Alcohols, Phenols, and Thiols

Alcohols, Phenols, and Thiols

Dr. Marlowe Louis F. Fabunan

1
Alcohols and Phenols
An alcohol contains
 A hydroxyl group
(—OH) attached to
a carbon chain.
A phenol contains
 A hydroxyl group
(—OH) attached to
a benzene ring.

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

2
Classification of Alcohols
Alcohols are classified
 By the number of alkyl groups attached to the carbon
bonded to the hydroxyl.
 As primary (1°), secondary (2°), or tertiary (3°).

Primary (1º) Secondary (2º) Tertiary (3º)

1 group 2 groups 3 groups
H CH3 CH3
| | |
CH3—C—OH CH3—C—OH CH3—C—OH
| | |
H H CH3 3
Learning Check
Classify each alcohol as
(P) primary, (S) secondary, or (T) tertiary.
OH
|
1. CH3—CH—CH2—CH3

2. CH3—CH2—CH2—OH
OH
|
3. CH3—CH2—C—CH2—CH3
|
CH3

4
Naming Alcohols

The names of alcohols

 In the IUPAC system replace -e of alkane name with -ol.
 that are common names use the name of the alkyl group
followed by alcohol.
Formula IUPAC Common Name
CH4 methane
CH3─OH methanol methyl alcohol
CH3─CH3 ethane
CH3─CH2─OH ethanol ethyl alcohol
5
More Names of Alcohols
In IUPAC names for longer carbon chains, the chain is
numbered from the end nearest the ─OH group.

CH3─CH2─CH2─OH 1-propanol
OH
│
CH3─CH─CH2─CH3 2-butanol
CH3 OH
│ │
CH3─CH─CH2─CH2─CH─CH3 5-methyl-2-hexanol
6 5 4 3 2 1

6
 Some Typical Alcohols
OH
|
“rubbing alcohol” CH3—CH—CH3
2-propanol (isopropyl alcohol)

antifreeze HO—CH2—CH2—OH
1,2-ethanediol (ethylene glycol)
OH
|
glycerol HO—CH2—CH—CH2—OH
1,2,3-propanetriol Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings

7
Learning Check
Give the IUPAC name for each of the following:
1. CH3—CH2—CH2—CH2—OH

OH CH3
| |
2. CH3—CH—CH—CH2—CH3
OH
3.

8
Learning Check

Write the structure of the following:

A. 3-pentanol

B. ethyl alcohol

C. 3-methylcyclohexanol

9
Naming Phenols
To name a phenol with two substituents,
 Assign C-1 to the carbon attached to the –OH.
 Number the ring to give the lowest numbers.
 Use prefixes o, m, and p for common names.
OH OH OH

Cl
Br

Phenol 3-chlorophenol 4-bromophenol

(m-chlorophenol) (p-bromophenol)
10
Phenols in Medicine
Phenol
 Is the IUPAC name for benzene with a hydroxyl
group.
 Is used in antiseptics and disinfectants.
OH
OH OH

OH
OH
CH2CH2CH2CH2CH2CH3

phenol resorcinol 4-hexylresorcinol

11
Derivatives of Phenol
 Compounds of phenol are the active ingredients in the
essential oils of cloves, vanilla, nutmeg, and mint.

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12
Learning Check
Write the structure of each of the following:

A. 3-pentanol

B. ethyl alcohol

C. p-methylphenol

13
Thiols
Thiols
 Are carbon compounds
that contain a –SH
group.

 Are named in the IUPAC

system by adding ­thiol to
the alkane name of the
longest carbon chain.

14
Thiols
Thiols
 Are carbon compounds
that contain a –SH
(Sulfhydryl) group.

 Are named in the IUPAC

system by adding ­thiol to
the alkane name of the
longest carbon chain.

15
 Naming Thiols

 In thiols with long carbon chains, the chain is numbered

to locate the –SH group.

