Chapter 15 Aldehydes, Ketones,

and Chiral Molecules

Aldehydes and Ketones

The carbonyl group
is found in aldehydes
and ketones.
In an aldehyde, an H
atom is attached to a
carbonyl group.
In a ketone, two
carbon groups are
attached to a
carbonyl group.

15.1 Structure and Bonding

15.2 Naming Aldehydes and Ketones
15.3 Some Important Aldehydes and Ketones

The Polar Carbonyl Group

Naming Aldehydes
In the IUPAC names for aldehydes, the -e in
the corresponding alkane is replaced by al.
Common names use a prefix with aldehyde:
form (1C), acet (2C), propion (3), and butry (4C)

The carbonyl group

(C=O):
Consists of a sigma and
pi bond.
Has a partially negative
O and a partially
positive C.
Has polarity that
influences the
properties of aldehydes
and ketones.
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Aldehydes in Flavorings

Naming Ketones
In the IUPAC name, the -e in the alkane name is
replaced with one.
In the common name, add the word ketone after
naming the alkyl groups attached to the carbonyl
group.
O
O
||
||
CH3-CCH3
CH3CCH2CH3
Propanone
2-Butanone
(Dimethyl ketone;
(Ethyl methyl ketone)
Acetone)

Several naturally occurring aldehydes are

used as flavorings for foods and fragrances.
O
C H

Benzaldehyde (almonds)
O
CH=CH C H

Cinnamaldehyde (cinnamon)

Ketones in Common Use

Learning Check
Classify each as 1) aldehyde or 2) ketone.
O
O
||
||
B. CH3CH
A. CH3CH2CCH3

Propanone,
Dimethylketone,
Acetone

O
CH3
|
||
C. CH3CCH2CH
|
CH3

O
D.

Solution

Learning Check

Classify as an 1) aldehyde or 2) ketone.

O
O
||
||
A. 2 CH3CH2CCH3
B. 1 CH3CH
O
CH3
|
||
C. 1 CH3CCH2CH
|
CH3

Name the following compounds.

O
||
A. CH3CH2CCH3
B.

O
CH3
|
||
C. CH3CCH2CH
|
CH3

O
D. 2

Solution

Learning Check

O
||
A. CH3CH2CCH3
B.
2-Butanone; ethyl methyl ketone
CH3
O
|
||
C. CH3CCH2CH
|
CH3
3,3-Dimethylbutanal

10

Draw the structural formulas for each:

A. 3-Methylpentanal

B. 2,3-Dichloropropanal
Cyclohexanone
C. 3-Methyl-2-butanone

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Chapter 15 Aldehydes, Ketones,

and Chiral Molecules

Solution
A. 3-Methylpentanal

CH3
O
|
||
CH3CH2CHCH2CH

Cl O
|
||
B. 2,3-Dichloropropanal ClCH2CHCH
O
||
C. 3-Methyl-2-butanone
CH3CHCCH3
|
CH3

15.4 Physical Properties

15.5 Chiral Molecules

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Physical Properties

The polar carbonyl group provides

dipole-dipole interactions.
+ -

Comparison of Boiling Points

+ -

C=O
C=O
Without a H on the oxygen atom,
aldehydes and ketones cannot hydrogen
bond.

15

Solubility in Water

Aldehydes and ketones have higher boiling

points than alkanes and ethers of similar
mass, but lower boiling points than alcohols.

16

Comparison of Physical Properties

The electronegative O atom of the carbonyl

group of aldehydes and ketones forms
hydrogen bonds with water.

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Learning Check

Solution

Select the compound in each pair that would

have the higher boiling point.
A. CH3CH2CH3 or CH3CH2OH

Select the compound in each pair that would

have the higher boiling point.
A. CH3CH2OH

B.

B.

or

C. CH3CH2OH or CH3OCH3

C. CH3CH2OH
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Learning Check

Solution

Indicate if each is soluble or insoluble in water.

A. CH3CH2CH3

Indicate if each is soluble or insoluble in water.

A. CH3CH2CH3
insoluble

B. CH3CH2OH

B. CH3CH2OH

soluble
O
||
C. CH3CH2CH2CH soluble
O
||
D. CH3CCH3
soluble

O
||
C. CH3CH2CH2CH
O
||
D. CH3CCH3
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22

Chiral Objects

Types of Isomers

23

Chiral compounds have the

same number of atoms
arranged differently in space.
A chiral carbon atom is
bonded to four different
groups.
Your hands are chiral. Try to
superimpose your thumbs,
palms, back of hands, and
little fingers.
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Achiral Structures are

Superimposable

Mirror Images

When the mirror image of an achiral structure

is rotated, the structure can be aligned with the
initial structure. Thus this mirror image is
superimposable.

