Aldehydes

Aldehydes and
and Ketones
Ketones

1
 Chapter Outline
23.1 Structures of 23.4 Chemical and Physical
Aldehydes and Ketones Properties of Aldehydes and Ketones

23.2 Naming Aldehydes and 23.5 Common Aldehydes and

Ketones Ketones
23.6 Condensation Polymers
23.3 Bonding and Physical
Properties

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 Structures of
Aldehydes & Ketones

3
• Both aldehydes and ketones contain a
carbonyl ( C=O) group.
O O

C C
R H Ar H
aldehydes

O O O

C C C
R R Ar R Ar Ar

ketones 4
• The general formula for the
saturated homologous series of
aldehydes and ketones is:

CnH2nO

5
•In a linear expression, the
aldehyde group is often written as:
CHO
O

C
H3C H is equivalent to CH3CHO

6
•In the linear expression of a ketone,
the carbonyl group is written as:
CO
O

C
H3C CH3 is equivalent to CH3COCH3

7
 Naming
Aldehydes & Ketones

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IUPAC Rules for Naming Aldehydes
1. To establish the parent name, select the
longest continuous chain of carbon
atoms that contains the aldehyde group.
2. The carbons of the parent chain are
numbered starting with the aldehyde
group. Since the aldehyde group is at
the beginning (or end) of a chain, it is
understood to be number 1.
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IUPAC Rules for Naming Aldehydes
3. Form the parent aldehyde name by
dropping the –e from the corresponding
alkane name and adding the suffix –al.
4. Other groups attached to the parent
chain are named and numbered as we
have done before.

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Naming Aldehydes
O

C
H3C H
ethanal

C 2 3 4 5 6
H 1 CH2CH2CHCH2CH3

CH3
4-methyhexanal 11
12
Common Names for Aldehydes
O O

C C
H H H CH3
formaldehyde acetaldehyde

C
H

13
benzaldehyde
 Dialdehydes
• In dialdehydes, the suffix –dial is added to
the corresponding hydrocarbon name.
O O

HCCH2CH2CH
butanedial
14
 IUPAC Rules for Naming Ketones
1. To establish the parent name, select
the longest continuous chain of
carbon atoms that contain the ketone
group.
2. Form the parent name by dropping the
–e from the corresponding alkane
name and add the suffix –one.
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 IUPAC Rules for Naming Ketones
3. If the chain is longer than four carbons, it is
numbered so that the carbonyl group has the
smallest number possible; this number is
prefixed to the parent name of the ketone.
4. Other groups attached to the parent chain are
named and numbered as we have done before.

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 Naming Ketones
O O

C 1 C 3 4 5
H3C CH3 H3C 2 CH2CH2CH3
propanone 2-petanone

1 2 C 4 5 6 7 8
H3CH2C 3 CH2CH2CHCH2CH3

6-methyl-3-octanone CH3
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 Common Names for Ketones

O O

C C
H3C CH3 H3C CH2CH3
propanone butanone
acetone methyl ethyl ketone, MEK

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 Bonding and
Physical Properties

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 Bonding
• The carbon atom of the carbonyl group
is sp2-hybridized and is joined to three
other atoms by sigma bonds.
• The fourth bond is made by
overlapping p electrons of carbon and
oxygen to form a pi bond between the
carbon and oxygen atoms.

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 Bonding
• Because the oxygen atom is considerably
more electronegative than carbon, the C=O
group is polar.
• Many of the chemical reactions of
aldehydes and ketones are due to this
polarity.

C O
 +  -
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 Properties
• Unlike alcohols, aldehydes and ketones
cannot hydrogen-bond to themselves,
because no hydrogen atom is attached
to the oxygen atom of the carbonyl
group.
• Aldehydes and ketones, therefore, have
lower boiling points than alcohols of
comparable molar mass.

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23
Chemical Properties of
Aldehydes & Ketones

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Reactions of Aldehydes & Ketones

• Oxidation
– aldehydes only
• Reduction
– aldehydes and ketones
• Addition
– aldehydes and ketones

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 Oxidation of Aldehydes
• Aldehydes are easily oxidized to carboxylic
acids by a variety of oxidizing agents,
including (under some conditions) oxygen
of the air.
O O
3 3
C + Cr2O72- + 8 H+ C + 3 Cr3+ + 4H2O
R H R OH

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 Tollens test
• The Tollens test (silver-mirror test) for
aldehydes is based on the ability of silver
ions to oxidize aldehydes.

