Chapter 14 Aldehydes, Ketones,

and Chiral Molecules

14.1
Aldehydes and Ketones

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

1
 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.

2
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
║ ║ ║
H−C−H CH3−C−H CH3−CH2−C−H
methanal ethanal propanal
(formaldehyde) (acetaldehyde) (propionaldehyde)
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 Naming Aldehydes

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Publishing as Benjamin Cummings
 Aldehydes in Flavorings
 Several naturally occurring aldehydes are used
as flavorings for foods and fragrances.
O

C H

Benzaldehyde
(almonds)
O
Copyright © 2007 by Pearson Education, Inc.
CH=CH C H Publishing as Benjamin Cummings

Cinnamaldehyde (cinnamon)
5
 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
║ ║
CH3−C−CH3 CH3−C−CH2−CH3
propanone 2-butanone
(dimethyl ketone) (ethyl methyl ketone)
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 Ketones in Common Use

Butter
flavoring

Nail polish remover,

Solvent
Propanone,
Dimethylketone, Copyright © 2007 by Pearson Education, Inc.
Acetone Publishing as Benjamin Cummings

7
Learning Check
Classify each as 1) aldehyde or 2) ketone.
O O
|| ||
A. CH3—CH2—C—CH3 B. CH3—C—H

CH3 O
O
| ||
C. CH3—C—CH2—C—H D.
|
CH3

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Solution
A. 2) ketone

B. 1) aldehyde

C. 1) aldehyde

D. 2) ketone

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Learning Check
Classify each as an aldehyde (1), ketone (2), alcohol (3),
or ether (4).
O
║
A. CH3─CH2─C─CH3 B. CH3─O─CH3

CH3 O OH
│ ║ │
C. CH3─C─CH2─C─H D. CH3─CH─CH3
│
CH3
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Solution
Classify each as an aldehyde (1), ketone (2),
alcohol (3), or ether (4).
O
║
A. CH3─CH2─C─CH3 B. CH3─O─CH3
(2) ketone (4) ether
CH3 O OH
│ ║ │
C. CH3─C─CH2─C─HD. CH3─CH─CH3
│
CH3
(1) aldehyde (3) alcohol 11
Learning Check
Name each of the following:
O
║
1. CH3─CH2─CH2─CH2─C─H

O
║
2. Cl─CH2─CH2─C─H
O
║
3. CH3─CH2─C─CH3

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Solution
O
║
1. CH3─CH2─CH2─CH2─C─H pentanal
O
║
2. Cl─CH2─CH2─C─H 3-chloropropanal

O
║
3. CH3─CH2─C─CH3 2-butanone;
ethyl methyl ketone
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Learning Check
Name the following compounds.
O
||
A. CH3—CH2—CH2—C—CH3 B. O

CH3 O
| ||
C. CH3—C—CH2—C—H
|
CH3

14
Solution

A. 2-pentanone; methyl propyl ketone

B. cyclohexanone

C, 3,3-dimethylbutanal

15
Learning Check

Draw the structural formulas for each:

A. 4-methylpentanal
B. 2,3-dichloropropanal
C. 3-methyl-2-butanone

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Solution

CH3 O
│ ║
A. 4-methylpentanal CH3─CH─CH2─CH2─C─H

Cl O
│ ║
B. 2,3-dichloropropanal Cl─CH2─CH─C─H

CH3 O
│ ║
C. 3-methyl-2-butanone CH3─CH─C─CH3
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Chapter 14 Aldehydes, Ketones,
and Chiral Molecules
14.2
Physical Properties

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

18
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.

