Aldehydes, Ketones, and Chiral

Molecules
Aldehydes and Ketones

Carbonyl Group in Aldehydes and

Ketones
A carbonyl group
In an aldehyde is attached
to at least one H atom.

In a ketone is attached to
two carbon groups.

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

Naming Aldehydes
An aldehyde
Has an IUPAC name in which the -e in the alkane
name is changed to -al.
Has a common name for the first four aldehydes that
use the prefixes form (1C), acet (2C), propion (3C),
and butyr (4C), followed by aldehyde.
O
O
O

HCH
CH3CH
CH3CH2CH
methanal
(formaldehyde)

ethanal
(acetaldehyde)

propanal
(propionaldehyde)
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Naming Aldehydes

Aldehydes in Flavorings
Several naturally occurring aldehydes are used
as flavorings for foods and fragrances.
O
H

Benzaldehyde
(almonds)

O
CH=CH C H
Cinnamaldehyde (cinnamon)

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

Naming Ketones
Ketones are named
In the IUPAC system by replacing the -e in the alkane
name with one. The carbonyl carbon is indicated by
a number.
With a common name by indicating the alkyl groups
attached to the carbonyl group in alphabetical order
followed by ketone.
O
O

CH3CCH3
CH3CCH2CH3
propanone
butan-2-one
6
(dimethyl ketone)
(ethyl methyl ketone)

Learning Check
Classify each as 1) aldehyde or 2) ketone.
O
O
||
||
A. CH3CH2CCH3
B. CH3CH
CH3
O
|
||
C. CH3CCH2CH
|
CH3

O
D.

Ketones in Common Use

Butter
flavoring

Nail polish remover,

Solvent
Propanone,
Dimethylketone,
Acetone

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

Learning Check
Classify each as an aldehyde (1), ketone (2), alcohol (3),
or ether (4).
O

A. CH3CH2CCH3
B. CH3OCH3
CH3
O

C. CH3CCH2CH

CH3

OH

D. CH3CHCH3

Solution
Classify each as an aldehyde (1), ketone (2),
alcohol (3), or ether (4).
O

A. CH3CH2CCH3
B. CH3OCH3
(2) ketone
(4) ether
CH3
O
OH

C. CH3CCH2CH
D. CH3CHCH3

CH3
(1) aldehyde
(3) alcohol

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Learning Check
Name each of the following:
O

1. CH3CH2CH2CH2CH

2. ClCH2CH2CH
O

3. CH3CH2CCH3
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Learning Check
Name the following compounds.
O
||
A. CH3CH2CH2CCH3

B.

CH3
O
|
||
C. CH3CCH2CH
|
CH3

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Learning Check
Draw the structural formulas for each:
A. 4-methylpentanal
B. 2,3-dichloropropanal

C. 3-methylbutan-2-one

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Physical Properties

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Polar Carbonyl Group

The polar carbonyl group
Provides dipole-dipole interactions.
+ + C=O
C=O
Does not have H on the oxygen atom.
Cannot form hydrogen bonds.

15

Boiling Points
Aldehydes and ketones have
Polar carbonyl groups (C=O).
+ C=O
Attractions between polar groups.
+ + C=O
C=O
Higher boiling points than alkanes and ethers of
similar mass.
Lower boiling points than alcohols of similar mass.
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Comparison of Boiling Points

58

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17

Learning Check
Select the compound in each pair that would have the
Higher boiling point.
A. CH3CH2CH3 or CH3CH2OH

O
B.

or

C. CH3CH2OH or CH3OCH3

18

Solubility in Water
The electronegative O atom of the carbonyl
group in aldehydes and ketones forms
hydrogen bonds with water.

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

19

Learning Check
Indicate if each is soluble or insoluble in water.
A. CH3CH2CH3
B. CH3CH2OH

O
||
C. CH3CH2CH2CH
O
||
D. CH3CCH3
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Solution
A. CH3CH2CH3

insoluble

B. CH3CH2OH

soluble

O
||
C. CH3CH2CH2CH

soluble

O
||
D. CH3CCH3

soluble

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Oxidation and Reduction

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Oxidation
Aldehydes are easily oxidized to carboxylic acids.
O
O
||
[O]
||
CH3CH
CH3COH
Acetaldehyde
Acetic acid

23

Oxidation and Reduction

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24

Tollens 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 Test
In the Benedicts Test,
Cu2+ reacts with aldehydes
that have an adjacent OH
group.
Aldehydes are oxidized to
carboxylic acids.
Cu2+ is reduced to give
Cu2O(s).
Copyright 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings
26

Learning Check
Write the structure and name of the oxidized product
when each is mixed with Tollens reagent.
1. butanal
2. acetaldehyde
3. ethyl methyl ketone

27

Solution
1. butanal

O
||
CH3CH2CH2COH
butanoic acid

2. acetaldehyde

O
||
CH3COH
acetic acid

3. ethyl methyl ketone None. Ketones are not

oxidized by Tollens reagent.
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Addition Reactions
When a polar molecule adds to the carbonyl group of
an aldehyde or ketone
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
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Acetal Formation
Alcohols add to the carbonyl group of aldehydes and
ketones.
The addition of two alcohols forms acetals.
IMPORTANT IN DISACCHARIDE AND
POLYSACHARIDES

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

30

Hemiacetal Formation
The addition of one alcohol to an aldehyde or ketone
forms an intermediate called a hemiacetal.
Usually, hemiacetals are unstable and difficult to
isolate.

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

31

Learning Check
Identify each as a 1) hemiacetal or 2) acetal.
OCH3
|
A. CH3CH2CH
|
OH
OCH2CH3
|
B. CH3CH2CCH2CH3
|
OCH2CH3
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Learning Check
Draw the structure of the acetal formed by adding
CH3OH to butanal.

33

Chiral Compounds
Chiral compounds
Have the same number of atoms
arranged differently in space.
Have one or more chiral carbon
atoms bonded to four different
groups.
Are mirror images like your
hands. Try to superimpose your
thumbs, palms, back of hands,
and little fingers.
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Mirror Images
The mirror images of
Chiral compounds cannot be superimposed.
Two compounds of bromochloroiodomethane can align
the H and I atoms, which places the Cl and Br atoms
on opposite sides.

Copyright 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

35

Achiral Structures are

Superimposable
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.

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Some Everyday Chiral and

Achiral Objects

37

Learning Check
Identify each as a chiral or achiral compound.

Cl

Cl
H

CH3

CH2CH3
A

Cl
CH3

Br

CH3

38

Fischer Projections
A Fischer projection
Is a 2-dimensional representation of a 3-dimensional
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.

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Drawing Fischer Projections

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

40

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.

Copyright 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

41

Learning Check
Indicate whether each pair is a mirror image that
cannot be superimposed.
CH2OH

CH2OH
A.

B.

CH3

and

CH3 C

Br

Br

Cl

Cl

C
H

CH3

and

CH3 C

H
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