General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,

by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.

 Lecture 17

Chapter 10

Alcohols, Ethers and Phenols

 Phenols

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 Nomenclature

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 Nomenclature

OH
CH3
5-Chloro-2-methylphenol
Cl
named on basis of phenol as parent
substituents listed in alphabetical order
lowest numerical sequence: first point of
difference rule
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 Nomenclature

OH OH OH
OH

OH

OH
1,2-Benzenediol 1,3-Benzenediol 1,4-Benzenediol

(common name: (common name: (common name:

pyrocatechol) resorcinol) hydroquinone)
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 Nomenclature

OH

p-Hydroxybenzoic acid

CO2H
name on basis of benzoic acid as parent
higher oxidation states of carbon outrank
hydroxyl group

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 Structure and Bonding

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 Structure of Phenol

phenol is planar

C—O bond distance is 136 pm, which is

slightly shorter than that of CH3OH (142 pm)

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 Physical Properties

The OH group of phenols allows hydrogen bonding

to other phenol molecules and to water.

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 Hydrogen Bonding in Phenols

O H O

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 Physical Properties

Compared to compounds of similar size and

molecular weight, hydrogen bonding in phenol
raises its melting point, boiling point, and
solubility in water.

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 Physical Properties

C6H5CH3 C6H5OH C6H5F

Molecular weight 92 94 96

Melting point (°C) –95 43 –41

Boiling 111 132 85

point (°C,1 atm)

Solubility in 0.05 8.2 0.2

H2O (g/100 mL,25°C)
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Just for general knowledge, will not be tested on 24 - 13
 Acidity of Phenols

most characteristic property of

phenols is their acidity

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 Compare

••O•• ••O•• ••
–
H
Ka = 10-10
+ +
H

Ka = 10-16
•• + + •••–
CH3CH2O H H CH3CH2O •
•• ••

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 Delocalized negative charge in phenoxide ion

– ••
•O •
• •

H H

H H

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 Delocalized negative charge in phenoxide ion

– ••
•O •
• • ••O••

H H H –H
••

H H H H

H H

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 Delocalized negative charge in phenoxide ion

••O••

H –H
••

H H

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 Delocalized negative charge in phenoxide ion

••O•• ••O••

H H H –H
••
••
H – H H H

H H

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 Delocalized negative charge in phenoxide ion

••O••

H H

••
H – H
H

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 Delocalized negative charge in phenoxide ion

••O•• ••O••

H H H – H
••
••
H – H H H

H H

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 Phenols are converted to phenoxide ions
in aqueous base

•O•• ••O•• ••
–
• H

–
+ HO + H2O

stronger acid weaker acid

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 Substituent Effects
on the
Acidity of Phenols

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 Electron-releasing groups have little or no effect

OH OH OH

CH3 OCH3
Ka: 1 x 10-10 5 x 10-11 6 x 10-11

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 Electron-withdrawing groups increase acidity

OH OH OH

Cl NO2
Ka: 1 x 10-10 4 x 10-9 7 x 10-8

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 Effect of electron-withdrawing groups is most
pronounced at ortho and para positions

OH OH OH
NO2

NO2

NO2
Ka: 6 x 10-8 4 x 10-9 7 x 10-8

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 Effect of strong electron-withdrawing groups
is cumulative

OH OH OH
NO2 O2N NO2

NO2 NO2 NO2

Ka: 7 x 10-8 1 x 10-4 4 x 10-1

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 Resonance Depiction

– ••
••O •• ••O••••

H H H H

H H H H

N ••• •• N •••
•O + O• •O + O•
• •
•• •• – – •• •• –

Just for general knowledge, will not be tested on

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 Sources of Phenols

Phenol is an important industrial chemical.

Major use is in phenolic resins for adhesives
and plastics.
Annual U.S. production is about 4 billion
pounds per year.

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 Industrial
Preparations
of Phenol

SO3H Cl CH(CH3)2

1. NaOH 2. H+ 1. O2
heat
1. NaOH
heat 2. H2O
OH H2SO4
2. H +
Just for general knowledge, will not be tested on
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 Laboratory Synthesis of Phenols

from arylamines via diazonium ions

O 2N 1. NaNO2, O2N
H2SO4,
H2O
NH2 OH
2. H2O, heat

(81-86%)

Just for general knowledge, will not be tested on

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 Naturally Occurring Phenols

Many phenols occur naturally

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 Example: Thymol

OH

CH3 CH(CH3)2

Thymol
(major constituent of oil of thyme)

Just for general knowledge, will not be tested on

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 Example: 2,5-Dichlorophenol

OH

Cl Cl

2,5-Dichlorophenol
(from defensive secretion of
a species of grasshopper)

Just for general knowledge, will not be tested on

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 Reactions of Phenols:
Electrophilic Aromatic
Substitution
Hydroxyl group strongly activates the ring
toward electrophilic aromatic substitution

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 Electrophilic Aromatic Substitution in Phenols

Halogenation
Nitration
Nitrosation
Sulfonation
Friedel-Crafts Alkylation
Friedel-Crafts Acylation

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 Halogenation

OH OH

ClCH2CH2Cl
+ Br2
0°C

Br
(93%)
monohalogenation in nonpolar solvent
(1,2-dichloroethane)

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 Halogenation

OH OH

H2O Br Br
+ 3Br2
25°C
F F

Br
(95%)
multiple halogenation in polar solvent
(water)
Just for general knowledge, will not be tested on
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 Electrophilic Aromatic Substitution in Phenols

Halogenation
Nitration
Nitrosation
Sulfonation
Friedel-Crafts Alkylation
Friedel-Crafts Acylation

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 Nitration

OH OH

HNO3 NO2

acetic acid
5°C
CH3 CH3

OH group controls (73-77%)

regiochemistry

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 Electrophilic Aromatic Substitution in Phenols

Halogenation
Nitration
Nitrosation
Sulfonation
Friedel-Crafts Alkylation
Friedel-Crafts Acylation

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 Nitrosation

NO
OH NaNO2 OH

H2SO4, H2O
0°C
(99%)
only strongly activated
rings undergo nitrosation
when treated with nitrous
acid
Just for general knowledge, will not be tested on
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 Electrophilic Aromatic Substitution in Phenols

Halogenation
Nitration
Nitrosation
Sulfonation
Friedel-Crafts Alkylation
Friedel-Crafts Acylation

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 Sulfonation

OH OH
H3C CH3 H3C CH3
H2SO4

100°C

SO3H
OH group controls
(69%)
regiochemistry

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 Electrophilic Aromatic Substitution in Phenols

Halogenation
Nitration
Nitrosation
Sulfonation
Friedel-Crafts Alkylation
Friedel-Crafts Acylation

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 Friedel-Crafts Alkylation

OH OH
CH3 (CH3)3COH CH3

H3PO4
60°C
H3C C CH3

(CH3)3COH reacts CH3

with H3PO4 to give
(63%)
(CH3)3C+
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 Electrophilic Aromatic Substitution in Phenols

Halogenation
Nitration
Nitrosation
Sulfonation
Friedel-Crafts Alkylation
Friedel-Crafts Acylation

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