ALDEHYDES

AND
KETONES
Benzaldehyde is found in the kernels of bitter
almonds
Cinnamaldehyde is found in Ceylonese and Cinnamon oils
KEY QUESTIONS:
• What are the Aldehydes and Ketones?
• How do we name Aldehydes and Ketones?

• What are the physical properties of

Aldehydes and Ketones?
• What are the characteristic reaction of
Aldehydes and Ketones?
• What is Keto-Enol Tautomerism?
What are ALDEHYDES and KETONES?

ALDEHYDES has a functional group which its carbonyl

group (C=O) bonded at least to one hydrogen atom.

KETONES has a functional group which its

carbonyl group (C=O) bonded to two carbon
atoms.
 Naming ALDEHYDES and KETONES?
ALDEHYDES
• In IUPAC system, change the suffix –e of
the parent alkane to –al.
• For unsaturated aldehydes, the ending of
the parent alkane changes from –ane to –
enal: “-en-” shows the carbon-carbon
double bond and “-al” the aldehyde.
 Naming ALDEHYDES and KETONES?

KETONES
• In IUPAC name, change the suffix –e of the
parent alkane to –one, indicating the
presence of carbonyl group.
ALDEHYDES and KETONES with –OH and –NH2
• -OH substituent is indicated by hydroxy
• -NH2 substituent is indicated by amino-
Both numbered and alphabetized along with
any other substituent that might be present.
 Common Names
We derive the common name for an
aldehyde from the common name of
carboxylic acid. The word “acid” is dropped
and the suffix “-ic” or “-oic” is changed to
“–aldehyde”.

• Formaldehyde is derived from the formic acid.

• Acetaldehyde is derived from acetic acid.
 Common Names

We derive the common name for ketones by

naming each alkyl or aryl group bonded to
the carbonyl group as a separate word,
followed by the word “ketone”
The alkyl or aryl groups are generally listed
in order of increasing molecular weight.
 Physical Properties

Oxygen is more electronegative than carbon.

Therefore a carbon-oxygen double bond is
polar, with oxygen bearing a partial negative
charge and a carbon bearing a partial
positive charge
 Physical Properties
• Polar compounds
• No possible H-bonding between aldehyde
and ketone molecules, which explains why
these compounds have lower boiling
points than ROH and RCOOH.
• Intermolecular Force (IMF): Dipole-
dipole
• Soluble in water, but as the molecule
increases in size, aldehydes and ketones
become less soluble in water.
• Have strong odors
 Physical Properties
• Ketones are generally pleasant, are many
are used in perfumes and as flavoring
agents.
• Aldehydes may vary: formaldehyde with
unpleasant odor. Higher aldehydes have
pleasant odors and are used in perfumes
 Characteristic Reactions
1. OXIDATION
Aldehydes are oxidized to Carboxylic Acids
by a variety of Oxidizing Agents, including
K2Cr2O7.

Aldehydes are also oxidized to Carboxylic

Acids by the oxygen in the air.
 Characteristic Reactions
1. OXIDATION
Ketones resist oxidation by most oxidizing
agents, including K2Cr2O7 and O2.

Ketones [O]
------------------> No
Reaction
Tollens’ Reagent – A reagent with a mild
oxidizing agent use to distinguish between
Aldehydes and Ketones
 Characteristic Reactions
1. OXIDATION
Tollens’ Reagent – contains silver nitrate
and ammonia in water, readily reacts with
aldehyde, which acts as reducing agents,
reduces the complex silver ion to silver ion.

If the reaction is carried out properly, the

silver metal precipitates as a smooth mirror-
like deposits, leading to the name silver-
mirror test.
 Characteristic Reactions
1. OXIDATION
Tollens’
Reagent
The remaining solution, RCOO- (Carboxylic
anion) is then acidified with aqueous HCl,
which coverts the anion to Carboxylic Acid,
RCOOH.
Aqueous
HCl ------------------->
RCOOH
 Characteristic Reactions
1. OXIDATION
Tollens’
Reagent
1. Tollens’ Reagent
RCHO -------------------------->
2. Aqueous RCOOH
HCl
RCOR -------------------------->
1. Tollens’ Reagent No
2. Aqueous
Reaction HCl
Silver(I) – rarely used because of its high
cost, and because of the availability of
others for oxidation, but still used for
making (silvering) mirrors
 Characteristic Reactions
1. OXIDATION
 Characteristic Reactions
2. REDUCTION
In previous topics, the C = C double bond of
an alkene can be reduced by Hydrogen in
the presence of a transition metal catalyst to
a C – C single bond.
 Characteristic Reactions
2. REDUCTION
The same is true to C=O double bond of an
aldehyde or ketone:
Aldehydes
reduced to 1o OH

