ALDEHYDES AND

KETONES
Module 12
• The study of carbonyl containing compounds (-C=O) is important as we study
organic chemistry and in preparation for Biochemistry. Carbonyl compounds
are everywhere. In addition to their uses as reagents and solvents, they are
constituents of fabrics, flavorings, plastics, and drugs. Naturally occur- ring
carbonyl compounds include proteins, carbohydrates, and nucleic acids that
make up all plants and animals.
• The simplest carbonyl compounds are ketones and aldehydes. A ketone has
two alkyl (or aryl) groups bonded to the carbonyl carbon atom.
An aldehyde has one alkyl (or aryl) group and one hydrogen atom bonded to
the carbonyl carbon atom (1).
NOMENCLATURE FOR ALDEHYDES
• IUPAC names for Aldehydes
• Replace the final -e of the alkane name with -al.
• Carbonyl carbon of the aldehyde is always assigned carbon no. 1, and
is usually at the terminal position of the carbon chain.
• If the aldehyde group is a substituent of a large unit (usually a ring),
the suffix carbaldehyde is used.
NOMENCLATURE FOR KETONES
• IUPAC names for Ketones
• Replace the final -e in the alkane name with -one. The “alkane”
name becomes “alkanone.”
• In open-chain ketones, we number the longest chain that includes
the carbonyl carbon from the end closest to the carbonyl group, and
we indicate the position of the carbonyl group by a number.
• In cyclic ketones, the carbonyl carbon atom is assigned the
number 1
COMMON NAMES
• Ketones and aldehydes are often called by common names instead of
their systematic IUPAC names:
• For ketones:
• Name the two alkyl groups bonded to the carbonyl group.
• Assign Greek letters for the location of the substituent groups, beginning
with the carbon next to the carbonyl group.
• Historical names are also used. Dimethyl ketone is always called acetone,
and alkyl phenyl ketones are usually named as the acyl group followed by the
suffix -phenone.
• For aldehydes: Common names of aldehydes are derived from the
common names of the corresponding carboxylic acids:
 STRUCTURE AND PROPERTIES
• The carbonyl carbon atom is sp2 hybridized and bonded to three
other atoms through coplanar sigma bonds oriented about 120°
apart. The unhybridized p orbital overlaps with a p orbital of oxygen
to form a pi bond. The double bond between carbon and oxygen is
similar to an alkene C=C double bond, except that the carbonyl double
bond is shorter, stronger, and polarized.
 STRUCTURE AND PROPERTIES
• The double bond of the carbonyl group has a large dipole moment
because oxygen is more electronegative than carbon, and the bonding
electrons are not shared equally. In particular, the less tightly held pi
electrons are pulled more strongly toward the oxygen atom, giving
ketones and aldehydes larger dipole moments than most alkyl halides
and ethers. We can use resonance forms to symbolize this unequal
sharing of the pi electrons.
STRUCTURE AND PROPERTIES
• The first resonance form is more important because it involves more
bonds and less charge separation. The contribution of the second
structure is evidenced by the large dipole moments of the ketones
and aldehydes shown here.
• This polarization of the carbonyl group contributes to the reactivity of
ketones and aldehydes: The positively polarized carbon atom acts as
an electrophile (Lewis acid), and the negatively polarized oxygen acts
as a nucleophile (Lewis base) (1).
 PHYSICAL PROPERTIES OF
ALDEHYDES AND KETONES
• Boiling points of aldehydes and ketones are higher than the hydrocarbons
of the same molecular weight due to the presence of a polar carbonyl
group. However, aldehydes and ketones have lower boiling points than the
corresponding alcohols, since they cannot exhibit hydrogen bonds between
their molecules. This trend is shown below:
• The boiling point of aldehydes
and ketones increases as
molecular weight increases or as
carbon chain gets longer.
• The solubility in water of
aldehydes and ketones decreases
as molecular weight increases or
as carbon chain gets longer.
REACTIONS OF ALDEHYDES AND
KETONES
• The two general types of reactions for Aldehydes and ketones are:
OXIDATION
• Examples of oxidizing agents that can convert aldehydes into
carboxylic acids, include KMnO4 and hot HNO3 but CrO3 in aqueous
acid is a more common choice. The oxidation occurs rapidly at room
temperature and generally results in good yields. Example is shown
below:
 OXIDATION WITH TOLLEN’S REAGENT
• An alternative reagent used in the laboratory for the oxidation of
aldehyde is the solution of silver oxide, Ag2O, in aqueous ammonia,
also known as the Tollens’ reagent. Aldehydes are oxidized by Tollens’
reagent in high yield without harming carbon–carbon double bonds
or other acid-sensitive functional groups in a molecule which is the
problem encountered when using CrO3. This reaction of aldehyde
with Tollens reagent is called selective oxidation.
HEMIACETALS AND ACETALS