Derivatives of Hydrocarbons

Aldehydes, Ketones, and Chiral Molecules

Chapter 5
5.1 Structure and Bonding
5.2 Naming Aldehydes and Ketones
5.3 Some Important Aldehydes and
Ketones
5.4 Physical Properties of Aldehydes and
Ketones
5.5 Chiral Molecules
5.6 Oxation and Reduction
5.7 Addition Reactions
 Introduction
o carbonyl compounds : compounds with
C
carbonyl group
O

o examples of carbonyl compounds :

O O
R C H R C R'

aldehyde ketone

o general formula : CnH2nO

Carbonyl Containing Compound
Formula Family Formula Family

Ester
Aldehyde

Ketone Amide

Carboxylic Acid
 Aldehydes and Ketones
Only differ by location of carbonyl

Aldehydes RCHO

Ketones RC(=O)R’

Results in different properties and reactions

 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.

5
 Structure
• The functional group of an aldehyde is a
carbonyl group bonded to a hydrogen atom
– in methanal, the simplest aldehyde, the
carbonyl group is bonded to two hydrogens
– in other aldehydes, it is bonded to one
hydrogen and one carbon
• The functional group of a ketone is a carbonyl
group bonded to two carbons

O O O
HCH CH3 CH CH3 CCH3
Meth anal Ethanal Prop anone
(Formaldehyde) (Acetaldeh yd e) (Aceton e)
Naming Aldehydes and Ketones
Naming Aldehydes

9
Example
 Aldehydes in Flavorings
• Several naturally occurring
aldehydes are used as flavorings for
O
foods and fragrances.
C H

Benzaldehyde
(almonds)
O
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CH=CH C H Publishing as Benjamin Cummings

Cinnamaldehyde (cinnamon)

12
 Ketones in Common Use

Butter
flavoring

Nail polish remover,

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

16
Table 8.1: IUPAC nomenclature and common names for aldehyde and ketone compounds.

Compound Common name

Structure formula IUPAC

nomenclature
Aldehyde HCHO Methanal Formaldehyde

CH3CHO Ethanal Asetaldehyde

CH3CH2CHO Propanal Propionaldehyde

CH3CH2CH2CHO Butanal Butyraldehyde

Ketone CH3COCH3 Propanone Acetone

CH3CH2COCH3 2-butanone Methyl ethyl ketone

CH3CH2CH2COCH3 2-penthanone n–propyl methyl ketone

CH3CH2COCH2CH3 3-penthanone Diethyl ketone

Learning Check

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Solution

19
20
Solution

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Learning Check

22
Solution

23
 Learning Check
Name the following compounds.
O
|| O
A. CH3—CH2—CH2—C—CH3 B.

CH3 O
| ||
C. CH3—C—CH2—C—H
| 24
CH3
Solution

25
Learning Check

26
 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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Physical Properties

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Publishing as Benjamin Cummings
 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

33
 Solution

A. CH3—CH2—OH
O
B.

C. CH3—CH2—OH

34
 Solubility in Water
The electronegative O atom of the
carbonyl group in aldehydes and
ketones forms hydrogen bonds
with water.

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35
 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

36
 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

37
Synthesis of Aldehydes and
ketones
 Preparation of Aldehydes
Oxidation of primary alcohol

Hydration of alkynes

ALDEHYDES

Ozonolysis of alkenes

Hydrolysis of gem halides

i) Oxidation of 10 Alcohol
General equation :
H H
PCC
R C OH [O] R C O
H aldehyde
10 alcohol

• Oxidation of primary alcohols to aldehyde using pyridium chlorochromate

(PCC) in anhydrous media such as dichloromethane.

Example : H
H
PCC H3 C C O
H3 C C OH [O]
H ethanal
ethanol
ii) Hydration of Alkynes

General equation :
H2SO4 H OH enol
R C C R' + H2O R C C R'
HgSO4
alkyne
tautomerism

O
R CH2 C R'

aldehyde
Keto- Enol Tautomerism

• The name enol is derived from the IUPAC designation of it as both an

alkene (-en-) and alcohol (-ol).

• Keto and enol forms are examples of tautomers, constitutional isomers in

equilibrium with each other that differ in the location of hydrogen atom and a
double relative to a heteroatom, most often O, S, or N.