O O

C + 2 Ag+ NH3 + 2 Ag (s)

C
H2O
R H R O-NH4+

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 Fehling and Benedict Tests
• Fehling and Benedict solutions contain
Cu2+ ions in an alkaline medium.
• In these tests, the aldehyde group is
oxidized to an acid by Cu2+ ions.
O O

C +2
+ 2 Cu NaOH + 2 Cu2O (s)
C
H2O
R H blue R O-Na+ brick red

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 Tollens, Fehling & Benedict Tests
• Because most ketones do not give a
positive with Tollens, Fehling, or Benedict
solutions, these tests are used to distinguish
between aldehydes and ketones.
O

C + 2 Cu+2 NaOH no reaction

H2O
R R

C + 2 Ag+ NH3
no reaction
H2O 29
R R
Biochemical Oxidation of Aldehydes

• When our cells ‘burn’ carbohydrates, they

take advantage of the aldehyde reactivity.
• The aldehyde is oxidized to a carboxylic
acid and is eventually converted to carbon
dioxide, which is then exhaled.
• This stepwise oxidation provides some of
the energy necessary to sustain life.

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 Reduction of Aldehydes & Ketones
• Aldehydes and ketones are easily
reduced to alcohols.
O
H2/Ni
heat RCH2OH
C
R H primary
alcohol
O
H2/Ni OH
C heat
R R RCHR
secondary 31
alcohol
Addition Reactions of Aldehydes & Ketones

• Common addition reactions:

– Addition of alcohols
• hemiacetal, hemiketal, acetal, ketal
– Addition of hydrogen cyanide (HCN)
• cyanohydrin
– Aldol Condensation (self-addition)

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 Addition of Alcohols
• Aldehydes react with alcohols in the
presence of a trace of acid to form
hemiacetals:
O OH
H+
+ CH3OH HC CH2CH3
C
H CH2CH3
OCH3
propanal
1-methoxy-1-propanol
(propionaldehyde methyl hemiacetal)

33
 Addition of Alcohols
• In the presence of excess alcohol and strong
acid such as dry HCl, aldehydes or
hemiacetals react with a second molecule of
the alcohol to give an acetal:
OH OCH3
dry HCl
HC CH2CH3 + CH3OH HC CH2CH3 +H2O

OCH3 OCH3
1,1-dimethoxypropane
(propionaldehyde dimethyl acetal)
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 Addition of Alcohols to
Aldehydes and Ketones

OH OH OR' OR'

C C C C
R R R R
OR' OR' OR' OR'
H R H R
hemiacetal hemiketal acetal ketal

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 Addition of Hydrogen Cyanide
• The addition of HCN to aldehydes and ketones
forms a class of compounds known as
cyanohydrins: O
OH
+ HCN -
C HO
H CH3 HC CH3

CN
acetaldehyde acetaldehyde
O cyanohydrin
- OH
C + HCN HO
H3C CH3 H3CC CH3

CN
acetone acetone
cyanohydrin 36
 Aldol Condensation (Self-Addition)
• In a carbonyl compound, the carbon atoms are
labeled alpha (), beta (), gamma (), delta (),
and so on, according to their positions with respect
to the carbonyl group.
-C-C-C-C=O
 
• The hydrogen atoms attached to the -carbon have
the unique ability to be more easily released as
protons than other hydrogens within the molecule.

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 Aldol Condensation (Self-Addition)
• An aldehyde or ketone that contains -
hydrogens may add to itself or to another -
hydrogen containing aldehyde or ketone.
O

C
H CH3 O OH O
dilute
H H
NaOH CH C
C
H C H H3C H2C H

aldol
H
(3-hydroxybutanal)
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Common Aldehydes &
Ketones

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 Formaldehyde (Methanal)
• Formaldehyde is made from methanol by
reaction with oxygen (air) in the presence
of a silver or copper catalyst.
Ag
• 2 CH3OH + O2  2H2C=O + 2H2O
heat

• Formaldehyde is widely used in the

synthesis of polymers.
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 Acetaldehyde (Ethanal)
• Its principal use is as an intermediate in
the manufacture of other chemicals, such
as acetic acid and 1-butanol.

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 Acetone and Methyl Ethyl Ketone
• Acetone is used as a solvent in the
manufacture of drugs, chemicals, and
explosives. It is also used as a
solvent.
• Methyl ethyl ketone (MEK) is also
widely used as a solvent, especially
for lacquers.

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Condensation Polymers

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 Phenol-Formaldehyde Polymers
(Bakelite)
• Each formaldehyde molecule reacts with two phenol
molecules to eliminate water. The polymer is then
formed. OH OH

O
+ +
C
H H

OH OH
H2
C
+ H2O

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 Phenol-Formaldehyde Polymers
(Bakelite)
• Polymers of this type are still used,
especially in electrical equipment,
because of the insulating and fire-resistant
properties.

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