Aldehydes and Ketones

Carbonyle Group

In organic chemistry, a carbonyl group is a functional group composed

of a carbon atom double-bonded to an oxygen atom : C=O. However the
carbonyl group is best described as a hybrid of the following resonance
structures.
Carbonyl group characterizes the following types of compounds (where -CO
denotes a C=O carbonyl group)
Oxygen of carbonyl group has a slight negative charge and partial positive
charge on carbon.

The partial positive charge on carbon makes it venerable to nucleophile and

partial negative charge on oxygen is attractive to electrophile.

Carbonyl group has sp3 hybridization and a trigonal planer structure.

The planer structure leaves open space above and below making it susceptible to
attack from both sides. Aldehydes and ketones follow nucleophilic addition
while other compounds prefer nucleophilic substitution. The partial negative
charge on oxygen makes it attractive for protons and it can be easily protonated.
Aldehydes and Ketones

General structures and structures of 1st member of aldehyde and

ketones family are shown below:

Physical properties

a) Boiling point increases as molecular weight increases and follows the

same trend as followed by alkane and alkene. Formaldehyde is gas at
room temperature. Acetaldehyde boils at 20ºC. Rests of all the members
are liquids.
b) Density of aldehyde and ketones is lesser than water.
c) Aldehydes and ketones are polar compounds.
d) They don’t have hydrogen bonding but form hydrogen bonding
with the compound which have hydrogen bonding.
e) First four members are soluble in water.
f) They are excellent organic solvents.

Chemical Properties

Aldehydes and ketones shows nucleophile addition reaction or acts

as Bronstred-lowry acid by donating its ∀-hydrogen.

The carbon which is attached to carbonyl carbon is called ∀-carbon.

The next carbon is called ∃-carbon and another in sequence is called (-carbon.
The hydrogen which is attached to these carbon is called ∀-hydrogen, ∃-
hydrogen and (-hydrogen respectively.
 The ∀-hydrogen of ketones and aldehyde is acidic in nature. The
ionization of a ∀-hydrogen forms a carbanion. The carbanion is resonance hybrid
of the two structures. This type of resonance is possible only through
participation by carbonyl group. This type of resonance is not possible for
carbanion formed by ionization of (-hydrogen or ∃-hydrogen from saturated
carbonyl compound.

The carbonyl group thus effects the acidity of ∀-hydrogen by

helping to accommodate negative charge on it. This carbanion is called enolate
anion.

The ∀-carbon of enolate ion is negatively charged. It can act as a

nucleophile. When ∃-carbon is also a carbonyl (called a ∃-dicarbonyl), the enol
formed is more stabilized due to internal hydrogen bonding and resonance.
 Aldehydes are more reactive than ketones as well as more acidic
than ketones. The reason is same for both. Aldehyde has only one alkyl group
while ketones have two alkyl groups. Alkyl group is electron donating group.
Hence more electrons are released from ketones than from aldehyde. This
intensifies negative charge on carbonyl oxygen. Thus intensification of negative
charge due to ketones will be more than aldehyde. The excess negative charge
can not be distributed easily hence ketones are less reactive and less acidic than
aldehydes.

Ketones show tautomerism with enol.

Tautomerism refers to a state of equilibrium between two different

structures of the same compound. Usually the tautomers differ in the point of
attachment of a hydrogen atom. Tautomerism is a reaction at equilibrium and
not a resonance. In resonance structure neither atom moves nor structure
actually exists. Therefore tautomerism is not resonance.

A structure with -OH attached to a doubly bonded carbon is called enol.

There is equilibrium between the two structures. Equilibrium almost always lies
in favor of ketones and tends to move toward ketones. The mechanism is shown
below.
Acetal Preparation

The aldehyde is dissolved in excess of an anhydrous alcohol with a

small amount of anhydrous acid. The result is formation of acetal. The reaction is
reversible with water and small quantity of acid. Alcohol reacts as a nucleophile
and follows addition reaction mechanism. Ketones also react in the same pattern.
The product formed is called ketal. Initially hemiacetal and hemiketal are formed
from aldehyde and ketones respectively. Acetal and ketal are formed
subsequently.

The aldehyde products can be easily recognized by the presence of lone

hydrogen which is not present in ketones products. Hemiacetal and hemiketal
can be distinguished by the presence of alcohols, while acetal and ketal both do
not have alcohol. The ‘hemi’ products can be catalyzed either by base or an acid.
However in formation of acetal and ketal from ‘hemi’ the presence of acid is
must because hydroxyl group must be protonated. Hence this part of reaction
has acid as the catalyst.

