Chapter 14

Lecture
Outline
Prepared by
Andrea D. Leonard
University of Louisiana at Lafayette

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Organic Compounds that Contain
Oxygen, Halogen, or Sulfur
Four families of compounds that contain a C atom
singly bonded to O, S, or X (F, Cl, Br, or I) are:
1. Alcohols, which contain an OH (hydroxyl) group

2. Ethers, which have two alkyl groups bonded to

an O atom

2
Organic Compounds that Contain
Oxygen, Halogen, or Sulfur
3. Alkyl halides, which contain a halogen atom X
(X = F, Cl, Br, or I)

4. Thiols, which contain a SH (sulfhydryl) group

3
Structure and Properties of Alcohols

•Alcohols contain a hydroxyl (OH) group.

•Alcohols are classified by the number of C atoms

bonded to the C with the OH group.

A primary (1o) alcohol has

an OH group on a C bonded
only to 1 C atom.
1o 4
Structure and Properties of Alcohols

A secondary (2o) alcohol has

an OH group on a C bonded
only to 2 C atoms.

2o

A tertiary (3o) alcohol has

an OH group on a C bonded
3o only to 3 C atoms.

5
Structure and Properties of Alcohols

•An alcohol contains an O atom with a bent shape

like H2O, with a bond angle of 109.5o.

•Alcohols have two polar bonds, C—O and O—H,

with a bent shape, therefore it has a net dipole.

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Structure and Properties of Alcohols

•Alcohols have an H atom bonded to an O atom,

making them capable of intermolecular hydrogen
bonding.

•All of these properties give alcohols much stronger

intermolecular forces than alkanes and alkenes.

7
Structure and Properties of Alcohols

•Therefore, alcohols have higher boiling and melting

points than hydrocarbons of comparable size and
shape.

stronger intermolecular forces

higher boiling and melting point
8
Structure and Properties of Alcohols

•Alcohols are soluble in organic solvents.

•Low molecular weight alcohols (6 C’s or less)
are soluble in water.
•Higher molecular weight alcohols (6 C’s or more)
are not soluble in water.

2 C’s in chain 8 C’s in chain

water soluble water insoluble
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Nomenclature of Alcohols
HOW TO Name an Alcohol Using the IUPAC System

Example Give the IUPAC name of the following alcohol.

Find the longest carbon chain containing the

Step [1]
C bonded to the OH group.

•Change the –e ending of

the parent alkane to the
6 C’s in longest chain suffix –ol.
hexane ----> hexanol 10
Nomenclature of Alcohols
HOW TO Name an Alcohol Using the IUPAC System
Number the carbon chain to give the OH group
Step [2]
the lower number, and apply all other rules
of nomenclature.

Answer
3-hexanol
5-methyl-3-hexanol

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Nomenclature of Alcohols

•When an OH group is bonded to a ring, the OH

is automatically on C1.

•The “1” is usually omitted from the name.

•The ring is then numbered to give the next

substituent the lower number.

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Nomenclature of Alcohols

•Common names are often used for simple alcohols.

•Name all the C atoms of the molecule as a single

alkyl group.

•Add the word alcohol, separating the words with

a space.

13
Nomenclature of Alcohols

•Compounds with two OH groups are called diols

or glycols.

•Compounds with three OH groups are called triols.

1,2-ethanediol
1,2-cyclopentanediol

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Interesting Alcohols
Common alcohols
•Methanol (CH3OH) is a useful as a solvent and
a starting material for plastics, but it is toxic due
to its oxidation in the liver.

•Ethanol (CH3CH2OH) is the alcohol present in

alcoholic beverages, and it is formed from the
fermentation of carbohydrate chains.

•2-Propanol [(CH3)2CHOH), isopropyl alcohol] is

the major component of rubbing alcohol, which is
used to sterilize skin and medical instruments.

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Interesting Alcohols
Common Diols and Triols

•Ethylene glycol (HOCH2CH2OH), a diol, is the major

component of antifreeze; it is sweet tasting but
extremely toxic.

•Glycerol [(HOCH2)2CHOH], a triol, is used in

lotions, liquid soap, and shaving cream; it is also
sweet tasting, but nontoxic, so it can be used
in food products.

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Interesting Alcohols
Carbohydrates
Carbohydrates are very long, alcohol-containing,
and naturally occurring polymers, synthesized
primarily by plants.

•Starch is the main carbohydrate in seeds and the

roots of plants, and it can be metabolized by
humans into glucose.

