ALDEHYDES

AND
KETONES
Principles of Chemistry lecture
BS Psychology 2-4
 01
Structural
Characteristics of
Carbonyl Groups
CARBONYL GROUPS
A carbonyl group is a chemically organic
functional group composed of a carbon
atom double-bonded to an oxygen atom
(C=O)

The carbonyl oxygen atom shares two of

its six valence electrons with the carbonyl
carbon atom. Its remaining four valence
electrons remain as two sets of electron
lone pairs.

The carbonyl carbon atom shares two of

its four valence electrons with the
carbonyl oxygen atom, and its remaining
two electrons form two single bonds to
other atoms.
CARBONYL GROUPS
The bond is polarized toward
oxygen such that oxygen is
partially negative while the
carbon is partially positive. So
electron density is higher on the
oxygen side of the bond and
lower on the carbon side.
CARBONYL GROUPS
The carbonyl carbon is sp2
hybridized.
The geometry of the
carbonyl carbon is trigonal
planar.
 ALDEHYDES & KETONES
The simplest carbonyl groups are aldehydes and ketones
that are usually attached to another carbon compound.

They are simple in the sense that they don't have other
reactive groups like -OH or -Cl attached directly to the
carbon atom in the carbonyl group- unlike, for example,
carboxylic acids containing -COOH.

Formaldehyde (CH2O) is the simplest compound with a

carbonyl group.
 ALDEHYDES & KETONES

Aldehydes – at least one bond on the carbonyl group is a

carbon-to-hydrogen bond

Ketones – both available bonds on the carbonyl carbon atom

are carbon-to-carbon bonds.
 ALDEHYDES
In aldehydes, the carbonyl group has a hydrogen atom attached to it together with
either a second hydrogen atom or, more commonly, a hydrocarbon group which
might be an alkyl group or one containing a benzene ring.

When writing formula for these, the aldehyde group (the carbonyl group
with the hydrogen atom attached) is always written as -CHO and never as
-COH. As it could easily be confused with an alcohol.

o Methanal is written as HCHO

o Ethanal is written as CH3CHO

 KETONES
In ketones, the carbonyl group has two hydrocarbon groups attached,
which as mentioned, can either be alkyl groups or ones containing
benzene rings.

Propanone is normally written CH3COCH3.

Notice that ketones never have a hydrogen atom attached

to the carbonyl group.
 WHERE DO ALDEHYDES AND
KETONE DIFFER?
An aldehyde differs from a ketone by having a
hydrogen atom attached to the carbonyl group. This
makes the aldehydes very easy to oxidize.

Ketones don't have that hydrogen atom and are

resistant to oxidation. They are only oxidized by
powerful oxidizing agents which have the ability to
break carbon-carbon bonds.
02
Nomenclature of
Aldehydes and
Ketones
 Summary of Aldehyde
Nomenclature rules
The aldehyde funtional group is
Aldehydes take their name from given the #1 numbering location

01 their parent alkane chains. The

-e is removed from the end and 02 and this number is not included
in the name.
is replaced with -al.

For the common name of

aldehydes start with the common
When the -CHO functional group is
attached to a ring the suffix
03 parent chain name and add the
suffix -aldehyde. Substituent 04 -carbaldehyde is added, and the
carbon attached to that group is C1.
positions are shown with Greek
letters.
The IUPAC system names are given on top while the common name is given
on the bottom in parentheses.
The IUPAC system names are given on top while the common name is given
on the bottom in parentheses.
Aldehydes Common Names
 Summary of Ketone Nomenclature rules

1. Ketones take their name from their parent alkane

chains. The ending -e is removed and replaced with
-one.
2. The common name for ketones are simply the
substituent groups listed alphabetically + ketone.
3. Some common ketones are known by their generic
names. Such as the fact that propanone is commonly
referred to as acetone.
The IUPAC system names are given on top while the common
name is given on the bottom in parentheses.
Ketone Common Names
Naming Aldehydes and Ketones in the Same Molecule

Because aldehydes have a higher priority than ketones,

molecules which contain both functional groups are named as
aldehydes and the ketone is named as an "oxo" substituent. It is
not necessary to give the aldehyde functional group a location
number, however, it is usually necessary to give a location
number to the ketone.
 Naming Dialdehydes and Diketones

For dialdehydes the location numbers for both carbonyls are

omitted because the aldehyde functional groups are expected to
occupy the ends of the parent chain. The ending –dial is added to
the end of the parent chain name.
 Naming Dialdehydes and Diketones

For diketones both carbonyls require a location number. The

ending -dione or -dial is added to the end of the parent chain.
 Naming Cyclic Ketones and Diketones
Remember the prefix cyclo is
included before the parent
chain name to indicate that it is
in a ring. As with other ketones
the –e ending is replaced with
the –one to indicate the
presence of a ketone.

