF PHENOL

1. Reduction of phenol removes the OH group to give benzene. This can be very useful
in converting phenol to other aromatic compounds without an OH group.

heat
+ Zn + ZnO

phenol zinc dust benzene

2. Phenol reacts with a solution of neutral iron (III) chloride where phenol acts as a
ligand forming a purple complex.