•Cellulose, the major component of wood, cotton,

and flax, gives rigidity to plants, however it
cannot be metabolized by humans.
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Interesting Alcohols
Carbohydrates

Glucose

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Interesting Alcohols
Carbohydrates

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Reactions of Alcohols
Dehydration
•Dehydration is the loss of H2O from a starting
material.
•It occurs when an alcohol is treated with a strong
acid like H2SO4, and forms an alkene product.

•Dehydration is an example of an elimination

reaction, in which parts of the starting material are
“lost” and a multiple bond is formed.
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Reactions of Alcohols
Dehydration
•Examples:

21
Reactions of Alcohols
Dehydration
•Asymmetric alcohols can form two possible products.
H H H
H C1 C2 C3 CH3 + H2O
H
H H H H2SO4 1-butene
H C1 C2 C3 CH3
H H H
H OH H
H C1 C2 C3 CH3 + H2O
2-butanol
H
major product: 2-butene
•Zaitsev Rule: the major product has the most alkyl
groups bonded to the C═C. 22
Reactions of Alcohols
Oxidation
Oxidation results in an:
•increase in the number of C—O bonds
•decrease in the number of C—H bonds

The symbol [O] indicates an oxidation reagent

(commonly K2Cr2O7) has been added.
23
Reactions of Alcohols
Oxidation
•Primary (1o) alcohols first oxidize to aldehydes
(RCHO), replacing 1 C—H with 1 C—O.
•Aldehydes are further oxidized to carboxylic
acids (RCOOH), replacing 1 C—H with 1 C—O.

1o alcohol aldehyde carboxylic acid

(ROH) (RCHO) (RCOOH)
24
Reactions of Alcohols
Oxidation
•Secondary (2o) alcohols are oxidized to ketones
(R2CO).

25
Reactions of Alcohols
Oxidation
•Tertiary (3o) alcohols have no H atoms on the C
with the OH group, so they are not oxidized.

26
Focus on Health & Medicine
The Metabolism of Ethanol
•When ethanol is consumed it is quickly absorbed
in the stomach and small intestines.

•In the liver, the enzymes alcohol and aldehyde

dehydrogenase act as oxidizing reagents.

O O
[O] [O]
CH3CH—OH C C
CH3 H CH3 OH
ethanol acetaldehyde acetic acid

•Consuming more ethanol than can be metabolized

leads to a buildup of acetaldehyde, which is toxic.
27
Focus on Health & Medicine
The Metabolism of Methanol
•Methanol is oxidized into formaldehyde and then
to formic acid by the same enzymes as ethanol.

•Both of these compounds are extremely toxic, and

consumption of methanol leads to decreased
blood pH, blindness, and finally death.

O O
[O] [O]
CH3—OH C C
H H H OH
methanol formaldehyde formic acid
28
Focus on Health & Medicine
Health Effects of Alcohol Consumption
•Alcohol consumption in small amounts causes
dizziness, giddiness, and decrease of social
inhibitions.
•Large amounts of alcohol causes decreased
coordination and reaction time.
•Even larger amounts result in coma or death.
•Chronic excessive alcohol consumption leads
to cirrhosis of the liver.
•Pregnant women should not drink alcohol as the
ethanol crosses the placenta and affects the fetus,
which lacks the enzymes to metabolize it properly.
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Structure and Properties of Ethers

•Ethers have two alkyl groups bonded to an O atom.

•The two alkyl groups can be the same, or they

can be different.

30
Structure and Properties of Ethers

•An ether has an O atom with a bent shape like H2O,

with a bond angle of 109.5o.

31
Structure and Properties of Ethers

•The ether O can be found contained in a ring.

•A ring that contains a heteroatom is called a
heterocycle.
•A 3 carbon ether heterocycle is called an epoxide.

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Structure and Properties of Ethers
Physical Properties
•Ether has two polar C—O bonds with a bent
shape, therefore it has a net dipole.

•Ether does not contain an H atom bonded to an

O atom, so ether cannot form intermolecular
hydrogen bonds.

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Structure and Properties of Ethers
Physical Properties
These facts give ethers:

•stronger intermolecular forces than alkanes

•weaker intermolecular forces than alcohols

As a result, ethers of comparable size and shape

tend to have:

•higher melting and boiling points than hydro-

carbons

•lower melting and boiling points than alcohols

34
Structure and Properties of Ethers
Physical Properties

35
Structure and Properties of Ethers
Physical Properties
•Ethers are soluble in organic solvents.
•Low molecular weight ethers (5 C’s or less) are
soluble in water, as water can hydrogen bond to
the ether’s O atom.

