Distinguishing carbonyl-containing compounds (aldehydes & ketones) from other functional
groups
Carbonyl compounds (aldehydes and ketones) show well-defined reactions with certain types of
Nitrogen-containing compounds:
1) NH3:
+ NH3 + H2O
+ NH3 + H2O
e.g.
2) Hydrazine: (N2H4)
+
+ H2O
e.g.
+
+ H2O
3) Phenylhydrazine:
+ + H2O
e.g.
+ + H2O
4) Brady’s reagent (2,4-dinitrophenylhydrazine or 2,4-DNPH):
+ + H2O
a phenylhydrazone
(bright yellow crystals)
e.g.
+ + H2O
a phenylhydrazone
(bright yellow crystals)
Both aldehydes and ketones react with Brady’s reagent to give the above phenylhydrazone,
which is a bright yellow (or sometimes orange) crystalline solid.
NB: The test for the presence of a carbonyl compound is to react the sample with Brady’s
reagent and observe whether a yellow (or orange) precipitate forms.
➢ Distinguishing aldehydes from ketones
2 common reagents are used:
1) Tollen’s reagent (an Ag+ soln. e.g. AgNO3) [called the ‘silver mirror’ test]
Ag+ is reduced to a precipitate of Ag and the aldehyde is oxidised to a carboxylic acid:
Ag + + Ag (s)
(silver precipitate, i.e. a ‘silver mirror’)
e.g.
Ag + + Ag (s)
(silver precipitate, i.e. a ‘silver mirror’)
BUT:
Ag +
No reaction (Ketones do not react with Tollen’s reagent)
2) Benedict’s/ Fehling’s soln. (a Cu2+ soln.) [‘brick red’ ppt. formed]
Cu2+ is reduced to form a brick-red precipitate of Cu2O [copper (I) oxide] and the aldehyde is
oxidised to the carboxylic acid:
Cu 2+ (aq) + Cu2O (s)
(brick red precipitate)
e.g.
Cu 2+ (aq)
+ Cu2O (s)
(brick red precipitate)
BUT:
Cu 2+ (aq)
No reaction (Ketones do not react)
➢ The Haloform reaction
This is a special reaction that is specific to an aldehyde or ketone that contains a –CH3 group
directly attached to the carbonyl carbon. NaOH and I2 are added to the aldehyde or ketone
and a positive result is indicated by the formation of a yellow precipitate of iodoform (CH3I).
I2/ NaOH
+ CH3I (s)
Iodoform
(yellow precipitate)
The CH3 gp. directly attached to the carbonyl carbon of the aldehyde or ketone is replaced by O-.
The free CH3 gp. is able to bond with an I atom from I2 to form iodoform.
e.g.
I2/ NaOH
+ CH3I (s)
Iodoform (yellow ppt.)
e.g.
I2/ NaOH
+ CH3I (s)
Iodoform (yellow ppt.)
BUT:
I2/ NaOH
No reaction (no CH3 gp. present on the carbonyl C)