• This type of isomerism is called tautomerism.

O OH
|| |
CH3-C-CH3 CH3-C = CH2
acetone acetone
(keto form) (enol form)
iii) Ozonolysis of Alkenes
General equation :
H H H H
i) O3
R C C R' R C O + O C R'
ii) Zn/H3O+
alkene aldehyde

Example 1 :
H H H
i) O3
H3C C C CH2 CH3 H3 C C O +
ii) Zn/
2-pentene H 3 O+ ethanal H propanal
O C CH2 CH3
iii) Ozonolysis of Alkenes
Example 2 :
CH3
i) O3 O O
C CH2 CH CH2 C
ii) Zn/ H
H 3 O+ CH3 H

4-methylcyclopentene 3-methylpentandial
iv) Hydrolysis of Gem Halides
To produce aromatic aldehyde

Example :
H
X X H O
CH3 C C

hv or  H 2O
+ 2X2

Toulene Gem halides Benzaldehyde

iv) Hydrolysis of Gem Halides
Example :
H
Cl Cl H O
CH3 C
C

hv or  H 2O
+ 2Cl2

Br Gem halides
Br Br
4-bromotoulene
4-bromobenzaldehyde
 Preparation of Ketones
Oxidation of secondary alcohol

Hydration of alkynes
KETONES

Ozonolysis of alkenes

Friedel-Crafts acylation
i) Oxidation of 20 Alcohol
General equation :
OH O
K2Cr2O7
R C R' [O] R C R'
H+
H ketone
20 alcohol

•Secondary alcohols are oxidised to ketones using oxidation agent such as PCC,
chromic acid or potassium dichromate and sulfuric acid.

Example :
OH O
K2Cr2O7
H3C C CH3 [O] H3 C C CH3
H+
H propanone
propanol
 ii) Hydration of Alkynes
Example :
OH H
H2SO4
H3C C C H + H2O H3C C C H enol
HgSO4
propyne
tautomerism

O H
H3 C C C H
H
propanone
iii) Ozonolysis of Alkenes
Example :

CH2 CH3 O
i) O3
H3C C C CH2 CH3 H3C C CH2 CH3
ii) Zn/
H H 3 O+ 2-butanone

3-methyl-3-hexene
+
O C CH2 CH3
H

propanal
iv) Friedel-Crafts Acylation
To produce aromatic ketone

Example :
O
H3 C C
O
AlCl3
+ H3C C Cl

Chloroethane
Benzene Aromatic
Ketone
Reaction of Aldehydes and
Ketones
 K2Cr2O7
H2SO4, H2O
Oxidation

• Aldehydes are much more easily oxidized than ketones.

• Strong oxidizing agents such as potassium

permanganate, potassium dichromate, readily oxidize
aldehydes and they are also oxidized by such mild
oxidizing agents as silver oxide.

• Example
O O
|| ||
CH3(CH2)4 - C-H + K2Cr2O7 H+ CH3(CH2)4 – C - OH
hexanal hexanoic acid
Reduction

• Aldehydes are reduced to primary alcohols and ketons to secondary

alcohols by a variety of reducing agents. Catalytic hydrogenation
over a metal catalyst and reduction with sodium borohydride or
litium aluminium hydride are common.

H H
| H+ |
R- C=O R- C-OH
aldehyde alcohol 10

R’ R’
| H+ |

R- C=O R-C-OH
ketone alcohol 20
• Example

H
| LiAlH4
CH3- C=O CH3CH2OH
ethanal H+ ethanol
(alcohol 1o)

CH3 NaBH4 /H+

| or
CH3-C=O CH3-CH(CH3)OH
propanone H2/pt propanol
(alcohol 2°)
 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. Copyright © 2007 by Pearson Education, Inc.
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58
 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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59
 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

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 Addition Reactions

| + - + - |
—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.

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63
 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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64
 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.

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65
 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

66
 Solution

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

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

67
 Learning Check
Draw the structure of the acetal formed by
adding CH3OH to butanal.

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Solution

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Chiral Molecules

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72
 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

73
 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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74
 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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75
Some Everyday Chiral and Achiral Objects

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 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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 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

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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.

81
 Drawing Fischer Projections

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82
 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
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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