Addition-Elimination Reactions of Aldehydes and Ketones: The Reaction With 2,4-Dinitrophenylhydrazine

ADDITION-ELIMINATION
REACTIONS OF
ALDEHYDES AND
KETONES
This page looks at the reaction of

aldehydes and ketones with 2,4-
dinitrophenylhydrazine (Brady's
reagent) as a test for the carbon-
oxygen double bond. It also looks
briefly at some other similar reactions
which are all known as addition-
elimination (or condensation)
reactions.
The reaction with 2,4-

dinitrophenylhydrazine
2,4-dinitrophenylhydrazine is often
abbreviated to 2,4-DNP or 2,4-DNPH.
A solution of 2,4-
dinitrophenylhydrazine in a mixture of
methanol and sulphuric acid is known
as Brady's reagent.
What is 2,4-dinitrophenylhydrazine?
Although the name sounds
complicated, and the structure looks
quite complicated, it is actually very
easy to work out.
Start with the formula of hydrazine.
That's almost all you need to
remember!
Hydrazine is:
In phenylhydrazine, one of the

hydrogens is replaced by a phenyl
group, C6H5. This is based on a
benzene ring.
Note: I'm using the common symbol for a

benzene ring. If you aren't familiar with this,
there is a carbon atom at each corner of the
hexagon, together with a hydrogen atom if
there isn't anything else attached. The circle
in the middle of the hexagon suggests the
delocalised electrons.
If you want to read more about the structure

of benzene, you could follow this link to
another part of the site. It isn't important for
the purposes of the present page, and you
might have to explore quite a lot of other
pages to help you to understand that one.
If you do choose to follow this link, use the

BACK button (or HISTORY file or GO menu
if you get seriously waylaid) on your
browser to return to this page.
In 2,4-dinitrophenylhydrazine, there are

two nitro groups, NO2, attached to the
phenyl group in the 2- and 4- positions.
The corner with the nitrogen attached
is counted as the number 1 position,
and you just number clockwise around
the ring.
Doing the reaction

Details vary slightly depending on the
nature of the aldehyde or ketone, and
the solvent that the 2,4-
dinitrophenylhydrazine is dissolved in.
Assuming you are using Brady's
reagent (a solution of the 2,4-
dinitrophenylhydrazine in methanol and
sulphuric acid):
Add either a few drops of the aldehyde
or ketone, or possibly a solution of the
aldehyde or ketone in methanol, to the
Brady's reagent. A bright orange or
yellow precipitate shows the presence
of the carbon-oxygen double bond in
an aldehyde or ketone.
This is the simplest test for an
aldehyde or ketone.
The chemistry of the reaction

The overall reaction is given by the
equation:
R and R' can be any combination of
hydrogen or hydrocarbon groups (such
as alkyl groups). If at least one of them
is a hydrogen, then the original
compound is an aldehyde. If both are
hydrocarbon groups, then it is a
ketone.
Look carefully at what has happened.
Provided you take care to draw the two

starting molecules lined up right,
working out the structure of the product
is easy.
The product is known as a "2,4-
dinitrophenylhydrazone". Notice that all
that has changed is the ending from "-
ine" to "-one". That's possibly
confusing!
The product from the reaction with
ethanal would be called ethanal 2,4-
dinitrophenylhydrazone; from
propanone, you would get propanone
2,4-dinitrophenylhydrazone - and so
on. That's not too difficult!
The reaction is known as
a condensation reaction. A
condensation reaction is one in which
two molecules join together with the
loss of a small molecule in the process.
In this case, that small molecule is
water.
In terms of mechanisms, this is
a nucleophilic addition-
elimination reaction. The 2,4-
dinitrophenylhydrazine first adds
across the carbon-oxygen double bond
(the addition stage) to give an
intermediate compound which then
loses a molecule of water (the
elimination stage).
Note: This mechanism isn't required by any

of the UK A level syllabuses, and so you
won't find it anywhere on this site. Sorry!
Using the reaction

The reaction has two uses in testing for
aldehydes and ketones.
 First, you can just use it to test for
the presence of the carbon-oxygen
double bond. You only get an
orange or yellow precipitate from a
carbon-oxygen double bond in an
aldehyde or ketone.
 Secondly, you can use it to help to
identify the specific aldehyde or
ketone.
The precipitate is filtered and
washed with, for example,
methanol and then recrystallised
from a suitable solvent which will
vary depending on the nature of
the aldehyde or ketone. For
example, you can recrystallise the
products from the small aldehydes
and ketones from a mixture of
ethanol and water.
The crystals are dissolved in the
minimum quantity of hot solvent.
When the solution cools, the
crystals are re-precipitated and can
be filtered, washed with a small
amount of solvent and dried. They
should then be pure.
If you then find the melting point of
the crystals, you can compare it
with tables of the melting points of
2,4-dinitrophenylhydrazones of all
the common aldehydes and
ketones to find out which one you
are likely to have got.
Some other similar reactions

If you go back and look at the
equations, nothing in the 2,4-
dinitrophenylhydrazine changes during
the reaction apart from the -NH2 group.
You can get a similar reaction if the -
NH2 group is attached to other things.
In each case, the reaction would look
like this:
In what follows, all that changes is the

nature of the "X".
with hydrazine
The product is a "hydrazone". If you

started from propanone, it would be
propanone hydrazone.
with phenylhydrazine
The product is a "phenylhydrazone".
with hydroxylamine
The product is an "oxime" - for

example, ethanal oxime.
Questions to test your understanding
If this is the first set of questions you have

done, please read the introductory page before
you start. You will need to use the BACK
BUTTON on your browser to come back here
afterwards.
questions on addition-elimination reactions of

aldehydes and ketones
answers
Where would you like to go now?

To the aldehydes and ketones
menu . . .
To the menu of other organic
compounds . . .
To Main Menu . . .
© Jim Clark 2004 (modified November 2015)

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ADDITION-ELIMINATION

This page looks at the reaction of

The reaction with 2,4-

In phenylhydrazine, one of the

Note: I'm using the common symbol for a

If you want to read more about the structure

If you do choose to follow this link, use the

In 2,4-dinitrophenylhydrazine, there are

Doing the reaction

The chemistry of the reaction

Provided you take care to draw the two

Note: This mechanism isn't required by any

Using the reaction

Some other similar reactions

In what follows, all that changes is the

The product is a "hydrazone". If you

The product is a "phenylhydrazone".

The product is an "oxime" - for

Questions to test your understanding

If this is the first set of questions you have

questions on addition-elimination reactions of

Where would you like to go now?

© Jim Clark 2004 (modified November 2015)

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