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Discussion
Structure, Nomenclature and Properties of
Aldehydes and Ketones
Structures of Aldehydes and Ketones
 Both aldehydes and ketones contain the carbonyl group
C = O , a carbon-oxygen double bond.
 Aldehydes have at least one hydrogen atom bonded to the carbonyl carbon.
 Ketones have alkyl or alkyl or aryl groups bonded to the carbonyl carbon.

Naming Aldehydes and Ketones

 The IUPAC naming of aldehydes follows a similar process to that used for other organic
molecules.
- The longest continuous carbon chain (parent chain) that contains the carbonyl is given the name
of the corresponding alkane modified by dropping the last –e and adding –al.
- The parent chain is numbered from the aldehyde end the carbonyl group is understood to be
number 1.
- Other groups attached to the parent chain are named and numbered in the usual IUPAC fashion.

 The IUPAC naming of ketones is the same as that for aldehydes except for the following:
- The longest continuous carbon chain (parent chain) that contains the carbonyl is given the name of
the corresponding alkane modified by dropping the last –e and adding –one.
- If the parent chain is longer than four carbons, it is numbered so that the carbonyl group has the
smallest number possible; this number is prefixed to the parent ketone name.

Bonding and Physical Properties

 The carbonyl group in aldehydes and ketones is very polar, with the oxygen pulling
electrons from the carbon.
 Unlike alcohols, aldehydes and ketones do not hydrogen-bond to themselves. They have
lower boiling points than alcohols of comparable molar mass.
 Aldehydes and ketones with four or fewer carbons are at least partly water soluble.
 Lower-molar-mass aldehydes have a penetrating, dis-agreeable odor, while higher-molar-
mass aldehydes and ketones are more fragrant, some being used in flavorings and
perfumes.

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Chemical Properties of Aldehydes and Ketones

 Aldehydes are easily oxidized to carboxylic acids. Under similar conditions, ketones are
unreactive.
 In the Fehling and Benedict tests, Cu 2+ is reduced to form Cu2O; a reddish brown precipitate.
Aldehydes are oxidized; simple ketones do not react.
 Both aldehydes and ketones can be reduced aldehydes yield primary alcohols, while
ketones yield secondary alcohols.
 A hemiacetal is formed when an alcohol adds across an aldehyde carbonyl double bond. If
an alcohol adds to a ketone, a hemiketal is produced.
- The carbon in a hemiacetal or hemiketal is bonded to both an ether oxygen and an alcohol
oxygen.

 With an excess of alcohol, two alcohols can react with a carbonyl to form ab acetal (from an
aldehyde) and a ketal (from a ketone).
- The carbon in an acetal or ketal is bonded to two ether oxygens.

 Intramolecular hemiacetal/hemiketal formation is significant in carbohydrate chemistry.

 Cyanohydrins are formed by the addition of HCN to a carbonyl group.
- The Cyanohydrins carbon is bonded to an hydroxyl group and a cyano ( CN) group.

 In an aldol condensation, two carbonyl-containing molecules (either aldehydes or ketones)

connect together.
- One aldehyde or ketone adds across the carbonyl group of the second aldehyde or ketone
- The alpha hydrogen from one molecule adds to the carbonyl oxygen of the molecules, while the
remainder of the first molecule, adds to the carbonyl carbon.

Common Aldehydes and Ketones

 Formaldehyde (methanal) is produced from methanol by air oxidation and is used primarily
in the manufacture of polymers.
 Acetaldehyde and methyl ethyl ketone (MEK) are formed by oxidation from the secondary
alcohols 2-propanol and 2-butanol, respectively.
- These ketones are excellent organic solvents and are found in many commercial products such
as paints, lacquers, varnishes, and fingernail polish remover.

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Condensation Polymers
 Condensation polymers form when monomers combine and eliminate a small-molecule
product such as water.
 Common examples of condensation polymers are the phenol-formaldehyde polymers, also
known as phenolics. These thermosetting polymers are widely used in electrical equipment
because of their insulating and fire-resistant properties.