REACTIONS OF THE

CARBONYL GROUP IN
ALDEHYDES AND
KETONES
L.O.:
The mechanism of nucleophilic
addition reactions of carbonyl
compounds
How carbonyl compounds react
when oxidised or reduced.

A test for an aldehyde using Fehlings solution.

a) In a clean test tube mix together equal volumes of
Fehling's solution A and Fehling's solution B. The
resultant Fehling's test reagent should be a clear dark
blue solution.
b) Add 5 drops of this test reagent to 1 cm3 of sodium
carbonate solution in a test tube containing a few antibumping granules and then add 1 cm3 of ethanal (or
propanal) to this same test tube.
c) Warm the test tube gently for approximately two
minutes in a beaker half filled with hot water and then
gradually bring the beaker of water to boiling and
maintain this temperature for a few minutes.
d) Using the test tube holder, carefully lift the test tube
out of the boiling water and allow its contents to stand
for several minutes.

Tollens silver mirror test

Prepare a sample of Tollens reagent by adding 5
drops of sodium hydroxide solution to 2 cm3 of silver
nitrate solution in a test tube. To this test tube add just
enough dilute ammonia solution to dissolve the brown
precipitate completely.
Using a beaker of hot water (50 oC to 60 oC), gently
warm approximately 5 cm3 of this test reagent in a test
tube.
Add 10 drops of the aldehyde to the warmed test
reagent in the test tube. Wait a few minutes and note
what happens.

Carbonyl groups consists of a carbonoxygen double bond

The bond is polar due to the difference in
electronegativity

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism

Nucleophilic addition

STEP 1

Step 1

CN acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism

Nucleophilic addition

STEP 1

STEP 2

Step 1

CN acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2

A pair of electrons is used to form a bond with H+

Overall, there has been addition of HCN

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism

Nucleophilic addition

STEP 1

STEP 2

Step 1

CN acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2

A pair of electrons is used to form a bond with H+

Overall, there has been addition of HCN

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

ANIMATED MECHANISM

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Watch out for the possibility of optical isomerism in hydroxynitriles
CN attacks from above

CN attacks from below

Many reducing agents will reduce

ketones and aldehydes to alcohols.
NaBH4 (sodium tetrahydroborate(III)
) generates the nucleophile H-, the
hydride ion.
Write the mechanism of the reaction
of a ketone/aldehyde with H-.

Will NaBH4 react with an alkene?

NO! H- is repelled by the electron den

CH2 = CHCHO

2[H]

>

CH2 =CHCH2OH

CARBONYL COMPOUNDS - REDUCTION

Example

COMPOUND X

What are the products when Compound X is reduced?

H2

NaBH4

CARBONYL COMPOUNDS - REDUCTION

Example

What are the products when Compound X is reduced?

COMPOUND X

H2

NaBH4

C=O is polar so is attacked by the nucleophilic H

C=C is non-polar so is not attacked by the nucleophilic H

Oxidati
on
Fehling test (Cu2+).
Silver mirror test (Ag+)

Is it more difficult to oxidise a

ketone than an aldehyde? Why

THE SILVER MIRROR TEST

Tollens Reagent contains [Ag(NH3)2 ]+

When an aldehyde is warmed with Tollens

reagent, metallic silver is formed.
Aldehyde is oxidised to carboxylic acid
and Ag+ reduced to metallic silver
RCHO + [o] -> RCOOH

oxidation

[Ag(NH3)2]+ + e- -> Ag + 2NH3 reduction

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FEHLINGS SOLUTION
It contains a copper(II) complex ion
giving a blue solution. On warming, it will
oxidise aldehydes. The copper(II) is
reduced to copper(I) and a red precipitate
of copper(I) oxide, Cu2O, is formed.
Ketones do not react with Tollens
Reagent or Fehlings Solution
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