RO UT ES

TO PHE NO L
A guide for A level students

KNOCKHARDY PUBLISHING
 KNOCKHARDY PUBLISHING

PHENOL
INTRODUCTION
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 PHENOL
CONTENTS
• Prior knowledge
• Synthesis from benzene
• Reactions of the OH group
• Reactions of the ring
• Benzene diazonium chloride - preparation
• Benzene diazonium chloride - reactions
• Revision check
 PHENOL
Before you start it would be helpful to…

• know the functional groups found in organic chemistry

• know the arrangement of bonds around atoms
• recall and explain electrophilic substitution of aromatic rings
 PHENOL

Structure phenol is an aromatic alcohol with formula C6H5OH

the OH group is attached directly to the benzene ring
it is an almost colourless crystalline solid
 PHENOL

Structure phenol is an aromatic alcohol with formula C6H5OH

the OH group is attached directly to the benzene ring
it is an almost colourless crystalline solid

Preparation You cannot put an OH group directly onto a benzene ring by

electrophilic substitution, so phenol has to be synthesised in
a multi-stage process
 PHENOL

Structure phenol is an aromatic alcohol with formula C6H5OH

the OH group is attached directly to the benzene ring
it is an almost colourless crystalline solid

Preparation You cannot put an OH group directly onto a benzene ring by

electrophilic substitution, so phenol has to be synthesised in
a multi-stage process

Step 1 - Nitration of benzene

reagents conc. nitric acid and conc. sulphuric acid (catalyst)
conditions reflux at 55°C
equation C6H6 + HNO3 ——> C6H5NO2 + H2O
mechanism electrophilic substitution
 PHENOL

Structure phenol is an aromatic alcohol with formula C6H5OH

the OH group is attached directly to the benzene ring
it is an almost colourless crystalline solid

Preparation You cannot put an OH group directly onto a benzene ring by

electrophilic substitution, so phenol has to be synthesised in
a multi-stage process

Step 2 - Reduction of nitrobenzene

reagents tin and conc. hydrochloric acid
conditions reflux
equation C6H5NO2 + 6 [H] ——> C6H5NH2 + 2H2O
mechanism reduction
 PHENOL

Structure phenol is an aromatic alcohol with formula C6H5OH

the OH group is attached directly to the benzene ring
it is an almost colourless crystalline solid

Preparation You cannot put an OH group directly onto a benzene ring by

electrophilic substitution, so phenol has to be synthesised in
a multi-stage process

Step 3 - Diazotisation of phenylamine

reagents nitrous acid and hydrochloric acid (use sodium nitrite)
conditions keep below 10°C
equation C6H5NH2 + HNO2 + HCl ——> C6H5N2+ Cl¯ + 2H2O
reaction type diazotisation
 PHENOL

Structure phenol is an aromatic alcohol with formula C6H5OH

the OH group is attached directly to the benzene ring
it is an almost colourless crystalline solid

Preparation You cannot put an OH group directly onto a benzene ring by

electrophilic substitution, so phenol has to be synthesised in
a multi-stage process

Step 4 - Substitution of diazo group by OH

reagents water
conditions warm above 10°C
equation C6H5N2+ Cl¯ + H2O ——> C6H5OH + N2 + HCl
reaction type hydrolysis / substitution
 PHENOL - REACTIONS OF THE OH GROUP

Water phenol is a weak acid

it dissolves very slightly in water to form a weak acidic solution
it is a stronger acid than aliphatic alcohols
the ring helps weaken the O-H bond and stabilises the resulting anion

C6H5OH(aq) C6H5O¯(aq) + H+(aq)

 PHENOL - REACTIONS OF THE OH GROUP

Water phenol is a weak acid

it dissolves very slightly in water to form a weak acidic solution
it is a stronger acid than aliphatic alcohols
the ring helps weaken the O-H bond and stabilises the resulting anion

C6H5OH(aq) C6H5O¯(aq) + H+(aq)

