Chapter 14 Alcohols, Phenols,

Ethers, and Thiols Alcohols

„ In an alcohol, a
14.1 Structure and Classification of Alcohols hydroxyl group
14.2 Naming Alcohols, Phenols, and Thiols (—OH) is attached
14.3 Some Important Alcohols and Phenols to a carbon chain.
„ In a phenol, a
14.4 Ethers
hydroxyl group
(—OH) is attached
to a benzene ring.

1 2

Classification of Alcohols Learning Check

ƒ Alcohols are classified as primary, secondary, or Classify each alcohol as
tertiary. 1) primary, 2) secondary, or 3) tertiary.
ƒ Classification is determined by the number of OH
alkyl groups attached to the carbon bonded to |
the hydroxyl.
Primary (1º) Secondary (2º) Tertiary (3º) A. ___CH3—CH—CH2—CH3
1 group 2 groups 3 groups
H CH3 CH3
| | | B. ___ CH3—CH2—CH2—OH
CH3—C—OH CH3—C—OH CH3—C—OH
| | | C. ____HO—CH2—CH2—CH2—CH2—CH3
H H CH3
3 4

Solution Naming Alcohols

Classify each alcohol as
ƒ The IUPAC system replaces the -e in the
1) primary, 2) secondary, or 3) tertiary. name of the alkane main chain with –ol.
OH
ƒ Common names for simple alcohols use the
| alkyl name followed by alcohol.
A. 2 CH3—CH—CH2—CH3 CH4 methane CH3OH methanol
(methyl alcohol)
B. 1 CH3—CH2—CH2—OH
CH3CH3ethane CH3CH2OH ethanol
C. 1 HO—CH2—CH2—CH2—CH2—CH3 (ethyl alcohol)

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1
 Naming Alcohols Some Typical Alcohols
ƒ In the IUPAC names for longer chains, the chain OH
is numbered from the end nearest the -OH group. |
“rubbing alcohol” CH3—CH—CH3
CH3—CH2—CH2—OH 1-propanol 2-propanol (isopropyl alcohol)
OH
| antifreeze HO—CH2—CH2—OH
CH3—CH—CH2—CH3 2-butanol 1,2-ethanediol (ethylene glycol)
CH3 OH OH
| |
|
CH3—CH—CH2—CH—CH3
4-methyl-2-pentanol glycerol HO—CH2—CH—CH2—OH
1,2,3-propanetriol
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Learning Check Solution

Name the following: A. CH3—CH2—CH2—CH2—OH
A. CH3—CH2—CH2—CH2—OH 1-butanol
OH CH3
OH CH3 | |
| | B. CH3—CH—CH—CH2—CH3
B. CH3—CH—CH—CH2—CH3 OH 3-methyl-2-pentanol
OH

C. C. cyclopentanol

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Learning Check Solution

Write the structure of each of the following: Write the structure of the following:
A. 3-pentanol OH
A. 3-pentanol |
CH3—CH2—CH—CH2—CH3
B. ethyl alcohol
B. ethyl alcohol CH3—CH2—OH
OH
C. 3-methylcyclohexanol
C. 3-methylcyclohexanol

CH3
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2
 Naming Phenols Examples of Phenols
„ A phenol is a benzene ring with a hydroxyl OH OH OH
group.
„ For two substituents, assign C-1 to the
carbon attached to the –OH.
Cl
„ Number the ring to give the lowest
numbers. Br

„ The prefixes o, m, and p are used for Phenol 3-Chlorophenol 4-Bromophenol

(m-Chlorophenol) (p-Bromophenol)
common names.

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Phenols in Medicine Derivatives of Phenol

„ Many phenols are used as antiseptics and „ Compounds of phenol are the active
disinfectants. ingredients in the essential oils of cloves,
vanilla, nutmeg, and mint.
OH OH OH

OH OH
CH2CH2CH2CH2CH2CH3

Phenol Resorcinol 4-Hexylresorcinal

(antiseptic) (antiseptic)
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Thiols Naming Thiols

„ Thiols are carbon ƒ In thiols with long carbon chains, the chain
compounds that contain is number to locate the -SH group.
the –SH group.
CH3—CH2—CH2—SH 1-propanethiol
„ In the IUPAC name, SH
thiol is added to the |
alkane name of the CH3—CH—CH3 2-propanethiol
longest carbon chain.

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3
 Thiols in Nature Ethers
Thiols: ƒ Ethers contain an -O- between two carbon
ƒ Often have groups.
strong or
disagreeable ƒ Simple ethers are named by listing the alkyl
odors. names in alphabetical order followed by ether.
ƒ Are used to
detect gas leaks. CH3—O—CH3 dimethyl ether
ƒ Are found in CH3—O—CH2—CH3 ethyl methyl ether
onions, oysters, CH3—CH2—O—CH2—CH3 diethyl ether
and garlic.
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IUPAC Names for Ethers Learning Check