With cycloalkanes which

contain two ketones both
carbonyls need to be given a
location numbers. Also, an –e is
not removed from the end, but
the suffix –dione is added.
Naming Carbonyls and Hydroxyls in the Same Molecule
When and aldehyde or ketone is present in a molecule which also contains
an alcohol functional group the carbonyl is given nomenclature priority by
the IUPAC system. In the case of alcohols the OH is named as a hydroxyl
substituent. However, the l in hydroxyl is generally removed.
 Naming Carbonyls and Alkenes in the Same Molecule
When and aldehyde or ketone is present in a molecule
which also contains an alkene functional group the
carbonyl is given nomenclature priority by the IUPAC
system.

When carbonyls are included with an alkene the following

order is followed:

(Location number of the alkene)-(Prefix name for the

longest carbon chain minus the -ane ending)-(an -en
ending to indicate the presence of an alkene)-(the
location number of the carbonyl if a ketone is present)-
(either an –one or and -anal ending).

Remember that the carbonyl has priority so it should get

the lowest possible location number. Also, remember that
cis/tran or E/Z nomenclature for the alkene needs to be
included if necessary.
ALDEHYDES
KETONES
Let’s try!
You may chat your answers in
the class meeting’s chatbox.
Give the IUPAC name for each compound:
Correct answers:

5-bromo-2-pentanone

1,2-cyclobutanedione
Give the structure corresponding to each name:
CORRECT ANSWERS:

2,3-pentanedione trans-2-methyl-3-hexenal
03
ISOMERI
SM
CONSTITUTIONAL ISOMERISM
● Also known as structural isomerism.
● Same molecular formula but different
bonding arrangement
 TYPES OF
CONSTITUTIO
NAL ISOMERS
 Skeletals/Chain Isomerism
● Difference in the arrangement of the carbon chain, same position of carbonyl
01 ●
group
Only possible for Aldehydes (with 4 or more carbon atoms) and Ketones (with
5 or more carbon atoms
Examples: C4H8O (mf)

Aldehydes
Ketones
 Position Isomerism

02 ● Difference in the position of the carbonyl group; same carbon chain

arrangement
● Only Ketones having 5 or more carbon atoms can exhibit position isomerism

Ketones - Aliphatic ketones show position isomerism

Examples: C5H10O (mf)

 Why can’t
The –CHO Aldehydes?
group is and should always be
present at the terminal of the carbon chain.
 Functional Group Isomerism
● Aldehydes and Ketones with the same number of carbon atoms and same
03 ●
degree of saturation.
Aldehydes and ketones are functional isomers of each other.

Examples: C3H6O
 METAMERISM
● Presence of different alky groups attached to each side of the
04 ●
functional group
Only ketones can exhibit metamerism

ALDEHYDES KETONES
can only have one alkyl polyvalent functional group
group connected to it as (having more than one
hydrogen atom is already bond connected to it
attached to its side
Example : C5H10O (mf)
 TAUTOMERISM
● Difference in the location of double bonds and one
proton (hydrogen)
03 ● Led by the presence of acidic or base conditions
(catalysts)
● Chemical equilibrium between two isomers
● Interconversion through the movement of a proton
and shifting of bonding electrons
● For aldehydes and ketones, they undergo the keto-
enol tautomerism
 KETO FORM ENOL
Contains a carbonyl bond (either
Presence of a double bond
aldehydes or ketones) – two
separate transfer syeps and a hydroxyl group
Example :
 04
Physical & Chemical
Properties of Aldehydes
and Ketones
The presence of alkyl groups tends
to lower both boiling points and
melting points, as does the presence
of unsaturation in the carbon chain.
Lower-molecular-mass ketones are
colorless liquids at room
temperature
The boiling point of aldehydes and
ketones are intermediate between
those of alcohols and alkanes of
similar molecular mass.
 Aldehydes and ketones have higher
boiling points than alkanes because of
dipole-dipole attractions between
molecules
BOILING POINT

The boiling point of

aldehydes and ketones is
lower than those of
corresponding alcohols
and carboxylic acids, and
a higher boiling point than
non-polar compounds
(hydrocarbons).
 Lower molecular mass ketones are
1 colorless liquids at room
temperature.

Aldehydes and ketones have higher

boiling points than alkanes because
2 of dipole-dipole attractions
between molecules.

The ordering of the respective boiling

3 points for carbonyl compounds, alcohols,

and alkanes of similar molecular mass is:
alcohols > carbonyl compounds > alkanes.
 The hydrogen bonding causes
lowmolecular-mass aldehydes and
ketones to be water soluble
 As the hydrocarbon portions get
larger, the water solubility of
aldehydes and ketones decreases
SOLUBILITY
Aldehydes and ketones that have fewer carbon
atoms are soluble in both organic solvents and
water. However, if there are six or more
carbon atoms present, the compound is then
soluble in organic solvents but not in water.
 Aldehydes with higher molecular mass
1 (above C8) are more fragrant, especially
benzaldehyde derivates.

Ketones have generally pleasant odors,

2 are used often in perfumes and air
fresheners.