NaOH phenol reacts with sodium hydroxide to form a salt - sodium phenoxide
it is ionic and water soluble

C6H5OH(aq) + NaOH(aq) ——> C6H5O¯ Na+(aq) + H2O(l)

 PHENOL - REACTIONS OF THE OH GROUP

Water phenol is a weak acid

it dissolves very slightly in water to form a weak acidic solution
it is a stronger acid than aliphatic alcohols
the ring helps weaken the O-H bond and stabilises the resulting anion

C6H5OH(aq) C6H5O¯(aq) + H+(aq)

NaOH phenol reacts with sodium hydroxide to form a salt - sodium phenoxide
it is ionic and water soluble

C6H5OH(aq) + NaOH(aq) ——> C6H5O¯ Na+(aq) + H2O(l)

Sodium phenol reacts with sodium to form an ionic salt - sodium phenoxide
hydrogen is also produced
this reaction is similar to that with aliphatic alcohols such as ethanol

2C6H5OH(s) + 2Na(s) ——> 2C6H5O¯ Na+(s) + H2(g)

 PHENOL - REACTIONS OF THE AROMATIC RING

ELECTROPHILIC SUBSTITUTION

Bromine the OH group is electron releasing

it increases the electron density of the delocalised system
it makes substitution much easier compared to benzene
the electron density is greatest at the 2,4 and 6 positions
substitution takes place at the 2,4 and 6 positions
phenol reacts readily with bromine water WITHOUT A CATALYST
it is so easy that multiple substitution takes place
other electrophiles such as NO2+ react in a similar way
 BENZENE DIAZONIUM CHLORIDE

Structure has the formula C6H5N2+ Cl¯

a diazonium group is attached to the ring
the aromatic ring helps stabilise the ion

PREPARATION
reagents phenylamine, nitrous acid and hydrochloric acid
conditions keep BELOW 10°C
equation C6H5NH2 + HNO2 + HCl ——> C6H5N2+ Cl¯ + 2H2O

notes nitrous acid is unstable and is made in situ from sodium nitrite

C6H5NH2 + NaNO2 + 2HCl ——> C6H5N2+ Cl¯ + NaCl + 2H2O

the solution is kept cold to slow down decomposition

of the diazonium salt

C6H5N2+ Cl¯ + H2O ——> C6H5OH + HCl + N2

 DIAZONIUM SALTS - REACTIONS

Benzene diazonium chloride undergoes two main types of reaction

SUBSTITUTION OF
THE DIAZONIUM GROUP nitrogen expelled

COUPLING REACTIONS nitrogen atoms are retained

 DIAZONIUM SALTS - SUBSTITUTION

OH
reagents water (HYDROLYSIS)
conditions warm above 10°C
equation C6H5N2+ Cl¯ + H2O ——> C6H5OH + HCl + N2

use the only reasonably simple way to substitute OH

phenol is an antiseptic and is used to make polymers

I
reagents potassium iodide solution
conditions warm
equation C6H5N2+ Cl¯ + KI ——> C6H5I + KCl + N2
 DIAZONIUM SALTS - COUPLING

reagents phenol and sodium hydroxide

conditions alkaline solution below 10°C
equation C6H5N2+Cl¯ + C6H5OH + NaOH ——> C6H5-N=N-C6H4OH + NaCl + H2O

(4-hydroxyphenol)azobenzene
YELLOW

use making azo dyes

AZO GROUP
 REVISION CHECK
What should you be able to do?

Recall the structures of phenol and benzene diazonium chloride

Explain and understand the difference in reactivity between phenol and benzene
Recall the reagents and conditions used in the steps to convert benzene into phenol
Recall the different types of reaction undergone by benzene diazonium chloride

CAN YOU DO ALL OF THESE? YES NO

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WELL DONE!
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 RO UT ES
TO PHE NO L
THE END

© 2004 JONATHAN HOPTON & KNOCKHARDY PUBLISHING

AMIDES - CHEMICAL PROPERTIES