The carbonyl group is formed by joining together the

C atom and the O atom by a double bond.

Compounds having the aldehyde and ketone
functional groups are named carbonyl compounds.
Differences among aldehydes and ketones are due to
the positioning of the carbonyl group in their
molecules.
The C=O group in aldehydes is always located at the
end of the alkyl stem, so aldehydes can be represent
as



R C H
O
Unlike aldehydes, the ketone carbonyl group is situated
away from the ends of the parent carbon chain.
This means that the carbonyl group in ketones is
sandwiched between two alkyl stems and is
represented as






The group stamped a polar region in the aldehyde and
ketone molecules. Most reactions of aldehydes and
ketones will be centred at the carbonyl group.

R C R
O
Nomenclature:
The names of aldehydes and ketones are
simply derived by dropping "-e" from the root
and adding "-al" or "-one" respectively. A
position number is needed for ketones since
the carbonyl group may be on any number of
several carbons in the "middle" of a chain. The
carbonyl on the aldehyde is always on the
number one carbon so no position number is
needed.

Aldehyde -al
Propanal
Ketone -one Propanone
or
acetone
(common
name)
Preparation of Aldehydes and Ketones
Aldehydes can be prepared by the oxidation of
primary alcohols with hot, acidified potassium
manganate (VII) solution or potassium
dichromate(VI) solution.



R-C-OH + (O) R-C=O + H2O
H
H
H
aldehyde
Ketones are prepared by the oxidation of
secondary alcohols by hot acidified KMnO4
solution. Ketones resist oxidation, thus
distillation is not required.



R1-C-OH + (O) R1-C=O + H2O
R2
H
R2
Ketone
Physical Properties of
Aldehydes and Ketones
Physical Properties of Aldehydes and Ketones
a). Solubility in water
The small aldehydes and ketones are freely soluble in
water but solubility falls with chain length. For
example, methanal, ethanal and propanone - the
common small aldehydes and ketones - are miscible
with water in all proportions.
The reason for the solubility is that although
aldehydes and ketones can't hydrogen bond with
themselves, they can hydrogen bond with water
molecules.


As chain lengths increase, the hydrocarbon "tails" of the
molecules start to get in the way.
By forcing themselves between water molecules, they
break the relatively strong hydrogen bonds between
water molecules without replacing them by anything as
good. This makes the process energetically less
profitable, and so solubility decreases.

b). Boiling points
The other aldehydes and the ketones are liquids, with
boiling points rising as the molecules get bigger. The size
of the boiling point is governed by the strengths of the
intermolecular forces.
The other aldehydes and the ketones are liquids, with
boiling points rising as the molecules get bigger. The size
of the boiling point is governed by the strengths of the
intermolecular forces.


c). Density of aldehyde and ketones is lesser than water.
d). Aldehydes and ketones are polar molecules. The bond
angles and hybridization are the same. They also have
dipole-dipole intermolecular bonding. Because of this,
they are held together with greater attraction than you
would find with alkanes of similar size and molecular
weight.
e). They dont have hydrogen bonding but form hydrogen
bonding with the compound which have hydrogen
bonding.
f). They are excellent organic solvents.


Chemical Properties of
Aldehydes and Ketones
Chemical Properties of Aldehydes and
Ketones
Reduction
Variety of agents can reduce aldehydes and ketones to
alcohols
NaBH
4
and H
2
commonly used



Condensation Reactions
Aldehydes and ketones react with derivatives of
ammonia in condensation reactions.
Aldehydes and ketones react with hydroxylamine at
room temperature to form an oxime.
C= O+ H2N- ON C=N-OH+H2O
hydroxylamine oxime
Aldehydes and ketones react with hydrazine at room
temperature to form a hydrazone.
C= O+ H2N- NH C=N-OH+H2O
hydrazine hydrazone
Aldehydes and ketones react with
phenylhydrazine, at room temperature to form
a phenylhydration.
C= O+ H2N- H- C=N-N- + H2O
H H
phenylhydrazine phenyldrazone
The most important condensation reaction is
with 2, 4-dinitrophenyldrazine to form a yellow-
orange precipatate of 2, 4-
dinitrophenylhydrazone.
O2N O2N
C= O+ H2N- H- NO2 C=N-N- NO2+ H2O
H H

A solution of 2, 4- dinitrophenylhydrazine in
methanol and sulphuric acid is called Bradys
reagent.
The formation of a yellow- orange precipitate is
a chemical test for the presence of the carbonyl
group in aldehydes and ketones.

