Carbonyl Chemistry

The topic is called carbonyl chemistry but we are looking specifically at aldehydes and ketones.

Properties

Aldehydes and ketones cannot form intramolecular hydrogen bonds i.e. they cant hydrogen bond with
themselves (compare this to carboxylic acids). Therefore their boiling points will be low.

But they can hydrogen bond with water. The oxygen atom on the
aldehydes and ketones can hydrogen bond with water, therefore
making them water soluble.

The main reaction in this topic is nucleophilic addition.

Nucleophiles
A nucleophile is an electron pair donor that is attracted to positive charges or partial charges like the +
charge on the carbon.

The common nucleophiles are: CN-, NH3 (or other amines), H2O, OH-, H- (from LiAlH4).

in this topic the only nucleophiles are H- and CN-

Nucleophilic Addition
We are going to be looking at the nucleophilic addition mechanism.

adding H- or CN- to an aldehyde or ketone

This is easily recognisable as it is very specific. And the product always contains an OH group.

LiAlH4 is a powerful reducing agent. Just think of it as a source of H-. The reaction is reduction but it is
still a nucleophilic addition mechanism. It is the opposite of the oxidation of alcohols stuff you did at
AS, you are going back from an aldehyde or ketone to an alcohol.
Addition of HCN

Adding a nitrile (CN-) nucleophile to the carbonyl group a hydroxynitrile i.e. contains both a CN and
OH functional group in the product.

Generating the nucleophile

The reagent that you would start with would ideally be HCN but it is a poisonous gas so you wouldnt
have this in the laboratory.

Instead, a mixture of KCN and acid is normally used, which generates HCN in the reaction mixture.
HCN would then dissociate into H+ and CN- as HCN is a weak acid:

HCN is a weak acid, so it wouldnt dissociate enough to make struggle to make CN-. KCN is a salt so
dissociates completely to make a lot of CN-.

the reaction is carried out at pH 8 to aid the dissociation of HCN to H+ and CN-, otherwise the
equilibrium lies too far to the left. H+ is required for the second part of the mechanism.

Mechanism

Part 1

The first part of the mechanism involves the nucleophile attacking the carbon with the + as shown
below:

I have drawn the nucleophile as CN- but this is a carbon nucleophile NOT a nitrogen nucleophile. The
minus is actually on the carbon atom, it is just commonly drawn as above.

There are always two arrows in this first part of the mechanism. The first arrow is to form a C-C bond
between the CN and the C of the carbonyl group.

The second arrow pushes two of the electrons from the double bond on to the oxygen, which then
becomes negatively charged to show that it has gained an extra electron. This arrow is necessary as
otherwise the carbon would have 5 bonds, which is seriously uncool.
Part 2

All you have to do now is remove the minus charge on the oxygen by picking up an H+. From the
intermediate, just draw an arrow to an H+ that would have come from the original HCN reagent:

if the pH is above 8 then it would be too strongly alkaline and there would not be enough H+ ions in
solution for this step to occur at a reasonable rate.

the product is called a hydroxynitrile as it contains both an alcohol (the hydroxyl part) and nitrile
functional group. Students sometimes call it an alcohol but its a hydroxynitrile.

Nitriles (CN-)

Nitriles are useful as they are a good way to increase the carbon chain by 1 carbon. Always look for this,
particularly in organic synthesis questions in Topic 18. Its amazing how often it appears.

Nitriles are also versatile i.e. they can be turned into other functional groups. Two main reactions:

1.
hydrolysis of a nitrile carboxylic acid

Using a mixture of H2O and HCl: -CN -CO2H

CH3CN + 2H2O + H+ CH3CO2H + NH4+

the N atom is lost as NH3. Under the acidic conditions NH3 NH4+

2.
reduction of a nitrile amine

Using either LiAlH4 or H2 gas: -CN -NH2

CH3CN + 2[H] CH3NH2

remember that reduction can be viewed as the addition of hydrogen.

Addition of H-
The mechanism for the addition of H- is identical to that above for the CN-. The only difference is that we
are adding an H atom therefore we make an alcohol.

The condition for this experiment is to use dry ether as the solvent. It does not like water!

As the reaction is a reduction, we can write out an equation using [H] as the reducing agent:

Aldehyde or ketone + [H] Alcohol

Chemical Tests
Brady's Reagent: (also known as 2,4-dinitrophenylhydrazine or 2,4-DNPH)

to test for a carbonyl group in an aldehyde or ketone

Test result: if an aldehyde or ketone is present a bright orange precipitate forms. You can then take
the melting point of the precipitate and compare it to the literature value. This is also how you distinguish
between two ketones or two aldehydes.

Sometimes people refer to as a test for carbonyls. Its not. Its a test for an aldehyde or ketone ONLY.
It doesnt test for carboxylic acids, esters, amides etc.

you dont need to know the structure of the reagent or precipitates but there have been the
occasional question on structures. You might as well know that 2,4-DNP is a nitrogen nucleophile and
the precipitate contains a C=N bond. It is a nucleophilic reaction.

Fehling's/ Benedicts Solution and Tollen's Reagent

to distinguish between an aldehyde and a ketone

Fehling's/Benedicts: more or less the same thing. Fehlings solution is Cu(II) ions dissolved in NaOH (blue
solution). Benedicts is also Cu(II) solution but dissolved in Na2CO3.

Test results: both give a red coloured copper(I) oxide precipitate when heated with an aldehyde, a
ketone won't react.

Tollen's (the silver mirror test): the reagent is silver nitrate dissolved in aqueous ammonia.
Test result: Tollens solution is heated with the aldehyde leaving a silver mirror on the test tube. A
ketone won't react.

these are all redox reactions. The aldehyde is oxidised to a carboxylic acid and the Cu(II) ions are
reduced to Cu(I) for Fehlings/Benedicts and in Tollens, the Ag+ ion is reduced to Ag. The ketone
doesnt react as it cannot be oxidised any further.

Iodoform reaction

to identify a methyl-carbonyl group (or methyl alcohol)

you can also do this reaction with a secondary alcohol. The iodine will oxidise the alcohol to the
ketone first and then you proceed as below.

Test result: a methyl ketone is reacted with iodine in NaOH solution to give pale yellow crystals and an
antiseptic smell. The crystals formed are CHI3 (iodoform).

Sometimes they ask about the other products, so here is an equation of all the products:

CH3COCH3 + 3I2 + 4NaOH CHI3 + CH3COONa + 3NaI + 3H2O

the I2, NaOH, CHI3, NaI and H2O will be in every equation. The only thing that changes is the starting
ketone and salt produce.

also note that the carbon chain has decreased by 1 carbon.