Carbonyl Chemistry

The carbonyl functional

group is C=O. It is found in a
wide range of organic
compounds, including
aldehydes, ketones, and
carboxylic acids. There are
others, some of which are in
the table.
 The Carbonyl Group
Naming aldehydes
Aldehydes are named after the number of carbon atoms they contain, including the carbon
atom in the carbonyl group, and their names end in al. The carbonyl group in aldehydes is
shown as –CHO in shortened structural formulae. Methanal is HCHO and ethanal is CH3CHO.

Naming ketones
Ketones are named after the number of carbon atoms they contain, including the carbon
atom in the carbonyl group, and their names end in one. The carbonyl group in ketones is
shown as –CO in shortened structural formulae. Propanone is CH3COCH3 and butanone is
CH3CH2COCH3.

Position isomers
Ketones with five or more carbon atoms have position isomers. For example, pentanone has
two position isomers. Pentan-2-one is CH3(CH2)2COCH3 and pentan-3-one is
CH3CH2COCH2CH3.

Chain isomers
Ketones with five or more carbon atoms have chain isomers. You name the main chain
containing the carbonyl group first, then base the numbering of any side chains on this
name. For example, the branched chain isomer of pentanone, CH3CH(CH3)COCH3, is called 3-
methylbutan-2-one and not 2-methylbutan-3-one.
 The Carbonyl Group

Naming carboxylic acids

The carbonyl group in carboxylic acids is attached to a carbon atom that also has a
hydroxyl group, –OH. It forms a new functional group, the carboxyl group, which is
shown as –COOH. Carboxylic acids are named after the number of carbon atoms
they contain, including the carbon atom in the carboxyl group, and their names end
in oic acid. Methanoic acid is HCOOH and ethanoic acid is CH3COOH.
 The Carbonyl Group
Distinguishing between aldehydes and ketones
Aldehydes are readily oxidized to carboxylic acids but ketones resist oxidation. For example, ethanal is
oxidized to form ethanoic acid: CH3CHO + [O] → CH3COOH

[O] represents the oxidizing agent This observation is the basis of two simple laboratory tests to
distinguish between aldehydes and ketones.

Tollens’ reagent
Aldehydes produce a silver mirror with Tollens’ reagent but ketones do not. The test is carried out in
this way. A small volume of aqueous sodium hydroxide is added to some aqueous silver nitrate. A
precipitate forms, which is changed to aqueous [Ag(NH3)2]+ ions by adding some aqueous ammonia.
The test substance is added and the mixture is warmed. Aldehydes reduce the [Ag(NH3)2]+ ions to silver,
and become oxidized to carboxylic acids in the process.

Fehling’s solution
Fehling’s solution is a blue solution containing a complex of Cu2+ ions. When heated with Fehling’s
solution, aldehydes reduce it to form a brick-red precipitate of copper(I) oxide, Cu2O. Ketones do not
react with Fehling’s solution, so no change is observed.
Identifying A Carbonyl Compound
Obviously the many and varied instruments will be able to easily identify a
carbonyl group, but there is another, chemical method we can use as well.

You can:

React the carbonyl to make a solid (solid derivative)

Measure the melting point of the derivative
Check the melting point

The solid derivatives can be made using Bradys Reagent (2-4-

dinitrophenylhydrazine). The carbonyl compound is mixed with this in
methanol and an orange crystaline solid is formed. The soild is filtered off
and recrystalised and the melting point is then measured against known
values.

If you are just testing for the presence of the carbonyl group then just
mixing with Bradys reagent will cause the orange crystals to appear. This
works for both aldehydes and ketones.
 Alcohols from Aldehydes and Ketones
You may remember from AS that primary alcohols can be oxidized to aldehydes, and
secondary alcohols to ketones. The oxidizing agent or oxidant is often potassium
dichromate(VI), K2Cr2O7, acidified with sulphuric acid. It can be represented as [O] in
equations:

The colour changes during the reaction from orange to green as dichromate(VI) ions are
reduced to blue-green chromium(III) ions. The process can be reversed, with aldehydes
being reduced to primary alcohols, and ketones being reduced to secondary alcohols.

Reducing aldehydes and ketones

Sodium tetrahydridoborate NaBH4 is commonly used to reduce carbonyl compounds
such as aldehydes and ketones. Lithium tetrahydridoaluminate LiAlH4 is a more powerful
reducing agent or reductant that may be used instead. Both reductants produce the
hydride ion H2. This acts as a nucleophile and attacks the carbon atom in the carbonyl
group of aldehydes and ketones. The reductant is shown as [H] in equations, just as an
oxidant is shown as [O].
Aldehydes and primary alcohols

This is the general equation for the reduction of aldehydes.