The mirror images of chiral compounds cannot

be superimposed.
When the H and I atoms are aligned, the Cl and
Br atoms are on opposite sides.

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26

Some Everyday Chiral and

Achiral Objects

Learning Check
Identify each as a chiral or achiral compound.
Cl
H C CH3
CH2CH3
A

Cl
H C CH3

Br

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Solution

Fischer Projections

Identify each as a chiral or achiral compound.

H C CH3
CH2CH3

Cl
H C CH3

Cl

H C CH3

Br

Chiral

H C CH3

27

Cl

Cl

Achiral

A Fischer projection:
Is a 2-dimensional representation of a 3dimensional molecule.
Places the most oxidized group at the top.
Uses vertical lines in place of dashes for
bonds that go back.
Uses horizontal lines in place of wedges
for bonds that come forward.

Chiral
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Drawing Fischer Projections

D and L Notations
By convention, the letter L is assigned to the
structure with the OH on the left.
The letter D is assigned to the structure with
the OH on the right.

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Learning Check

Solution

Indicate whether each pair is a mirror image

that cannot be superimposed (enantiomers).
H C CH3

and

CH3

Cl
H C CH3
H

A.

C H

CH3

CH2OH
and

CH3

B.

C H

H C CH3
H

C H

Yes

Br

Cl

Cl
and

H C CH3
Br

Br

Br

B.

CH2OH

CH2OH

CH2OH
A.

Indicate whether each pair is a mirror image

that cannot be superimposed (enantiomers).

Cl
and

CH3

C H

No

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Chapter 15 Aldehydes and

Ketones and Chiral Molecules

Oxidation

15.6 Oxidation and Reduction

15.7 Addition Reactions

35

Aldehydes are easily oxidized to carboxylic

acids.
O
O
||
[O]
||
CH3CH
CH3COH
Acetaldehyde
Acetic acid

36

Tollens Test

Benedicts Test

Tollens reagent,
which contains
Ag+, oxidizes
aldehydes, but
not ketones.
Ag+ is reduced to
metallic Ag,
which appears as
a mirror in the
test tube.

Benedicts reagent,
which contains Cu2+,
reacts with aldehydes
that have an adjacent
OH group.
When an aldehyde is
oxidized to a
carboxylic acid, Cu2+
is reduced to give
Cu2O(s).

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Learning Check

Solution
A. Butanal

O
||
CH3CH2CH2COH
Butanoic acid
B. Acetaldehyde
O
||
CH3COH
Acetic acid
C. Ethyl methyl ketone None. Ketones are not
oxidized by Tollens reagent.

Write the structure and name of the

oxidized product when each is mixed with
Tollens reagent.
A. Butanal
B. Acetaldehyde
C. Ethyl methyl ketone
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40

Addition Reactions

Acetal Formation

Polar molecules can add to the carbonyl groups

of aldehydes and ketones.
The negative part of the added molecule bonds
to the positive carbonyl carbon.
The positive part of the added molecule bonds
to the negative carbonyl oxygen.
| + + C=O + XY

|
COX
|
Y

41

Alcohols add to the carbonyl group of aldehydes

and ketones.
The addition of two alcohols forms acetals.

42

Hemiacetal Formation

Cyclic Hemiacetals

The addition of one alcohol to an aldehyde or

ketone forms an intermediate called a hemiacetal.
Usually, hemiacetals are unstable and difficult to
isolate.

Stable hemiacetals form when the C=O group

and the OH are both part of five- or six-atom
carbon compounds.

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Learning Check

44

Solution
Identify each as a 1) hemiacetal or 2) acetal.
OCH3
|
A. CH3CH2CH
1) hemiacetal
|
OH
OCH2CH3
|
B. CH3CH2CCH2CH3 2) acetal
|
OCH2CH3

Identify each as a 1) hemiacetal or 2) acetal.

OCH3
|
A. CH3CH2CH
|
OH
OCH2CH3
|
B. CH3CH2CCH2CH3
|
OCH2CH3
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Learning Check

46

Solution

Draw the structure of the acetal formed

by adding CH3OH to butanal.

Draw the structure of the acetal formed

by adding CH3OH to butanal.
OCH3
|
CH3CH2CH2CH
|
OCH3

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