CARBONYL COMPOUNDS

Aldehydes and Ketones

Carbon atom double bonded to an

oxygen atom
 Aldehydes and Ketones Cont’d.

 Carbon atom of the carbonyl is sp2 hybridized.

C=O bond is shorter, stronger, and more polar
than C=C bond in alkenes.

=>
CARBONYL COMPOUNDS
Consists of two main kinds
– Aldehyde – carbonyl group always appears on the
end of the hydrocarbon chain and has at least one
Hydrogen atom bonded to the carbonyl group.

– Ketone – carbonyl group is bonded to two carbon

atoms.
 Naming Aldehydes and Ketones

 The simplest aldehydes are known by their

common names, formaldehyde,
acetaldehyde, benzaldehyde, and so on. To
name aldehydes systematically in the IUPAC
system, the final –e of the name of alkane is
replaced by –al.

4
 Some ketones are best known by their
common names that give the names of the
two alkyl groups bonded to the carbonyl
group followed by the word ketone.
 Ketones are named systematically by
replacing the final –e of the corresponding
alkane name with –one.
 The numbering of the alkane chain begins at
the end nearest to the carbonyl group. The
location of the carbonyl group is indicated by
placing the number of the carbonyl carbon in
front of the name.
Prentice Hall © 2003 Chapter Sixteen 5
 Synthesis Cont’d.
• Oxidation of Alcohols
• Aldehydes and Ketones may be respectively
prepared by the controlled oxidation of
primary and secondary alcohols respectively
using an acidified solution of potassium
dichromate or permanganate.
 Oxidation of Primary Alcohols

• To aldehyde: pyridinium chlorochromate (PCC,

C5H6NCrO3Cl) in dichloromethane
• Other reagents produce carboxylic acids
Oxidation of Secondary Alcohols

• Effective with inexpensive reagents such as

Na2Cr2O7 in acetic acid
• PCC is used for sensitive alcohols at lower
temperatures
 Mechanism of Chromic Acid
Oxidation
• Alcohol forms a chromate ester followed by
elimination with electron transfer to give ketone
• The mechanism was determined by observing the
effects of isotopes on rates
 Friedel-crafts Acylation - Ketone
formations
• Acid chloride reacts with aromatic hydrocarbons
• The reaction is catalysed by a Lewis acid e.g.
Aluminium chloride AlCl3, Iron bromide FeBr3
• The product is Ketone.
O

C
O
AlCl3 CH3
+ CH3C
Cl
O O

C C
Cl
AlCl3
+
 Industrial Preparation
Ethanal has been extensively manufactured by the catalytic
addition of water to ethyne. (This reaction is discussed under
alkynes)

Propanone is also produced industrially by

dehydrogenation of 2 methyl propan - 2 -ol using
copper as catalyst at 350oC
 Physical Properties of Aldehydes and
Ketones
 The polarity of carbonyl group makes aldehydes
and ketones moderately polar compounds.
 Aldehydes and ketones don’t form hydrogen bonds
to each other, however, they form hydrogen bond
with water using lone pair of electrons on oxygen.
Dipole-dipole d+ C d+ d+
O d-
attraction d -
C O H H
(interaction) and
d-O
O d-
d+H d+
H
Hydrogen bonding
A B

Two factors that determine the solubility of carbonyl compounds in water are: (A) Dipole-dipole
attraction and (B) Hydrogen bonding.
16
 Aldehydes and Ketones are more polar, so have higher
boiling points than comparable alkane or ether.
 Aldehydes and ketones have lower boiling points compared
to alcohols and carboxylic acids of similar size because
they cannot hydrogen bond to each other.

 Polarity of carbonyl group contributes to its reactivity.

 The carbonyl carbon is surrounded by three regions of

electron density, and the bond angles between the three

substituents on carbon are 120o or close to it.
17
Physical Properties of Aldehydes and
Ketones Cont’d.
 Only methanal (formaldehyde) is a gas at
room temperature.
 Simple aliphatic aldehydes and ketones are
all colourless liquids at 20oC.
 The lower molecular mass aldehydes possess
unpleasant and pungent smells, whereas
ketones including benzaldehyde have
pleasant and sweet odours.