„ In the IUPAC system, the shorter alkyl Name each of the following compounds:
group and the oxygen are named as an
A. CH3—CH2 —O—CH2—CH3
alkoxy group attached to the longer alkane.
methoxy propane CH3
|
B. CH3—CH2—CH—CH2—CH2—OH
CH3—O—CH2—CH2—CH3
„ Numbering the longer alkane gives
1-methoxypropane. C. CH3—CH2—CH2—SH

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Solution Learning Check

Name each of the following compounds: Draw the structure of each compound.
A. CH3—CH2 —O—CH2—CH3 A. 2-Butanethiol
Diethyl ether or ethoxyethane (IUPAC)
CH3 B. Ethyl methyl ether
|
B. CH3—CH2—CH—CH2—CH2—OH
3-Methyl-1-pentanol C. 2-Methyl-1-butanol

C. CH3—CH2—CH2—SH
1-Propanethiol
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4
 Chapter 14 Alcohols, Phenols,
Solution Ethers, and Thiols
Draw the structure of each compound.
14.5 Physical Properties of Alcohols,
A. 2-Butanethiol
SH Phenols, and Ethers
| 14.6 Reactions of Alcohols
CH3—CH—CH2—CH3
B. Ethyl methyl ether CH3—CH2—O—CH3
C. 2-Methyl-1-butanol
CH3
|
HO—CH2—CH—CH2—CH3
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Boiling Points of Alcohols Boiling Points of Ethers

„ Alcohols contain a strongly
electronegative O in the OH „ Ethers have an O
groups. atom, but there is no
H attached.
„ Thus, hydrogen bonds form
between alcohol molecules. „ Thus, hydrogen
bonds cannot form
„ Hydrogen bonds contribute to
between ether
higher boiling points for
molecules.
alcohols compared to alkanes
and ethers of similar mass.
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Solubility of Alcohols and Ethers

in Water Reactions of Alcohols
„ Alcohols and ethers are more soluble in water „ Alcohols undergo combustion with O2 to produce
than alkanes because the oxygen atom can CO2 and H2O.
hydrogen bond with water. 2CH3OH + 3O2 2CO2 + 4H2O + Heat
„ Alcohols with 1-4 C atoms are soluble, but
„ Dehydration removes H- and -OH from adjacent
alcohols with 5 or more C atoms are not.
carbon atoms by heating with an acid catalyst.
H OH
| | H+, heat
H—C—C—H H—C=C—H + H2O
| | | |
H H H H
29 alcohol alkene 30

5
 Formation of Ethers Oxidation and Reduction
„Ethers form when dehydration takes place at low „ In organic chemistry, oxidation is a loss of
temperature. hydrogen atoms or a gain of oxygen.
H+ „ In an oxidation, there is an increase in the
number of C-O bonds.
CH3—OH + HO—CH3 CH3—O—CH3 + H2O
„ Reduction is a gain of hydrogen or a loss of
Two Methanol Dimethyl ether oxygen. The number of C-O bonds decreases.

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Oxidation of Primary Alcohols Oxidation of Secondary Alcohols

„ In the oxidation [O] of a primary alcohol, one H „ The oxidation of a secondary alcohol removes
is lost from the –OH and another H from the one H from –OH and another H from the
carbon bonded to the OH. carbon bonded to the –OH.
[O] [O]
Primary alcohol Aldehyde Secondary alcohol Ketone
OH O OH O
| [O] || | [O] ||
CH3—C—H CH3—C—H + H2O CH3—C—CH3 CH3—C—CH3 + H2O
| |
H H
Ethanol Ethanal 2-Propanol Propanone
(ethyl alcohol) (acetaldehyde) (Isopropyl alcohol) (Dimethylketone; Acetone)
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Oxidation of Tertiary Alcohols Learning Check

„ Tertiary alcohols are resistant to oxidation. Select the product for CH3—CH2—CH2—OH.
[O]
Tertiary alcohols no reaction 1) CH3—CH=CH2 2) CO2 + H2O
OH O
||
| [O] 3) CH3—CH2—C—H
CH3—C—CH3 no product
| A. H+, heat B. [O]
CH3 no H on the C-OH to oxidize
2-Methyl-2-propanol C. + O2

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6
 Solution Ethanol CH3CH2OH
Ethanol:
A. H+, heat 1) CH3—CH=CH2 ƒ Acts as a depressant.
O ƒ Kills or disables more
|| people than any other drug.
B. [O] 3) CH3—CH2—C—H ƒ Is metabolized at a rate of
12-15 mg/dL per hour by a
social drinker.
C. + O2 2) CO2 + H2O
ƒ Is metabolized at a rate of 30
mg/dL per hour by an
alcoholic.
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Oxidation of Alcohol in the Body Effect of Alcohol on the Body

ƒ Enzymes in the liver oxidize ethanol.
ƒ The aldehyde produced impairs coordination.
ƒ A blood alcohol level over 0.4% can be fatal.
O
||
CH3CH2OH CH3CH 2CO2 + H2O
Ethyl alcohol acetaldehyde

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Alcohol Contents in Common

Products

% Ethanol Product
50% Whiskey, rum, brandy
40% Flavoring extracts
15-25% Listerine, Nyquil, Scope
12% Wine, Dristan, Cepacol
3-9% Beer, Lavoris

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