Test of Aldehyde and ketones

2, 4-Dinitro phenyl hydrazine (Brady’s reagent)

1.
Positive for Aldehyde and Ketones Both

Aldehydes and ketones are characterized through the addition to the

carbonyl group of nucleophilic reagents, especially derivatives of ammonia.
All aldehyde or ketone will, for example react with 2,4-
dinitrophenylhydrazine to form an insoluble yellow or red solid

Structure of DNP

C N-NH NO2

NO2

NO2 NO2
R R
C=O + H2NHN NO2 ¾® C=NHN NO2
R¢ R¢
(2,4 DNP)

2, 4-Dinitro phenyl hydrazone Reacts with both aldehyde and ketone to

give ppt

(yellow crystalline solid -used for identification of aldehydes & ketones)

Aromatic aldehyde and ketone when reacts with DNP it give Red PPT.

2. Schiff test

Positive for Aldehyde

Negative for Ketones

The Schiff test is name developed by Hugo Schiff. It is use to test for
detection of Aldehydes .The Schiff reagent produce when dye formulation
takes place due to reaction of fuchsin and sodium bisulfite.

Schiff reagent use as a qualitative test for aldehydes, the unknown of

aldehyde sample is added to the decolorized Schiff reagent. Aldehyde Gives
magenta color with Schiff reagent. Schiff-type reagents are used for
various biological tissue staining methods, e.g. Feulgen stain and periodic
acid-Schiff stain. Human skin also contains aldehyde functional groups in
the termini of saccharides and so is stained as well when comes in contact
with Schiff Reagents.

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 3. Reaction with sodium bisulphite
Use to separate aldehyde and ketone with other functional group
(Not a test)

Aldehydes and ketones add on sodium hydrogen sulphite to form bisulphite

compounds.
OH
C O + NaHSO3 C
SO3-Na +

This bisulphite formation is confined to aldehydes, methyl ketones and

some cyclic ketones. Those carbonyl compounds, which form bisulphite
adduct can be separated from mixtures as they are crystalline solids,

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insoluble in NaHSO3 solution and / or purified by isolation, purification and
subsequent decomposition of these adducts in dilute acids.

Mechanism:

The effective nucleophile of the reaction is SO 32- ion rather than HSO 3- and
formation of SO 32- is achieved in slightly basic solution. NaHSO3 ¾®
Na+ + HSO 3-

HSO 3- H+ + SO 32-

OH-

H2O
- O O- OH
d+ s Slow H
+

C O + :S O -
C O C
fast
-
S O- SO3-Na +
O
.. O

For example,
H
Ph
C O + NaHSO3 Ph C SO3Na
H
OH
Benzaldehyde bisulphite adduct

(CH3)2CH-C-CH(CH3)2 + NaHSO3 No reaction

O

Hindered ketones like di-isopropyl ketone, di-t-butyl ketone does not

undergo any reaction with NaHSO3.

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 4. Tollens’ test
Positive for aldehyde

Negative for ketone

Positive for ketone having alpha hydroxy group

Tollens’ test, also known as silver-mirror test, because when silver ion is
get reduce to silver it get precipitate and produce mirror like image.

Tollens’ test is used as a test to distinguish between an aldehyde and a

ketone. Tollens’ reagent is a colorless, basic, aqueous solution containing
silver ions coordinated to ammonia [Ag(NH3)2+][Ag(NH3)2+]. And consist
of Ag+Ions which reduce to Ag when treated with aldehyde , and aldehyde
get oxidise to carboxylic acid .

Aqueous silver nitrate which consist of silver ion in +1 oxidation state is

mixed with aqueous sodium hydroxide.

Now aqueous ammonia is added drop-wise until the precipitated silver

oxide completely dissolves.

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Tollens’ reagent oxidizes an aldehyde into the corresponding carboxylic
acid.

The reaction is accompanied by the reduction of silver ions in Tollens’

reagent into metallic silver, which, if the test is carried out in a clean glass
test tube, forms a mirror on the test tube.

5.Fehling’s Test
Positive for aldehyde

Negative for ketone

Positive for ketone having alpha hydroxy group

Fehling’s solution is weaker oxidising agent than tollens

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Bernhard Tollens (1841-1918) was a Professor of Chemistry at the
University of Gottingen, Germany.
Aldehydes are easily oxidised, thus they also reduce Fehling’s solution (an
alkaline solution containing a complex of copper tartarate) to red cuprous
oxide. Aldehydes also reduce Benedict’s solution (an alkaline solution
containing a complex of copper citrate) to red precipitate of cuprous oxide.

Fehling reagent comprises of two solutions, Fehling solution A and Fehling

solution B. Fehling solution A is aqueous copper sulphate and Fehling
solution B is alkaline sodium potassium tartarate (Rochelle salt). These two
solutions are mixed in equal amounts before test.

R-CHO + 2CuO ¾® RCOO- + Cu2O¯ (Fehling’s and

Benedict’s test)

(Red)

Ketones are not easily oxidised, thus they do not reduce Fehling’s solution
or Tollen’s reagent. But a-hydroxy ketones (compounds containing the unit
-CH(OH)-C-R) readily reduce The compounds which respond to the test with
O
Fehling’s solution and ammoniacal silver nitrate are given below in the
tabulated manner.

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 Name of the compounds Fehling’s test Tollen’s Test

Glucose, Fructose P P

a–hydroxy ketone P P

a–hydroxy aldehyde P P

Glyoxal (OHC.CHO) Î P

Benzaldehyde & other aromatic Î P

aldehydes

Formic acid P P

Glyoxylic acid (OHC.CO2H) Î P

Succinaldehyde (OHCCH2CH2CHO) P P

Pyruvaldehyde (CH3COCHO) P P

6. Sodium nitroprusside test:

Positive for carbonyl compounds

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Treat some organic compound with few drops of freshly prepared solution of
sodium nitroprusside followed by excess of NaOH solution. A wine-red colour is
obtained.

7. Jones (Chromic Acid) Oxidation Test for Aldehydes

Positive for aldehyde

Positive test for primary and secondary alcohol

Aldehydes

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A positive test is marked by the formation of a green color within 5 seconds
upon addition of the orange-yellow reagent to a primary or secondary
alcohol.

Aldehydes also give a positive test, but tertiary alcohols do not.

A positive test for aldehydes and primary or secondary alcohols consists in
the production of an opaque suspension with a green to blue color.

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