CCB1013 Organic Chemistry

By Dr. Oh Pei Ching

Chapter 21:
Phenols and Aryl Halides–
Nucleophilic Aromatic Substitution

1
Phenols and Aryl Halides

A phenol that is a blistering agent in poison ivy

CCB1013 Organic Chemistry 2

 Learning Outcomes

By the end of this lecture, you should be able to:
• Identify the structure and nomenclature of phenols
• Understand the synthesis of phenols and reactions of
phenols as acids
• Understand the mechanism of aryl halides reactions
via nucleophilic aromatic substitution

CCB1013 Organic Chemistry 3

Structure and Nomenclature of Phenols

Phenol contains a hydroxyl group directly bonded to a
benzene ring.

Naphthols and phenanthrols have hydroxyl group

attached to a polycyclic benzenoid ring.

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 Nomenclature of Phenols

In many compounds, phenol is the base name.

Methylphenols are commonly called cresols.

Cl CH3
NO2

OH OH
OH

4-Chlorophenol 2-Nitrophenol 3-Methylphenol

(p-chlorophenol) (o-nitrophenol) (m-cresol)

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 Nomenclature of Phenols

The benzenediols also have common names:

OH OH OH
OH

OH
OH
1,2-Benzenediol 1,3-Benzenediol 1,4-Benzenediol
(catechol) (resorcinol) (hydroquinone)

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Naturally Occurring Phenols

(amino acid in protein)

(female sex hormone)

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 Physical Properties of Phenols

Phenol is similar with alcohol in some respect due to
the presence of hydroxyl group.

Phenol can form strong intermolecular hydrogen
bonds, thus have higher boiling points than
hydrocarbons of the same molecular weight.

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 Synthesis of Phenols

Laboratory Synthesis
 The most important laboratory synthesis of phenols is by
hydrolysis of arenediazonium salts.

Arenediazonium salt

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 Reactions of Phenols as Acids

Distinguishing and Separating Phenols from Alcohols
and Carboxylic Acids
 Phenols are more acidic than water, the following reaction goes
to completion and produces water-soluble sodium phenoxide:

 1-hexanol is a weaker acid than water, its reaction with aqueous

sodium hydroxide does not occur to a significant extent:

CCB1013 Organic Chemistry 10

 Reactions of Phenols as Acids

Distinguishing and Separating Phenols from Alcohols
and Carboxylic Acids
 Phenols dissolve in aqueous sodium hydroxide.
 Most alcohols with six carbon atoms or more do not dissolve
in aqueous sodium hydroxide.
 Phenols are not soluble in aqueous sodium bicarbonate
(NaHCO3).
 Carboxylic acids are soluble in NaHCO3.

CCB1013 Organic Chemistry 11

 Reactions of Phenols as Acids

Distinguishing and Separating Phenols from Alcohols
and Carboxylic Acids

Question:
 If you are given three unknown samples: one is benzoic acid;
one is phenol; and one is cyclohexyl alcohol; how would you
distinguish them by simple chemical tests?
 Recall acidity of
H H
O O O
H
O
> >

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 Reactions of Phenols as Acids

O O
H + Na OH + H2O
R O R O Na
(soluble in water)

O O Na
H
+ NaOH

(soluble in water)
O
H
+ NaOH No Reaction

(immiscible
with H2O)
CCB1013 Organic Chemistry 13
Reactions of Phenols as Acids
O O
H
O O Na
+ NaHCO3

+ CO2(g) + H2O
(gas evolved)
O
H
+ NaHCO3 No Reaction

O
H
+ NaHCO3 No Reaction

CCB1013 Organic Chemistry 14

Other Reactions of the O‒H Group of Phenols

O O
Carboxylic acid anhydride

R O R
base

OH O R
Phenol O
Acid chloride Ester

R Cl
base

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Other Reactions of the O‒H Group of Phenols

Phenols in the Williamson Synthesis

 Convert phenols to ether

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Reactions of the Benzene Ring of Phenols

Bromination
OH
Br Br
3 Br2
+ 3 HBr
OH H2O

Br (NO Lewis acid

required for the
OH brominations)

Br2
o
+ HBr
CS2, 5 C
Monobromination can be carried out
using carbon disulfide at low T to
reduce electrophilic reactivity of Br2 Br

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Reactions of the Benzene Ring of Phenols

Nitration

OH OH OH
NO2
20% HNO3
+
o
25 C

NO2
(30-40%) (15%)

More volatile Less volatile

(intramolecular (intermolecular
hydrogen bonding) hydrogen bonding)

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Reactions of the Benzene Ring of Phenols

Sulfonation OH
SO3H
conc. H2SO4
25oC
OH
conc. H2SO4
100oC

OH

conc. H2SO4
100oC

SO3H
CCB1013 Organic Chemistry 19
 END OF CHAPTER 21

Identify the structure and

nomenclature of phenols

Understand the synthesis of
phenols and reactions of phenols
as acids

Understand the mechanism of aryl
halides reactions via nucleophilic
aromatic substitution

Try to solve all review problems

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