•Higher molecular weight ethers (6 C’s or more)

are not soluble in water. 36
Naming Ethers

Simple ethers are usually assigned common names:

•name both alkyl groups bonded to the O atom
•arrange these names alphabetically
•finally, add the word “ether” to the end

CH3 O CH2CH3 CH3CH2 O CH2CH3

methyl ethyl ethyl ethyl

ethyl methyl ether diethyl ether

37
Naming Ethers

More complex ethers are named using the IUPAC

system:

•one alkyl group is named as a hydrocarbon chain

•the other is named as part of a substituent bonded

to that chain

CH3O— CH3CH2O—
methoxy ethoxy

38
Focus on Health & Medicine
Ethers as Anesthetics
•Diethyl ether was first demonstrated as an
anesthetic in 1846 by the dentist Dr. William Morton.
•Prior to this, patients undergoing surgery had to
tolerate excruciating pain.
•Modern variations include the three ethers below:

39
Alkyl Halides

•Alkyl halides contain a halogen atom X (where

X = F, Cl, Br, I).

•They are classified by the number of C atoms

bonded to the C with the halogen.

A primary (1o) alkyl halide

has an X group on a C
bonded only to 1 C atom.
1o

40
Alkyl Halides

A secondary (2o) alkyl halide

has an X group on a C
bonded only to 2 C atoms.

2o

A tertiary (3o) alkyl halide

has an X group on a C
bonded only to 3 C atoms.
3o
41
Alkyl Halides
Physical Properties

•Alkyl halides contain a polar C—X bond, thus

they contain a net dipole.

•They are not capable of intermolecular hydrogen

bonding.

•As a result, they have higher melting and boiling

points than similar alkanes, but lower than alcohols.

42
Alkyl Halides
Physical Properties
The boiling and melting points of an alkyl halide
will increase with:
•the size of the alkyl group
•the size of the halogen

All alkyl halides are insoluble in water. 43

Alkyl Halides
Nomenclature
HOW TO Name an Alkyl Halide Using the IUPAC System

Example Give the IUPAC name of the following

alkyl halide.

Step [1] Find the parent carbon chain containing

the halogen.

7 C’s = heptane
44
Alkyl Halides
Nomenclature
HOW TO Name an Alkyl Halide Using the IUPAC System

Step [2] Apply all other rules of nomenclature.

a) Number the chain, give the halogen the lowest

possible number.

45
Alkyl Halides
Nomenclature
HOW TO Name an Alkyl Halide Using the IUPAC System

Step [2] Apply all other rules of nomenclature.

b) Name and number, then alphabetize the

substituents.

Answer: 2-chloro-5-methylheptane
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Alkyl Halides
Interesting Alkyl Halides
•Chloromethane (CH3Cl) is produced by kelp, algae,
and emissions from volcanoes.

•Dichloromethane (CH2Cl2) is a solvent once used

to decaffeinate coffee.

•Trichloromethane (CHCl3, chloroform) and

tetrachloromethane (CCl4, carbon tetrachloride)
are useful industrially produced solvents that
are toxic if inhaled or ingested.

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Organic Compounds that Contain Sulfur

•Thiols contain a SH (sulfhydryl) group.

•Because S is just below O on the periodic table,

thiols are similar to alcohols.

•Thiols have a bent shape around the S atom.

48
Organic Compounds that Contain Sulfur

•However, thiols contain no O—H bonds, so they

are incapable of intermolecular hydrogen bonding.

•This gives thiols lower boiling and melting points

than similar alcohols.

CH3CH2—OH CH3CH2—SH
ethanol ethanethiol

bp 78 oC bp 35 oC

49
Organic Compounds that Contain Sulfur

To name a thiol in the IUPAC system:

•name the parent hydrocarbon chain as an alkane

•add the suffix “-thiol”

•number the chain to give the SH the lowest number

CH3—SH CH3CH2CH2—SH

methanethiol 1-propanethiol

50
Organic Compounds that Contain Sulfur

•Thiols have a characteristic foul odor (skunk,

onions, etc.)

•They can be oxidized to disulfides.

51
Organic Compounds that Contain Sulfur

•The disulfides can be converted back to thiols

with a reducing agent, [H], through a reduction
reaction.

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Organic Compounds that Contain Sulfur
•To make straight hair curly, the disulfide bonds
holding the hair proteins together are reduced.

•The hair is then turned around curlers, and an

oxidizing agent is applied.

•This re-forms the disulfide bonds in the hair, now

giving it a curly appearance.
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