CARBONYL COMPOUNDS

Aldehydes and Ketones

Carbon atom double bonded to an
oxygen atom
CARBONYL COMPOUNDS
– Aldehyde – carbonyl group always appears on the end
of the hydrocarbon chain and has at least one H 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.

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 Some ketones are best known by their
common names that gives 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.
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 SYNTHESIS
• 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
 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
 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.
 Aldehydes and ketones have lower boiling
points compared to alcohols of similar size.
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 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.

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 Reactions of Aldehydes and
Ketones
• Nucleophilic addition reactions
• Condensation reaction with Derivatives of
Ammonia
• Haloform reaction
• Reduction reactions
• Oxidation reactions
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 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.

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 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.

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 Nucleophilic Addition Reactions
(a) Addition of Hydrogen Cyanide

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

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 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
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 Condensation Reaction with Derivatives of
ammonia
• Hydroxyamine 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
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 Condensation Reaction with Derivatives of
ammonia
• Phenylhydrazine Phenylhydrazone
H 3C 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 C
NH-NH2
H CH3
-H2O
C O +

H 3C O2N NO2
O2 N NO2
25
 Condensation Reaction with Derivatives of
ammonia
• With semi carbazide Semi carbazone

26
 Halogenation of the Carbonyl
Functional Group
Aldehydes and Ketones react with phosphorus pentachloride
without the evolution of hydrogen chloride compared with
alcohols.The compound formed is a gem dichloro alkane

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 Acidity of α Hydrogens
Ionization of an α hydrogen in the presences of a base gives hybrid of
a carbanion.

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 Acidity of α Hydrogens
This resonance is possible only through the participation of the
carbonyl group. The α hydrogen of carbonyl compounds although
acidic enough to be abstracted by basic reagents, are nevertheless only
feebly acidic.

As a result the carbanions generated are strongly basic exceedingly

reactive molecules. In their reactions, they behave as nucleophiles:-
thus in Aldol condensation, the carbanion generated from one
molecule of aldehyde or ketone adds as a nucleophile to the carbonyl
of second molecule.

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 Aldol Condensation
The reaction is given by aldehydes and ketones containing at least one
α hydrogen. This reaction is not possible with HCHO and C6H5CHO
The carbonyl compound is treated with cold dilute alkali.

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 Aldol Condensation
Mechanism:

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 Aldol Condensation
With ketones e.g. Propanone

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 Dehydration of Aldol Products
β-hydroxy aldehydes and β-hydroxy ketones, are very easily
dehydrated, resulting in major products i.e α, β-unsaturated
carbonyl compounds have carbon - carbon double bond between
the α and β carbon atoms.

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 Classen's Condensation (Crossed Aldol)

Classen's condensation reaction takes place between an

aldehyde without α - hydrogen. An example is
benzaldehyde and acetone under the influence of a base. In
this case addition is followed by elimination of water to
give the overall condensation reaction.

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 Cannizarro Reaction
This reaction is characteristic of aldehydes which cannot undergo
aldol condensation i.e. they do not have α- hydrogen atoms such as
methanal and benzaldehyde:

This reaction involves the self-oxidation and reduction of the

aldehyde to benzoic acid and benzyl alcohol respectively.
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 Cannizarro Reaction
This reaction is thought to proceed by hydride ion transfer after the
addition of a hydroxyl ion to the carbonyl of the aldehyde. The hydride
ion then reduces the other aldehyde molecule to form the alcohol.

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 Cross Cannizarro Reaction
There are two different aldehydes in this reaction . One of the
aldehydes is oxidized to acid while the other aldehyde is reduced to
alcohol. For example, benzaldehyde reacts with methanol in the
presence of sodium hydroxide to produce, benzyl alcohol and
sodium methanoate.

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 Cross Cannizarro Reaction
The base attacks the aliphatic or the smaller aldehyde preferentially
and thus oxidized to acid and the aromatic one is reduced to
alcohol. The reaction below is not possible due to the foregoing
explanation.

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 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
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 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.

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 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.

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 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 (AgNH3)2+. When aldehydes are
warned 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

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

H3C H3C
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 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).

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 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.

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 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.

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 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

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