The order of boiling points for carbonyl

compounds (aldehydes and ketones),
3 alcohols, and alkanes of similar molecular
mass is: Alcohols > Carbonyl Compounds >
Alkanes
05
PREPARATION OF
ALDEHYDES &
KETONES
The term aldehyde stems from alcohol
dehydrogenation, indicating the
aldehydes are related to alcohols by
the loss of hydrogen.
 When this type of reaction is used for
aldehyde preparation, reaction conditions must
be sufficiently mild to avoid further oxidation of
the aldehyde to a carboxylic acid (Section 14.9).
Ketones do not undergo the further oxidation
that aldehydes do.
In the oxidation of an alcohol to an aldehyde or
a ketone, the alcohol molecule loses H atoms.
Recall that a decrease in the number of C-H
bonds in an organic molecule is one of the
operational definitions for the process of
oxidation.
Oxidation and Reduction of
Aldehydes and Ketones.
 OXIDATION
Aldehydes readily undergo oxidation
to carboxylic acids and ketones are
resistant to oxidation.
REDUCTION
Aldehydes and ketones are easily
reduced by hydrogen gas (H2), in the
presence of a catalyst (Ni, Pt or Cu) to
form alcohols. The reduction of
aldehydes produces primary alcohols,
and the reduction of ketones yields
secondary alcohols.
It is the addition of hydrogen atoms to
the carbon-oxygen double bond that
produces the alcohol in each of these
reactions.
This hydrogen addition process is very
similar to the addition of hydrogen to
the carbon-carbon double bond of an
alkene to produce an alkane
 Aldehyde reduction and ketone reduction to
produce alcohols are the “opposite” of the
oxidation of alcohols to produce aldehydes and
ketones. These “opposite” relationships can be
diagrammed as follows
 05
Sources of Aldehydes
And Ketones (Uses and
Benefits)
PERFUMES

Aldehydes are present in many organic

materials, everything from rose, citronella,
vanilla and orange rind. Scientists also can
create these compounds synthetically to use
as ingredients for sweet-smelling perfumes
and colognes.
INDUSTRIAL APPLICATION

Aldehydes are versatile compounds that can

help make resins, dyes and organic acids, as
well as perfumes for cologne, detergents and
soaps. Of all aldehydes, formaldehyde is
produced industrially on the largest scale.
Formaldehyde is found in the gaseous form.
However, formaldehyde with 40% solution in
water forms formalin. Formalin helps in the
preservation of biological specimens. The
compound- formaldehyde is essential during
many industrial processes such as
embalming, glue preparation, tanning and
manufacture of polymeric products.
Ketone behaves as an excellent solvent for certain
types of plastics and synthetic fibres. It also is
used for medicinal purposes such as chemical
peeling procedure as well as acne treatments.
Butanone, also known as methyl ethyl ketone, is
one of the common solvents. It is used in textile
production, varnishes production, paint remover
production, paraffin wax production, plastic
production, etc.
Aldehydes and ketones impart some very
characteristics fragrance in compounds. For
instance, ketones help in the formation a
compound “acetophenone” which is responsible
for fragrances such as cherry, jasmine,
honeysuckle, almond, strawberry, etc. However,
aldehydes are a well-known source of perfumes
and fragrances in comparison to ketones.
Aldehydes are an essential component in
particular sugars. Moreover, certain popular
flavours of baking such as cinnamon, vanilla during
baking are because of aldehydes.
 06
Sulfur-Containing
Carbonyl Groups
● The introduction of sulfur into a carbonyl group produces two
different classes of compounds, depending on whether the
sulfur atom replaces the carbonyl oxygen atom or the carbonyl
carbon atom.

● Thiocarbonyl compounds - Sulfur replaces carbonyl

oxygen atom.
 Thioformaldehy
de Methane
(Methanethial) → one carbon atom

Methanethial

Thial
→ Thioaldehyde, a functional group
similar to an aldehyde with a general
structure of RC(O)S, in which the oxygen
has been replaced by a sulfur atom.
 Thioacetone Propane
→ three carbon atom
(Propanethione)

Propanethione

Thione
Thioketones, organosulfur
compounds related to conventional
ketones with a general structure of
R2C=S,
in which the oxygen has been
replaced by a sulfur atom. Note that Thiocarbonyl compounds such as Thioformaldehyde and
Thioacetone are unstable and readily decompose.
 Sulfoxides
→ ● Sulfur replaces carbonyl
carbon atom and are more stable
than thiocarbonyl compounds

The oxidation of a thioether Dimethyl sulfoxide

(sulfide) constitutes the most (DMSO) - a sulfur
common route to a sulfuxide. analog of acetone
 → ● Sulfur replaces carbonyl
Sulfoxides carbon atom and are more stable
than thiocarbonyl compounds

DMSO is an odorless
liquid with unusual
properties. Due to
ACETONE the presence of the
polar sulfur-oxide
bond, DMSO is
miscible with water
and also quite
soluble in less polar
DMSO organic solvents.