What are Carbonyl

Compounds?
By Kiraj Potavadoo and Tom
James

What is a Carbonyl Group?

How are they named?

The carbon with the
The carbon with the
C=O group in ketones
CHO group in
is always labelled from
aldehydes is always
the shortest end.
labelled 1. Aldehydes
Ketones have the
have the suffix -al.
suffix -one. The
The longest straight
longest straight chain
chain is taken, to
is taken, to determine
determine the stem.
the stem. Any side
Any side chains are
added at the beginning chains are added at
the beginning with
with their associated
their associated
positioning numbers.
positioning numbers.

Reactions of Carbonyls Compounds

- Oxidation of Primary Alcohols
Primary alcohols can be oxidised to
aldehydes and then to carboxylic
Potassium
Dichromate
acids.
(K2Cr2O7) and
concentrated sulfuric acid
(H2SO4) are used as an
oxidising agent.
The aldehyde must be
distilled immediately to
prevent further oxidation.
To make a carboxylic
acid, the solution must be
heated under reflux,
before distilling the

Oxidising Aldehydes
Aldehydes can be
oxidised further
to form
carboxylic acids.
Acidified
Potassium
Dichromate can
be used as a
suitable oxidising
agent. Turning

Reactions of Carbonyls Compounds

- Oxidation of Secondary Alcohols
Secondary alcohols can be oxidised
to form ketones.
Potassium Dichromate
(K2Cr2O7) and
concentrated sulfuric acid
(H2SO4) are used as an
oxidising agent.
To make a ketone, the
solution must be heated
under reflux, before
distilling the product off.

Reduction of aldehydes and ketones

For both reduction
reactions, either Sodium
Borohydride (NaBH4) or
Lithium Aluminum
Hydride (LiAlH4) can be
used as a reducing agent.

Reduction is just the

opposite of oxidation so
the reactions look very
similar, just in reverse
and with [H] used
instead of [O].

Nucleophilic Addition of Aldehydes

and Ketones
The nucleophile splits by
heterolytic fission initially.
As in alkenes, it then
adds across the double
bond, except in carbonyls
it is across the C=O,
rather than a C=C. This
leaves an electron
proficient oxygen which is
attacked by an
electrophile in solution,
often a proton (H+). The
reactions are the same
for both aldehydes and
ketones.

Carbonyl compound tests

Bradys Reagent
2,4-dinitrophenylhydrazine (2,4-DNPH) is mixed
with methanol and sulfuric acid to form a solution.
When added to an aldehyde or a ketone, a positive
colour change to a yellow/orange precipitate is
formed.
This 2,4-DNPH derivative shows a C=O group is
present. However it does not work for esters or
carboxylic acids due to their extra resonance
structures, in which the carbonyl carbon has a
weaker positive charge, so is insufficiently
electrophilic to split the 2,4-DNPH.

Carbonyl compound tests continued

Tollens Reagent (Ammoniacal Silver Nitrate)
A weak oxidising agent made up of aqueous sodium
hydroxide and silver nitrate to make a brown silver
oxide precipitate. This is then added to dilute
ammonia until the solid dissolves. It determines
whether it is an aldehyde or a ketone.
An aldehyde produces positive silver mirror
precipitate, a ketone does not react.
It works as an aldehyde can be oxidised whereas a
ketone cannot, so the resulting carboxylic acid shows
the change, whereas the ketone remains as it is.

Carbonyl compound tests continued

2
Once a compound has been identified as
either a ketone or an aldehyde, it can be
possible to then accurately determine the
compound structure itself.
The 2,4-DNPH derivative is impure, and
when filtered and recrystallized, is made
pure. Once dry, this solid can be melted,
with its melting point recorded. This value
can then be compared to a data value/book,
to identify the original carbonyl compound.

Carbonyl compound tests continued

3
Alternatively, to determine an
alcohol, react with ceric nitrate
reagent (Ce (NO3)6) to produce a
colour change (yellow to red).
Carbonyl compounds do not react
with ceric nitrate. Production of a
magenta colour therefore indicates
the presence of an alcohol group.

Carbonyl compound tests continued

4
Plus, aldehydes react with Schiff's reagent
(bisulfite ion) to produce a colour change
(magenta-coloured addition product). The sulfur in
the bisulfite ion acts as a nucleophile and adds to
the carbonyl carbon. Because this is such a large
nucleophile, it will only add to a relatively simple
carbonyl. This requires that the carbonyl be part
of an aldehyde in which one of the R groups is the
very small hydrogen, or a ketone having small R
and R groups. A ketone with large groups
attached to the carbonyl will not react with
bisulfite.

Carbonyl compound tests continued

5
The iodoform test indicates the presence of
an aldehyde or ketone in which one of the
groups directly attached to the carbonyl
carbon is a methyl group. In the iodoform
test, the unknown is allowed to react with a
mixture of iodine and base. This forms the
carboxylic acid salt plus iodoform, a yellow
precipitate. Formation of a yellow precipitate
therefore indicates the presence of a methyl
group directly attached to the carbonyl.