CH3—CH2—CH2—SH 1-propanethiol
SH
|
CH3—CH—CH3 2-propanethiol

16
 Thiols
Thiols
 Often have
strong odors.
 Are used to
detect gas leaks.
 Are found in
onions, oysters,
and garlic.

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17
Learning Check

Draw the structure of each compound.

A. 2-butanethiol

B. 2-methyl-1-butanol

18
Learning Check

Name each of the following compounds:

OH
|
A. CH3—CH2 —CH—CH3

CH3
|
B. CH3—CH2—CH—CH2—CH2—OH

C. CH3—CH2—CH2—SH

19
Ethers
Ethers
 Contain an ─O─ between two carbon groups.
 That are simple are named by listing the alkyl names in
alphabetical order followed by ether
CH3─O─CH3 CH3─CH2─O─CH3

dimethyl ether ethyl methyl ether

20
IUPAC Names for Ethers

 In the IUPAC system, the shorter alkyl group and the

oxygen are named as an alkoxy group attached to the
longer alkane.
methoxy propane

CH3—O—CH2—CH2—CH3
1 2 3

 Numbering the longer alkane gives

1-methoxypropane

21
Ethers as Anesthetics
Anesthetics
 Inhibit pain signals to the brain.
 Such as ethyl ether CH3─CH2─O─CH2─CH3 were used
for over a century, but caused nausea and were
flammable.
 Developed by 1960s were nonflammable.
Cl F F Cl F H
│ │ │ │ │ │
H─C─C─O─C─H H─C─C─O─C─H
│ │ │ │ │ │
F F F H F H
Ethane(enflurane) Penthrane 22
MTBE
Methyl tert-butyl ether
CH3
│
CH3─O─C─CH3
│
CH3
 Is one of the most produced organic chemicals.
 Is a fuel additive
 Is used to improve gasoline combustion.
 Use is questioned since the discovery that MTBE has
contaminated water supplies.

23
Learning Check

Draw the structure of each compound.

A. diethyl ether

B. ethyl methyl ether

C. 2-methoxybutane

24
Cyclic Ethers
A cyclic ether
 Contains an O atom in a carbon ring.
 Is called a heterocyclic compound.
 Typically has 5 (furan) or 6 atoms (pyran) in the
ring.
O

O O O O
furan tetrahydrofuran pyran 1,4-dioxane

25
Dioxins
Dioxins are
 A group of ethers that are highly toxic.
 Formed during forest fires and as industrial by-
products.
 Often carcinogenic.

O
Cl O Cl O Cl
CH2 C OH

Cl Cl Cl O Cl

2,4,5-trichlorophenoxyacetic acid 2,3,7,8-tetrachlorodibenzodioxin

(2,4,5-T; agent orange) (TTCC, “dioxin”) 26
Learning Check
Name each of the following:

O
1. CH3

2. O

27
Lecture 4
13.3
Physical Properties of Alcohols,
Phenols, and Ethers

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28
Boiling Points of Alcohols
Alcohols
 Contain a strongly
electronegative O in the OH
groups.
 Form hydrogen bonds between
alcohol molecules.
 Have higher boiling points than
alkanes and ethers of similar
mass.

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29
Boiling Points of Ethers
Ethers
 Have an O atom, but
no H is attached.
 Cannot form hydrogen
bonds between ether
molecules.

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

30
Solubility of Alcohols and Ethers
in Water
 Alcohols and ethers are more soluble in water than
alkanes because the oxygen atom hydrogen bonds
with water.
 Alcohols with 1-4 C atoms are soluble, but alcohols
with 5 or more C atoms are not.