Prentice Hall © 2003 Chapter Sixteen 18

 Reactions of Aldehydes and Ketones

• Nucleophilic addition reactions

• Condensation reaction with Derivatives of
Ammonia
• Haloform reaction
• Reduction reactions
• Oxidation reactions
Prentice Hall © 2003 Chapter Sixteen 19
 Chemical Properties
The carbonyl functional group is one of the most
reactive groups in organic chemistry. Many important
reactions of aldehydes are consequent upon their high
polarity of the C = O which leaves the carbon atom
electron deficient and hence susceptible to attack by
nucleophiles. Most reactions of aldehydes and
ketones are addition reaction leading to the formation
of -OH.

Prentice Hall © 2003 Chapter Sixteen 20

 Nucleophilic Addition Reactions

(a) Addition of Hydrogen Cyanide

When an aldehyde or a ketone is treated with a solution of
sodium or potassium cyanide followed by some sulphuric acid
to generate hydrogen cyanide, an addition compound called a
cyanohydrin is formed.

Prentice Hall © 2003 Chapter Sixteen 21

 Nucleophilic Addition Reactions

(a) Addition of Hydrogen Cyanide

Prentice Hall © 2003 Chapter Sixteen 22

 Nucleophilic Addition Reactions
Addition reaction with Grignard Reagents
This reaction has been discussed under methods of preparation of
alcohols. Methanal gives primary alcohol. Aldehydes give
secondary alcohol while ketone leads to the formation of
tertiary alcohol.

23
 Condensation Reaction with Derivatives of
ammonia

• Ammonia derivatives add to aldehyde and

ketone to form derivatives that are important
for identification of aldehydes and ketones
• The product contains a carbon-nitrogen double
bond resulting from elimination of a molecule
of water from the initial addition product
CH3 CH3
H3C -H2O
NH2-R1
C O H3C C OH H3C C

R N-R1
NH-R1
24
 Condensation Reaction with Derivatives of
ammonia

• Hydroxylamine Oxime
H3C H3C
NH2-OH
C O C N-OH
-H2O
H H

• Hydrazine Hydrazone

H3C H3C
NH2-NH2
C O C N-NH2
-H2O
H3C H3C
Prentice Hall © 2003 Chapter Sixteen 25
 Condensation Reaction with Derivatives of
ammonia

• Phenylhydrazine Phenylhydrazone
H3C H3C
PhNH-NH2
C O C N-NHPh
-H2O
H3C H3C
• 2,4-dinitro 2,4-dinitro
phenylhydrazine Phenylhydrazone
(Brady’s reagent) (Yellow crystal)
H
H
N N C
NH-NH2
H CH3
-H2O
C O +

H3C O2N NO2

O2N NO2 26
 Haloform reactions of Aldehydes and Ketones

• Aldehydes and ketones containing a methyl

carbonyl fraction react with warm solution of
sodium hypoiodate to form yellow crystals with
distinctive smell

R R
I2 C O + 3HI
C O
NaOH
H3C I3C CHI3 + RCOONa
yellow crystal

Prentice Hall © 2003 Chapter Sixteen 27

 Reactions to distinguish between
Aldehydes and Ketones
• Oxidation reaction is used to differentiate
between the aldehydes and ketones.
• Aldehydes are easily oxidised while ketones
are not
• Aldehydes are easily oxidised using mild
oxidising agents which cannot oxidise the
Ketones
• Aldehydes are easily oxidised to the
corresponding carboxylic acids.
Prentice Hall © 2003 Chapter Sixteen 28
 Reactions to distinguish between
Aldehydes and Ketones
(a) Oxidation
Aldehydes are readily oxidized by acidified KMnO4 or K2Cr2O7 to
give carboxylic acid. Aromatic aldehydes are not readily oxidized as
their aliphatic counterparts.
To oxidize benzaldehyde it is better to use alkaline KMnO4, as the
product is not soluble in water but soluble in alkali to effect further
reaction. Also benzaldehyde undergoes light catalysed autoxidation to
benzoic acid.

Prentice Hall © 2003 Chapter Sixteen 29

 Reactions to distinguish between
Aldehydes and Ketones
(a) Oxidation
Ketones oxidize with difficulty with hot acidified KMnO4 or K2Cr2O7
to a mixture of acids each containing fewer carbon atoms than the
starting ketone.