For example, propanal is reduced to propan-1-ol, a primary alcohol:

Ketones and secondary alcohols

This is the general equation for the reduction of ketones.

For example, propanone is reduced to propan-2-ol, a secondary alcohol:

Nucleophilic addition

Oxygen is more electronegative than carbon, so the C=O bond is polar. The carbon
atom has a partial positive charge δ+ and the oxygen atom has a partial negative charge
δ-. The δ+ carbon atom can be attacked by nucleophiles such as the hydride ion :H-. The
reaction is a nucleophilic addition reaction in which the nucleophile forms a co-
ordinate bond with the carbon atom, and the C=O bond becomes a C-O bond. Note
that the nucleophilic reactions you met in Unit 2 were nucleophilic substitution
reactions in haloalkanes.

Here is the general reaction mechanism for the reduction of aldehydes and ketones.
Remember that a curly arrow shows the movement of a pair of electrons, such as a
lone pair of electrons or the pair of electrons in a covalent bond.
Aldehydes and ketones react with hydrogen cyanide, HCN, to produce hydroxynitriles.
For example:

The mechanism is another example of nucleophilic addition, and the nucleophile is the
cyanide ion :CN-. The production of hydroxynitriles from aldehydes and ketones is
interesting because an extra carbon atom is added to the carbon chain during the
reaction, and hydroxynitriles may have optical isomers.

Nucleophilic addition
Here is the general reaction mechanism for the reaction of aldehydes and ketones with
hydrogen cyanide. It is identical to the reaction mechanism for the reduction of
aldehydes and ketones, except that the nucleophile is CN- rather than H-.
The complete mechanism is drawn like this. In this example, the carbonyl compound
is an aldehyde, ethanal.

Hydrolysis of the nitrile group

One more carbon atom is added to the carbon chain when hydrogen cyanide reacts
with an aldehyde or ketone. For example, ethanal with two carbon atoms becomes
2-hydroxypropanenitrile with three carbon atoms.
The nitrile group is hydrolyzed in acidic conditions to become a carboxyl group. For
example:

Optical isomers
Ethanal reacts with hydrogen cyanide to form 2-hydroxypropanenitrile. This has an
asymmetric carbon atom, so it has optical isomers. 2-hydroxypropanenitrile can be
hydrolyzed to form 2-hydroxypropanoic acid (lactic acid), which also has an asymmetric
carbon atom. Note that not all hydroxynitriles have optical isomers. Methanal reacts
with hydrogen cyanide to produce hydroxyethanenitrile, which does not have an
asymmetric carbon atom.
Carboxylic acids contain the carboxyl group -COOH. They are synthesized in the
laboratory by oxidizing primary alcohols or aldehydes using acidified potassium
dichromate(VI). For example:
Weak acids
Carboxylic acids are weak acids. The strength of an acid can be shown by its pKa
value: the stronger the acid, the lower its pKa. The pKa of ethanoic acid is 4.8 at
25oC. The pH of 0.1 mol dm-3 ethanoic acid is 2.9 but the pH of 0.1 mol dm-3
hydrochloric acid is 1. Carboxylic acids react with carbonates to release carbon
dioxide gas.

This gives a simple test for the presence of carboxylic acids. Fizzing or
effervescence is seen when a carboxylic acid is added to sodium carbonate. For
example, this can reveal if an aldehyde, produced when an alcohol is oxidized,
has oxidized further to form a carboxylic acid.
Making esters
Carboxylic acids react with alcohols to produce esters. Concentrated sulfuric acid or
hydrochloric acid is added as a catalyst. Here is the general equation for the reaction,
called esterification:

The formulae are coloured so you can see which parts of the carboxylic acid and
alcohol contribute to the ester. Different combinations of carboxylic acid and
alcohol produce different esters:
Naming esters
Esters are named after the alcohol and carboxylic acid that would form them. The
first part of the name comes from the alcohol. For example, methyl comes from
methanol and ethyl from ethanol. The second part of the name comes from the
carboxylic acid. For example, methanoate comes from methanoic acid and
ethanoate from ethanoic acid. You can recognize the carboxylic acid part from the
structural formula, as it is the part that includes COO. Here are two examples: