Chapter 14

Aldehydes, Ketones
and
Chiral Molecules

Introduction
- the carbonyl compounds contain a carbonyl group
O
||
C
/\
The aldehydes contains at least one H atom bonded
to the carbonyl carbon.
or O
||
General formula of aldehydes: C
/\
R-CHO
R H
or R-CH = O
or O
General formula of Ketones: ||
R2CO
C
or R2C=O
2 /\
R R

1
 Introduction (cont)

-
Aldehydes and ketones have similar chemical and physical
properties

For aldehydes, the carbonyl group is always located

at the end of the carbon chain (carbon 1).

For ketones, the carbonyl group is always located

within the carbon chain.

Structure and physical properties

Carbonyl compounds are polar compounds and they
boil at higher temperature than hydrocarbon with the
same number of carbon.

-
Carbonyl compounds can form hydrogen bond with water, so
they are reasonably ewater soluble

When the carbon length increases, the carbonyl

compounds become less soluble in water.

2
 Nomenclature of Aldehydes
• If the CHO is bonded to a chain of carbons, find the
longest chain containing the CHO group, and
change the –e ending of the parent alkane to the
suffix –al (IUPAC system).

• Number the chain or ring to put the CHO group at

C1, but omit this number from the name.

• Apply all the other usual rules of nomenclature

Note: The simplest aldehyde is H2C=O

5

Example: Name the following compounds.

3
 Nomenclature of Ketones
(IUPAC system)
1. Find the longest continuous chain containing the
carbonyl group, and change the –e ending of the
parent alkane to the suffix -one.
2. Number the carbon chain to give the carbonyl carbon
the lowest number. Apply all of the usual rules of
nomenclature.
3. With cyclic ketones, numbering always begins at the
carbonyl carbon, but the “1” is usually omitted from
the name.
4. The ring is numbered clockwise or counterclockwise
to give the first substituent the lower number.
7

Nomenclature of Ketones (cont)

(Common names)

• The names are formed by naming both alkyl

groups on the carbonyl carbon, arranging them
alphabetically, and adding the word “ketone”.

2-butanone) (IUPAC name) Ethyl methyl ketone (common name)

• Three widely used common names for some

simple ketones do not follow this convention. 8

4
 Example: Name the following compounds.

Note: The simplest ketone is acetone

9

Several naturally occurring aromatic aldehydes

and ketones are responsible for the odours and
tastes of food flavorings.

- Vanillin
benzaldehyde (vanilla)

Cinnaminaldehyde Butanedione
(cinnamon) (butter flavour)
10

5
Physical properties of Aldehydes and Ketones
* Boiling points
Their boiling points is higher than the boiling points
of alkanes but lower than alcohols (of similar size).
no need to know numbers, just trend
Boiling points: bp
Butane 0C
Ethyl methyl ether 8C
propanal
49 C
Propanone 56 C
1-propanol
97 C
The dipole-dipole attraction is not as strong as a
hydrogen bond. 11

Physical properties of Aldehydes and Ketones

* Solubility in water
Aldehydes and Ketones do not form hydrogen bond
with each other, but the oxygen of the carbonyl
group does hydrogen bond with water.
- Aldehydes with one to four carbon atoms are very soluble in
water

As the nonpolar carbon chain increases, the solubility

in water decreases.
Aldehydes and ketones with five carbons are slightly
soluble in water, but with six or more carbon atoms
they are insoluble.
12

6
 Reactions involving Aldehydes and Ketones

Aldehydes can easily be oxidized further to carboxylic

acid whereas ketones generally do not undergo
further oxidation.
General equation:

Potassium permanganate and chromic acid can be

used as oxidizing agents.
13

Reactions involving Aldehydes and Ketones (cont)

Example:

- -

14

7
 Reactions involving Aldehydes and Ketones (cont)
Aldehydes and ketones can be distinguished by the
Tollen’s test.

The reaction gives a silver mirror precipitate using

aldehydes, but there is NO reaction with ketones.

Tollen's reagent carboxylic acid silver mirror

15

Example: Write the equation of the Tollen’s test

with:

(See Problem 14.5 page 505, 6th edition) (See Problem 14.4 page 517, 4th edition)
(See Problem 14.5 page 526, 5th edition) (See Problem 5 page 88, custom edition)
16

8
 Reactions involving Aldehydes and Ketones (cont)
Reduction reactions
- aldehyes and ketones can be reduced to the corresponding
alcohol by a variety of reducing agents

By example, hydrogenation (using hydrogen gas) in

presence of a metal catalyst leads to an alcohol.

General equation:

- -

17

Reactions involving Aldehydes and Ketones (cont)

Reduction reactions (cont)

- -

- -

(See Problem 14.6 page 506, 6th ed.) (See Problem 14.5 page 517, 4th ed.)
(See Problem 14.6 page 526, 5th ed.) (See Problem 6 page 88, custom ed.)
18

9
Reactions involving Aldehydes and Ketones (cont)
Hemiacetals and Acetals
The carbonyl compounds undergo addition across the
polar bond C=O in presence of acid catalyst.

- -

In presence of an excess of alcohol (R’OH), they

undergo substitution reaction to form an acetal.
19

Reactions involving Aldehydes and Ketones (cont)

- -

-
20

10
Reactions involving Aldehydes and Ketones (cont)
Similar reaction occur with ketones to lead to a
hemiacetal and acetal.

- -

-
21

Summary
Hemiacetal

Aldehydes (R-CH=O)

O
Acetal
||
R-C-H

Hemiacetal

Ketone (R1COR2)

Acetal
22

11
 Example: Identify each the following structures as
Hemiacetal, Acetal or neither.

(See Problem 14.7 page 509, 6th ed.) (See Problem 14.6 page 519, 4th ed.)
(See Problem 14.7 page 528, 5th ed.) (See Problem 7 page 90, custom ed.)
23

Extra problem
A. Draw the structure of the hemiacetal and acetal
formed when ethanol reacts with the following
compounds in presence of an acid catalyst.

1.

2.

Draw the structure of the actetal and hemiacetal formed

when ethanol is replaced by 1,2-ethanediol.

12
 Chiral molecules

We can distinguish several types of isomerism.

- the structural (or constitutional) isomers)

- The stereoisomers

24

TYPES OF ISOMERS (cont)

* Stereoisomers
Two molecules are stereoisomers if they have the
same molecular formula, same bond connectivity but
differ in the fixed arrangement of the atoms in 3D
space.

Example:

- the molecules are stereoisomers

25

13
 Stereoisomers (cont)

A and B are mirror images and they are not

superimposable.
they are enantiomers

26

Example:
Classify each following pair as constitutional isomers
or stereoisomers.

27

14
 Chirality

A molecule is chiral if its two mirror image

forms are not superimposable upon one another.

A molecule is achiral if its two mirror image forms

are superimposable.

28

Chiral and Achiral Molecules

Although everything has a mirror image, mirror
images may or may not be superimposable.
Some molecules are like hands. Left and right hands
are mirror images, but they are not identical, or
superimposable.

29

15
 The Chirality Center
- an atom with four idfferent groups attached to it is called a
chiral center

w
x C y
z
- chiral carbon

A molecule with a single chirality center always is

chiral.
We denote asymmetric atoms with an asterisk *
30

Example 1: Case of CFIClBr

Cl
F-C -I
|
Br

31

16
Example 2: Case of 3-bromohexane
things that can be chiral: C or CH. disregard CH2, CH3, double
bond, triple bond, etc.

|CH3CH2-C-CH2CH2CH
3
|
Br

carbon is chiral

32

Example 3: Case of 3-bromopentane

H
|
CH3CH2-C-CH2-CH3
|
Br

no chiral carbon

Note: A molecule with two or more chirality centers

may be chiral or it may not.
33

17
 Chiral molecules
Up to this point you would likely have thought
of 2-bromobutane as one molecule, especially when
you draw it without 3D information:

chiral carbon

In 3D reality, it can be either of these two different

molecules…

34

Chiral molecules (cont)

Example: case of 3-chlorocyclohexanone

But in 3D reality, it can be either of these two different

molecules…

A B
35

these two are mirror images and enantromers (try flipping B)

18
 These two possibilities are non-identical mirror
images of each other:

Molecule B turned 180o around the vertical axis clearly

shows the two compounds are not the same:

36

Chiral drugs

chiral carbon

Ibuprofen
37

when mirrored, there is an active and inactive version of the

drug

19
 8 chiral carbon atoms

Cholesterol

38

Example: Draw the mirror image of the compound

below.

39

20
 40

Fischer Projections
The Fisher projection is a simplified way to represent
tetrahedral carbon atoms in two dimensions.
Conversion of the Hashed-Wedged line structures
1) Vertical lines are away from you.
2) Horizontal lines are toward you.

41

21
 Nomenclature D, L
- the most oxidized group is draw at the top in the Fischer
projection

The designation as a D or L isomer is determined by

the position of the OH group attached to the chiral
carbon farthest from the most oxidized group at the top
in the Fischer projection.
Case of glyceraldehyde:

42

Nomenclature D, L (cont)

43

22
Example: Draw the mirror image of the following
compounds and identify each as D or L
isomer.

End

Practice exercises (Chapter 14)

(6th edition of the textbook)

14.1, 14.3, 14.5, 14.9, 14.11, 14.13, 14.15, 14.19,

14.21, 14.23b,d, 14.25, 14.27, 14.33, 14.35,
14.37, 14.39, 14.43, 14.45, 14.49, 14.51, 14.53,
14.55, 14.57, 14.59, 14.61

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 Practice exercises (Chapter 14)

(5th edition of the textbook)

14.1, 14.3, 14.5,14.9, 14.11, 14.13, 14.15, 14.19,

14.21, 14.23b,d, 14.25, 14.27, 14.31, 14.33, 14.35,
14.37, 14.39, 14.43, 14.45, 14.49, 14.51, 14.53,
14.55, 14.57, 14.59, 14.61, 14.63, 14.65, 14.67, 14.69

Practice exercises (Chapter 14)

(4th edition of the textbook)

14.1, 14.3, 14.5, 14.7, 14.9, 14.11, 14.13, 14.15

14.17, 14.19, 14.23b,c,d, 14.25, 14.27, 14.29,
14.31, 14.33, 14.35, 14.37, 14.41, 14.43, 14.45
14.47, 14.49, 14.51, 14.53, 14.55, 14.57, 14.59,
14.61, 14.63, 14.65, 14.67, 14.69, 14.71

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 Practice exercises (Chapter 14)

(Custom edition of the textbook)

1, 3, 5, 7, 9, 11, 13, 1517, 19, 23b,c,d, 25, 27, 29,

31, 33, 35, 37, 41, 43, 45, 47, 49, 51, 53, 55, 57,
59, 61, 63, 65, 67, 69, 71

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