Although acetal is hydrolyzed to aldehyde and ketones in aqueous acid,

they are stable in basic solution. This property is utilized to protect aldehyde and
ketones.

We can convert an aldehyde or ketones to acetal, carry out a reaction on

some other part of the molecule and then hydrolyze acetal by aqueous acid.
In a similar reaction aldehyde or ketones are dissolved in aqueous solution and
establish equilibrium with their hydrate a geminal diol.
Aldol condensation

A molecule which contains a function group of alcohol and aldehyde

in general is called aldol.An Aldol condensation is an organic reaction in which
an enolate ion reacts with a carbonyl compound to form a β-hydroxyaldehyde or
β-hydroxyketone, followed by dehydration to give a conjugated enone.

When acetaldehyde reacts with dilute sodium hydroxide it produces 3

hydroxy butanal. It is the compound containing alcohol and aldehyde function
groups. The general common name for the product is Aldol.
 The mechanism for Aldol condensation shows two important
properties of carbonyl compounds. First is acidity of their ∀-hydrogen and
second is the tendency of the carbonyl group to accept a nucleophile.

Step 1:

The reaction starts with an acid-base reaction. Hydroxide functions as a base and
removes the acidic α-hydrogen from ∀-carbon of one of the molecules giving the
resonance stabilized reactive enolate ion.
Step 2:

The nucleophilic enolate attacks the ketone at the electrophilic carbonyl carbon of
second molecule in a nucleophilic addition type process giving an intermediate
alkoxide anion.

Step 3:

This step involves an acid-base reaction. The alkoxide deprotonates a water

molecule creating hydroxide and the β-hydroxyketone, which is the aldol
product.
Although the reaction is conventionally called condensation, no condensation
has taken and the reaction is purely an addition reaction. The next step from
aldol to enal is condensation. The step may also be called dehydration. In some
reaction dehydration occurs so rapidly that product in aldol form can not be
isolated and the product formed is enal (alkene aldehyde).

Halogenation

Halogens react by substitution mechanism with ketones in presence of

base as well as acid. The substitution takes place exclusively at ∀-carbon. This
behavior is due to acidity of ∀-hydrogen and tendency of ketones to form enol.
 In presence of a base, reaction is slow and forms either enolate
anion or enol followed by rapid reaction of enolate ion or enol with halogen. The
base is consumed forming water. In the presence of acid, enol is formed and enol
reacts with halogen. The acid is recovered at the end of reaction. Thus in true
sense it is acid catalyzed reaction.

Haloform reaction

When methyl ketones are treated with the halogen in basic solution,
polyhalogenaton followed by cleavage of the methyl group occurs. The products
are the carboxylate ion and trihalomethane, otherwise known as haloform. The
reaction proceeds via successively faster halogenations at the α-position until all
the three hydrogen have been replaced. The halogenations get faster since the
halogen stabilizes the enolate negative charge and makes it easier to form. Then a
nucleophilic acyl substitution by hydroxide displaces the anion CX3 as a leaving
group that rapidly protonates.

This reaction is often performed using iodine and as a chemical test

for identifying methyl ketones. Iodoform is yellow and precipitates under the
reaction conditions.
The Wittig Reaction

The Wittig reaction is a chemical reaction of an aldehyde or ketone

with a triphenyl phosphoniumylide to give an alkene and triphenylphosphine
oxide.

Ketones behaves normal by initially undergoing nucleophilic addition to form

betine which easily breaks down to triphenylphosphine oxide and the alkene.
∀-∃ Unsaturated Carbonyls

α,β-Unsaturated carbonyl compounds are an important class of

carbonyl compounds with the general structure Cβ=Cα−C=O. In these
compounds, the carbonyl group is conjugated with an alkene (hence the
adjective unsaturated), from which they derive special properties. Examples of
unsaturated carbonyls are acrolein, mesityl oxide, acrylic acidand maleic acid.

α,β-Unsaturated aldehyde and ketone may react with nucleophile

reagent in two ways.
a) simple additioin process in which a nucleophile add across the
double bond of the carbonyl group.
b) A conjugate addition
 In some cases both the additions occur in the same mixture. The major
product formed depends upon nucleophile. Strong nucleophile favors simple
addition while weak nucleophile favors conjugate addition

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