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings 31

 Comparing Solubility and Boiling
Points
Compound Molar Boiling Soluble
Mass Point (°C) in Water?
Alkane CH3─CH2─CH3 44 -42 No

Ether CH3─O─CH3 46 -23 Yes

Alcohol CH3─CH2─OH 46 78 Yes

32
Solubility of Phenol
Phenol
 Is soluble in water.
 Has a hydroxyl group that ionizes slightly (weak
acid).
 Is corrosive and irritating to the skin.
OH O-

+ H2O + H 3 O+

33
Learning Check
Which compound would have the higher boiling
point? Explain.

ethyl methyl ether or 1-propanol

34
Learning Check
Which compound would be more soluble in water?
Explain.

ethanol or 2-pentanol

35
Lecture 4

13.4
Reactions of Alcohols and Thiols

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36
Combustion of Alcohols
Combustion is the reaction of an alcohol
with O2 to produce CO2 and H2O.
2CH3OH + 3O2 2CO2 + 4H2O + Heat

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37
Dehydration of Alcohols
Dehydration of an alcohol occurs
 When heated with an acid catalyst.
 With the loss of —H and —OH from adjacent carbon
atoms.
H OH
| | H+, heat
H—C—C—H H—C=C—H + H2O
| | | |
H H H H

alcohol alkene
38
Learning Check
Write the equations for the reactions when
2-propanol undergoes:
1. combustion

2. dehydration

39
 Formation of Ethers

 Ethers form when dehydration takes place at low

temperature.
H+
CH3—OH + HO—CH3 CH3—O—CH3 + H2O
two methanol dimethyl ether

40
Oxidation and Reduction

In the oxidation of an organic compound

 There is an increase in the number of C—O
bonds.
 There is a loss of H.

In the reduction of an organic compound

 There is an decrease in the number of C—O
bonds.
 There is a gain of H.

41
 Oxidation and Reduction

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42
 Oxidation of Primary (1)
Alcohols
When a primary alcohol is oxidized [O],
 One H is removed from the –OH.
 Another H is removed from the carbon bonded to the OH.
 An aldehyde is produced.
[O]
Primary alcohol Aldehyde
OH O
| [O] ||
CH3—C—H CH3—C—H + H2O
|
H
Ethanol Ethanal
(ethyl alcohol) (acetaldehyde)
43
Oxidation of Secondary (2)
Alcohols
When a secondary alcohol is oxidized [O],
 One H is removed from the –OH.
 Another H is removed from the carbon bonded to the OH.
 A ketone is produced.
[O]
secondary alcohol ketone
OH O
│ [O] ║
CH3—C—CH3 CH3—C—CH3 + H2O
│
H
2-propanol (isopropyl alcohol) 2-propanone(dimethyl ketone,
“acetone”) 44
 Oxidation of Tertiary (3)Alcohols
Tertiary alcohols do not readily oxidize.
[O]
Tertiary alcohol no reaction
OH
│ [O]
CH3─C─CH3 no product
│
CH3 no H on the C-OH to oxidize

2-methyl-2-propanol

45
 Learning Check

Select the compound that would result for each reaction

of CH3—CH2—CH2—OH.
O
||
1) CH3—CH=CH2 2) CO2 + H2O 3) CH3—CH2—C—H
A. H+, heat

B. [O]

C. O2, heat
46
Oxidation of Ethanol in the Body

In the body,
 Ethanol is oxidized by enzymes in the liver.
 Aldehyde product impairs coordination.
O O
║ ║
CH3─CH2─OH CH3─C─H CH3─C─OH
ethyl alcohol acetaldehyde acetic acid

2CO2 + H2O

47
Ethanol CH3─CH2─OH
Ethanol
 Acts as a depressant.
 Kills or disables more
people than any other drug.
 Is metabolized at a rate of
12-15 mg/dL per hour by a
social drinker.
 Is metabolized at a rate of 30 Copyright © 2007 by Pearson Education, Inc.
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mg/dL per hour by an
alcoholic.

48
 Effect of Alcohol on the Body
TABLE 13.2

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Learning Check
Select the product for the oxidation of
OH
│ [O]
CH3—CH—CH2—CH3

O ║

1) CH3—CH=CH—CH3 2) CH3—C—CH2 —CH3

OH
│
3) CO2 + H2O 4) CH3—CH—CH2—CH3
50
Oxidation of Thiols
When thiols undergo oxidation,
 An H atom is lost from each of two –SH groups.
 The product is a disulfide.
[O]
CH3—SH + HS—CH3 CH3—S—S—CH3 + H2O

51