21 - Carbonyls Upper 8th Form Notes

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21: Carbonyls

Carbonyls are organic molecules containing the C=O (carbonyl) bond. The geometry around the carbonyl
group is planar, with bond angles of about 120°. Aldehydes have the general formula RCHO, while ketones
have two alkyl (or aryl) groups attached to the carbonyl: R1R2CO.

O O

H
ethanal propanone
Aldehydes and ketones are usually volatile liquids, since they cannot form hydrogen bonds to each other.
Only the lowest members are soluble in water (The CO functional group is hydrophilic as the lone pairs on
the CO group can accept H-bonds from water molecules, but the alkyl groups are hydrophobic. The longer
the alkyl chain, the less soluble the carbonyl).
Aldehydes and ketones are both attacked by nucleophiles, and can both be reduced to alcohols. However,
only aldehydes can be readily oxidised, and this is the basis for tests to distinguish between them.
Aldehydes and ketones are obtained by oxidation of primary and secondary alcohols, respectively.

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Reactions given by both aldehydes and ketones

Reduction to alcohols

Both aldehydes and ketones may be reduced by nucleophilic reagents, such as sodium borohydride, NaBH 4
(which is used dissolved in water), heated under reflux. Aldehydes are reduced to primary alcohols, and
ketones to secondary ones – the reverse of their mode of formation, by oxidation of alcohols:

CH3CHO + 2[H] → CH3CH2OH (ethanol)

(CH3)2CO + 2[H] → (CH3)2CHOH (propan-2-ol)

The advantage of using NaBH4 is that C=C bonds are not reduced, since they are not attacked by nucleophiles
(whereas H 2 gas and nickel would reduce both C=O and C=C). NaBH 4 effectively provides a hydride ion, H-,
which attacks the δ+ C as a nucleophile. H+ from an acid or the solvent (i.e. water) adds on to the resulting
oxy-anion (this is known as a workup). The mechanism is called nucleophilic addition.
Acid work up:

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21 - Carbonyls Upper 8th Form Notes

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Aqueous work up:

overall CH3COCH3 + 2 [H] CH3CH(OH)CH3

Extension of the carbon chain – addition of cyanide ions

Many other nucleophiles can react in a very similar way to the hydride ion using a nucleophilic addition
mechanism. Addition of cyanide ions, CN-, can be a very useful way of extending the carbon chain (for other
ways of extending the chain, see Friedel-Crafts acylation and alkylation in the ‘Arenes’ topic). Addition of
cyanide uses aqueous potassium cyanide in the presence of dilute sulphuric acid, forming hydroxynitrile
compounds. HCN is not used as it produces such a low concentration of cyanide ions, however when using
KCN, the pH must not be too acidic, as it would convert too much of the cyanide ions into HCN. The
mechanism is as follows:

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21 - Carbonyls Upper 8th Form Notes

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H
δ OH
O O

C C
C N
N N

2-hydroxy-2-methylpropanenitrile

KCN
overall CH3COCH3 + HCN CH3C(OH)(CN)CH3

It is worth noting that the addition of a CN- or H- to a carbonyl can result in a chiral product with a chiral
carbon. In the case of CN- this will occur with the addition to an aldehyde or an asymmetric ketone, while in
the case of H- this will occur with the addition to an asymmetric ketone. The carbon that the addition occurs
at will have 4 different groups bonded to it making it chiral (see topic notes 12 – Halogenoalkanes and
stereoisomeris). In most cases of nucleophilic addition resulting in a chiral product the product will be a
racemic mixture of equal numbers of both enantiomers.

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REMINDER OF L8th Carbonyl chemistry – See notes II – Carbonyls and organic synthesis

Condensation reaction with 2,4-dinitrophenylhydrazine.

2,4-dinitrophenylhydrazine dissolved in methanol (2,4-DNPH, Brady's reagent) is used to detect carbonyl

compounds (both aldehydes and ketones). Conditions for the test are as follows: Add a few drops of 2,4-
DNPH dissolved in methanol to the suspected carbonyl, and if necessary acidify with a little dilute sulfuric
acid. If either an aldehyde or a ketone is present, a yellow-orange precipitate is formed. The precipitate can
be used to identify the original carbonyl compound by recrystallising it, measuring its melting point, and
comparing to known values.

Oxidation of aldehydes

Aldehydes may readily be oxidised to carboxylic acids (using K 2 Cr 2 O 7 and dilute H 2 SO 4 ), and this is the basis
of common tests, which will distinguish them from ketones (i.e. the orange dichromate will turn green when
it reacts with an aldehyde and will not change colour with a ketone).

The silver mirror test – Tollens’ reagent

Tollens’ reagent, or ammoniacal silver nitrate, is obtained by adding sodium hydroxide dropwise to silver
nitrate solution to form a precipitate of silver oxide. Concentrated ammonia solution is then added until the
precipitate just redissolves. When a few drops of aldehyde are added, and the tube is warmed in hot water,
a silver mirror is deposited on the surface of the tube. The silver ion complex oxidises the aldehyde to a
carboxylic acid, and is itself reduced to silver.

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21 - Carbonyls Upper 8th Form Notes