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 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

Aldehydes and ketones have

 Higher boiling points than alkanes and ethers of
similar mass.
 Lower boiling points than alcohols of similar mass.
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Learning Check

Select the compound in each pair that would have the

Higher boiling point.
A. CH3—CH2—CH3 or CH3—CH2—OH
O
B.
or

C. CH3—CH2—OH or CH3—O—CH3

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Solution

A. CH3—CH2—OH

B. O

C. CH3—CH2—OH

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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

24
Learning Check
Indicate if each is soluble or insoluble in water.
A. CH3—CH2—CH3

B. CH3—CH2—OH
O
||
C. CH3—CH2—CH2—C—H

O
||
D. CH3—C—CH3

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Solution

A. CH3—CH2—CH3 insoluble

B. CH3—CH2—OH soluble
O
||
C. CH3—CH2—CH2—C—H soluble

O
||
D. CH3—C—CH3 soluble

26
Chapter 14 Aldehydes, Ketones and
Chiral Molecules

14.3
Oxidation and Reduction

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 Oxidation
 Aldehydes are easily oxidized to carboxylic acids.
O O
|| [O] ||
CH3—C—H CH3—C—OH
Acetaldehyde Acetic acid

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 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.
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29
Benedict’s Test

In the Benedict’s Test,

 Cu2+ reacts with aldehydes
that have an adjacent OH
group.
 Aldehydes are oxidized to
carboxylic acids.
 Cu2+ is reduced to give
Cu2O(s).

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30
 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

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Solution
1. butanal O
||
CH3—CH2—CH2—C—OH
butanoic acid

2. acetaldehyde O
||
CH3—C—OH
acetic acid

3. ethyl methyl ketone None. Ketones are not

oxidized by Tollen’s reagent.

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Chapter 14 Aldehydes, Ketones and
Chiral Molecules

14.4
Addition Reactions
| + - + - |
—C=O + X—Y —C—O—X
|
Y

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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 + X—Y — C—O—X
|
Y
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Acetal Formation

 Alcohols add to the carbonyl group of aldehydes and

ketones.
 The addition of two alcohols forms acetals.

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings 35

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.

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Cyclic Hemiacetals

A stable cyclic hemiacetal forms when the C=O

group and the —OH are both part of a five- or
six-atom carbon compound.

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

37
Learning Check

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

O—CH3
|
A. CH3—CH2—C—H
|
OH

O—CH2CH3
|
B. CH3—CH2—C—CH2—CH3
|
O—CH2CH3
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Solution

O—CH3
|
A. CH3—CH2—C—H 1) hemiacetal
|
OH

O—CH2CH3
|
B. CH3—CH2—C—CH2—CH3 2) acetal
|
O—CH2CH3
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Learning Check

Draw the structure of the acetal formed by adding

CH3OH to butanal.

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Solution

Draw the structure of the acetal formed by adding

CH3OH to butanal.
O—CH3
|
CH3—CH2—CH2—C—H
|
O—CH3

41
Chapter 14 Aldehydes, Ketones,
and Chiral Molecules
15.5
Chiral Molecules

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings
42
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. Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings

43
 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.

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44
 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

46
Enantiomers
Have same
 mp,
 bp,
 same chemistry
 Except: reaction with other chiral molecules

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 Smell:
R-(-)-carvone S-(+)-carvone

Spearmint Caraway
(Dill)
(Manderine Orange Peel)

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Enantiomers
 Have same
 mp,
 bp,
 same chemistry
 Except: reaction with other chiral molecules

•Except: rotation of plane of polarized light

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 Learning Check
Identify each as a chiral or achiral compound.

Cl Cl Cl

H C CH3 H C CH3 H C CH3

CH2CH3 H Br

A B C

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 Solution
Identify each as a chiral or achiral compound.

Cl Cl Cl

H C CH3 H C CH3 H C CH3

CH2CH3 H Br

A B C

chiral achiral chiral

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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

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53
 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.

54
Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings
Learning Check
Indicate whether each pair is a mirror image that
cannot be superimposed.
CH2OH CH2OH

A. H C CH3 and CH3 C H

Br Br

Cl Cl
B. H C CH3 and CH3 C H
H H
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Solution
Indicate whether each pair is a mirror image that
cannot be superimposed

CH2OH CH2OH Yes

A. H C CH3 and CH3 C H

Br Br

Cl Cl No

B. H C CH3 and CH3 C H

H H

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