Ketones reduced
to 2o OH

Under the same condition, the reduction of C=O

double bond is slower than of C=C double bond
 Characteristic Reactions
2. REDUCTION
The reagent most commonly used is Sodium
borohydride, NaBH4.
This reagent behaves as if it were the source
of hydride ions, H:- .
 Characteristic Reactions
2. REDUCTION
Of the two hydrogens added to the carbonyl group
in this reduction, one comes from the reducing
agent and the other comes from aqueous acid.
Reduction of cyclohexanone, for example, with
this reagent gives cyclohexanol:
 Characteristic Reactions
2. REDUCTION
 Characteristic Reactions
2. REDUCTION
An advantage of using NaBH4 over the H2
/metal reduction is that NaBH4 does not reduce
carbon carbon double bonds.
1. NaBH4
2. H3O+
2 - propenol
2 -
propenal
H2
propanol
Ni
 Characteristic Reactions
2. REDUCTION

1. NaBH4
2. H3O+

H2
Ni
 Characteristic Reactions
3. ADDITION OF ALCOHOLS
Addition of a molecule of alcohol to the
carbonyl group of an aldehyde or ketone
forms a hemiacetal (a half-acetal). The
functional group of a hemiacetal is a carbon
bonded to one -OH group and one -OR
group.
 Characteristic Reactions
3. ADDITION OF ALCOHOLS
In forming a hemiacetal, the H of the
alcohol adds to the carbonyl oxygen and the
OR group of the alcohol adds to the
carbonyl carbon.
 Characteristic Reactions
3. ADDITION OF ALCOHOLS
Hemiacetals are generally unstable and can
react further with alcohols to form acetals
plus water. This reaction is acid-catalyzed.
The functional group of an acetal is a
carbon bonded to two -OR groups.
 Characteristic Reactions
3. ADDITION OF ALCOHOLS
All steps in hemiacetal and acetal formation
are reversible. As with any other
equilibrium, we can make this one go in
either direction by using Le Chatelier’s
principle. If we want to drive it to the right
(formation of the acetal), we either use a
large excess of alcohol or remove water
from the equilibrium mixture. If we want to
drive it to the left (hydrolysis of the
acetal to the original aldehyde or ketone and
alcohol), we use a large excess of water.
 Characteristic Reactions
3. ADDITION OF ALCOHOLS
 Characteristic Reactions
3. ADDITION OF ALCOHOLS
Draw the hemiacetal and then the acetal
formed in each reaction. In each case,
assume an excess of the alcohol

(a)Propanal + methanol --------->

(b) Cyclopentanone + methanol ---------->

 Keto-Enol Tautomerism

A carbon atom adjacent to a carbonyl group

is called an α-carbon, and a hydrogen atom
bonded to it is called an α -hydrogen.
 Keto-Enol Tautomerism
A carbonyl compound that has a hydrogen
on an α-carbon is in equilibrium with a
constitutional isomer called an enol. The
name “enol” is derived from the IUPAC
designation of it as both an alkene (-en-) and
an alcohol (-ol).
A molecule containing an -OH
ENOL group bonded to a carbon of a
carbon–carbon double bond.
 Keto-Enol Tautomerism

Keto and enol forms are examples of Tautomers,

constitutional isomers in equilibrium with each other
that differ in the location of a hydrogen atom and a
double bond. This type of isomerism is called keto-
enol tautomerism. For any pair of keto-enol
tautomers, the keto form generally predominates at
equilibrium.
Keto-Enol Tautomerism
 END OF
CHAPTER