Prentice Hall © 2003 Chapter Sixteen 30

 Reactions to distinguish between
Aldehydes and Ketones
Silver mirror test - Tollen's test
Aldehydes show strong reducing properties. One test for reducing
action uses Tollen's reagent, ammoniacal solution of silver (I) nitrate
(v), containing the complex ion Ag(NH3)2+. When aldehydes are
warmed with this reagent, the complex ion is reduced to metallic
silver, which forms a mirror on the walls of the test tube.

This reaction will be negative in ketones which cannot be easily

oxidised. HO
H
C O Ag(NH3)2 C O + 2Ag

H3C H3C
Prentice Hall © 2003 Chapter Sixteen 31
 Reactions to distinguish between
Aldehydes and Ketones
Fehlings test
Aldehyde also reduces fehlings solutions which contains a complex
ion of copper (II) Cu2+ with 2, 3 dihydroxybutanedioic acid (tartaric
acid). Fehling's solution A is copper (II) sulphate. Fehling's solution
B is a mixture of sodium hydroxide and sodium potassium tartarate.
Take a little bit of A solution and add solution B until the precipitate
of Cu(OH)2 formed is just redissolved to give deep blue solution. Add
the aldehyde and warm. Aldehydes reduce the Cu++ ions which is
converted to Cu2O ‘copper (I) ions’ (red/ brown precipitate).

Chapter Sixteen 32
 Reactions to distinguish between
Aldehydes and Ketones
Fehlings test
Aldehyde also reduces fehlings solutions which contains a complex
ion of copper (II) Cu2+ with 2, 3 dihydroxybutanedioic acid (tartaric
acid). Fehling's solution A is copper (II) sulphate Fehling's solution B
is a mixture of sodium hydroxide and sodium potassium tartarate.
Take a little bit of A solution and add solution B until the precipitate
of Cu(OH)2 formed is just redissolved to give to deep blue solution.
Add the aldehyde and warm. Aldehydes reduced
the Cu++ to Cu2O (red/ brown precipitate).
H HO
2
C O
2Cu C O + 4H + Cu2O
NaOH/H20
H3C H3 C
Prentice Hall © 2003 Chapter Sixteen 33
 Reduction to Alcohols

Carbonyl compounds can be reduced in two ways. Firstly,it can

be reduced to alcohol, primary or secondary .Secondly, it can
be reduced to hydrocarbon. Aldehyde can be reduced to
primary alcohols and ketones to secondary alcohols either by
catalytic hydrogenation or by use of chemical reducing agents
like lithium aluminium hydride LiAlH4 and sodium
borohydride NaBH4.

Prentice Hall © 2003 Chapter Sixteen 34

 Reduction to hydrocarbon

Aldehydes and ketones can be reduced to hydrocarbons by the

action of zinc / HCl or basic condition .The carbonyl is
reduced to methylene group.
(i) Amalgamated zinc and on HCl referred to as Clemmensen
reduction for compounds sensitive to base.

Prentice Hall © 2003 Chapter Sixteen 35

 Reduction to hydrocarbon

Wolf - Kishner reduction:

This method is useful for compounds that are sensitive to acid
and it involves the reduction with hydrazine and a strong base
like KOH or potassium butoxide.

Prentice Hall © 2003 Chapter Sixteen 36

 Addition of Alcohols

In the presence of dry HCl as catalyst aliphatic

aldehydes react with dry alcohol to obtain
acetal;

Prentice Hall © 2003 Chapter Sixteen 37

 Addition of Alcohols

This reaction is also possible in aliphatic ketones giving

a ketals instead of actals. In this case the hydrogen will
be replaced by an alkyl group

Prentice Hall © 2003 Chapter Sixteen 38

 AROMATIC CARBONYLS

Reactions of aromatic aldehydes and ketones involving substitution in the

ring. The carbonyl group deactivates the ring towards electrophilic
aromatic substitution and are meta - directing - group. These reactions
are slower than the reactions of benzene and require more stringent
conditions.

Prentice Hall © 2003 Chapter Sixteen 39

THANKS FOR LISTENING

40