2, 4-dinitrophenyldrazine
2, 4- dinitrophenylhydrazone
Hydration
Formaldehyde dissolves readily in water
Acetaldehyde somewhat also
Form hydrates

Addition Reactions
Aldehydes and ketones react with hydrogen
cyanide in sodium hydroxide solution at 10-20
celcius to form cyanohydrin.
H H
CH3-C=O+H-C= N CH3-C-OH
C=
2- hydroxypropanenitrile
(ethanal cyanohydrin)
The reaction can also be carried put by adding
dilute sulphuric acid to a mixture of carbonyl
compound and potassium cyanide at 10-20
celcius.
The CN group in cyanohydrin can be
hydrolysed by heating with a dilute acid to form
a hydroxyacid. This is a method to prepare 2-
hydroxycarboxylic acid.
H + H
CH3-C=OH+H-H2O CH3-C-OH
C= N COOH
2-hydroxycarboxylic acid
This is a useful way to add a carbon atom to the
carbon chain.
The CN group can also be reduced to an amine
group using hydrogen gas in the presence of hot
nickel catalyst or by using lithium
tetrahydridoaluminate (III)

Oxidation
Aldehydes are oxidised rather easily to
carboxylic acids by heating with acidified
potassium manganate (VII) or potassium
dichromate (VI) solution.
H OH
R-C=O+[O] R-C=O
Aldehyde carboxylic acid
In alkaline conditions, the aldehyde is oxidised to
the salt of the corresponding carboxylic acid.
The carboxylic acid is formed upon addition of a
dilute acid.
H O-
R-C=O+[O]+OH- R-C=O+H2O
Aldehyde salt of carboxylic acid
O OH
R-C=O+H+ R-C=O
carboxylic acid
Benzaldehyde is oxidised to benzoic acid, which
is soluble in hot water, but when cooled, will
precipitate out as a white solid.
H OH
-C=O+[O] -C=O
Benzaldehyde benzoic acid

Ketones resist oxidation under normal conditions.
However they undergo oxidative cleavage when
boiled for a long time to form a mixture of products.
There will be a loss of carbon atoms in the form of
carbon dioxide.
An important industrial application of the oxidation
of ketones is the oxidation of cyclohexanone by nitric
acid to hexanedioic acid, which is a monomer in the
synthesis of nylon-6,6.

O O O
HO-C-CH2CH2CH2CH2-C-OH

cyclohexanone hexanedioic acid
Tollens reagent
When adding the aldehyde or ketone to Tollens'
reagent, the test tube is put in a warm water bath. If
the reactant under test is an aldehyde, Tollens' test
results in a silver mirror. If the reactant is a ketone, it
will not react because a ketone cannot be oxidized
easily. A ketone has no available hydrogen atom on the
carbonyl carbon that can be oxidized - unlike an
aldehyde, which has this hydrogen atom.

Fehling reagent
An aldehyde is added to the Fehling solution and the
mixture is heated. The aldehyde oxidizes to an acid
and cupric ions, which were complexed with the
tartrate ion, are reduced to cuprous ions, which
precipitate as red cuprous oxide. Ketones (except
alpha hydroxy ketones such as are present in ketoses
and other metabolites) and aromatic aldehydes do
not respond to the Fehling test.
Benedict's test
Benedict's reagent will detect the presence of
aldehydes.
Benedict's reagent contains blue copper(II) ions (Cu
2+
)
which are reduced to copper(I) (Cu
+
). These are
precipitated as red copper(I) oxide which is insoluble in
water.

Uses of Aldehydes and
Ketones

Hundreds of aldehydes and ketones are used as
flavoring, odouring and preserving agents e.g.,
vanillin and cinnamonaldehyde (flavors).
Glyceraldehyde is an intermediate in carbohydrate
metabolism and testosterone and progesterone are
hormones that relate to the biological role of these
compounds.
Aldehydes and ketones are being used by chemists
daily basically to synthesize other compounds.
In industry these compounds are used as solvents.
Uses of Aldehydes
A 40% formaldehyde known as formalin solution
can be used to preserve dead animals.
It is also used in the manufacture of polymeric
plastics like bakelite, melamine and urea-
formaldehyde glues.
Formaldehyde is used in the tanning of leather,
decolouring of vat dyes and as a reducing agent in
silvering of mirrors.
It is also used in manufacture of plywood.
Paraldehyde is a sweet smelling liquid used in
medicine as a hypnotic.

Acetaldehyde is used primarily as a starting
material in the manufacture of acetic acid, ethyl
acetate, vinyl acetate, polymers and drugs.

It is also used in silvering of mirrors.

Mataldehyde a polymer of acetaldehyde is used
as a solid fuel and for killing slugs when mixed
with bran.


Benzaldehyde is an almond extract used as a
flavoring agent as well as in perfumery.

It is used in the manufacture of dyes like
malachite green.

In the chemical industry it is also used as a
starting material for making a number of
organic compounds such as cinnamic acid,
benzoic acid, benzoyl chloride etc.

Uses of ketones
Acetone is a common fingernail polish remover and
is a solvent for lacquers and varnishes.
Acetone is used as a cleaning fluid and is very
flammable.
It is also used to prepare a number of compounds
such as chloroform, ketene acetic anhydride etc.
It finds further use in the manufacture of smokeless
powders cordite, celluloid.
2-Butanone (MEK, methyl ethyl ketone) finds use as
a solvent and paint stripper.
Carvone is used as spearmint flavoring. It is used as
caraway seed flavoring.