Aldehydes and Ketones

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 Aldehydes and ketones
Aldehydes and ketones are organic
compounds that belong to another very
important family of compounds – the family
containing the carbonyl group, C=O
This functional group is found in three main
families of compounds: aldehydes, ketones
and carboxylic acids and its derivatives like
esters, acid chlorides, acid anhydrides and
amides

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 Carbonyl compounds
 These are compounds that contain the
carbonyl functional group

Examples: Aldehydes, ketones, carboxylic

acids, esters, amides, acyl halides, etc.

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 Aldehydes and ketones
The functional group of an aldehyde is a
carbonyl group bonded to a hydrogen atom

The R group can be a hydrogen atom or an

sp1, sp2, or sp3 hybridized carbon atom

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 Aldehydes and ketones
Ketones on the other hand are compounds in
which the carbonyl group is attached to two
carbon atoms

Similar to the aldehydes, the R group can be

an sp1, sp2, or sp3 hybridized carbon atom

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 Aldehydes and ketones
As we have already seen, the carbon-oxygen
double bond consists of a sigma bond formed
by the overlapping of the sp2 hybridized
orbitals of carbon and oxygen and one pi
bond formed by the overlapping of the
parallel 2p orbitals
This is very similar to the bond we find in
alkenes

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Importance of carbonyl compounds
Earlier we saw structures and the chemistry of
alkenes with their double bonds;

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Importance of carbonyl compounds
We can extend our study of double bonds to
exploring the chemistry of the carbon-oxygen
double bond
Although it bears many similarities to the
carbon-carbon double bonds, the carbon-
oxygen double is not “just another double
bond”
The chemistry of this functional group is
quite unique, versatile and different
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 Bonding in a carbonyl group
Let us examine the bonding in a carbonyl
group:

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 Many important differences...
While they appear to be similar, there are
many important differences;
These differences make the chemistry of the
carbonyl group the cornerstone of synthetic
(organic) chemistry
Much of our ability to make new molecules
depends on the manipulation of carbonyl
groups because they allow us to make
carbon-carbon bonds

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 Aldehydes and ketones
This bond is a very polar bond due to the
differences in electronegative values of the
carbon and the oxygen
It is due to the unsymmetrical distribution of
electrons in this bond that carbonyl
compounds are quite reactive to electron-
rich species, i.e. nucleophiles

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 Nomenclature
The IUPAC system for naming aldehydes and
ketones follows a similar pattern of selecting
the longest continuous chain containing the
carbonyl group as its parent compound
In aldehydes, the carbonyl carbon will
assume position number 1 on the carbon
chain and the substituents are numbered
relative to the position of the carbonyl group
on the chain

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 Nomenclature
Because the carbonyl carbon is at the
beginning of the chain, there is no need to
use a number to locate it
The name of the aldehyde is obtained by
changing the suffix “–e” of the parent alkane
to “–al”, such as methanal, ethanal, propanal
For unsaturated aldehydes, the presence of a
carbon-carbon double bond is indicated by
the infix “–en–”
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 Nomenclature
As with other molecules with both an infix
and suffix, the location of the suffix
determines the numbering pattern

For monocyclic molecules in which the –CHO

is attached directly to the ring, the molecule
is named by adding the suffix –carbaldehyde
to the name of the ring
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 Nomenclature

Ketones are named by selecting the longest

continuous chain containing the carbonyl
group as the parent compounds and then
indicating its presence by changing the suffix
from “ –e” to “–one”
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 Nomenclature
The parent chain is numbered from the
direction that gives the carbonyl group the
smaller number

All other substituents on the chain or ring are

numbered with respect to the position of the
carbonyl group and as this group is not at the
end of the chain, a number is used to indicate
its location on the chain or the ring system 16
Nomenclature

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 Nomenclature
There are many compounds that have several
functional groups on them and naming them
can be a very confusing and problematic
exercise
When naming these compounds, use the
table below to help with identifying the
parent compound
The table contains the order of precedence of
functional groups to deduce the name
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 Nomenclature
Functional group Suffix if higher in Prefix if lower in
precedence precedence
–COOH –oic acid –

–CHO –al oxo–

O
–one oxo–

–OH –ol hydroxy–

–NH2 –amine amino–

–SH –thiol mercapto–

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 Nomenclature
Take the following examples:

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Reactions of aldehydes and ketones
Aldehydes and ketones undergo a number of
reactions that are based around the very
polar bond – the carbonyl group
The basis of all these reactions is governed by
the unsymmetrical distribution of electrons
in this bond that carbonyl compounds are
quite reactive to electron-rich species, i.e.
nucleophiles
This is because of the difference in electro-
negativities of the oxygen and carbon
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Recall – Example of alkene reaction...
Addition of HCl to ethene

Addition of H2O to ethene

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Resonance of the carbonyl group...
In resonance terms, the carbonyl group can
be described as a combination of the two
major contributing forms...

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Reactivity of the carbonyl group...
There are several centres of reactivity in a
molecule containing a carbon-oxygen double
bond
This versatility contributes to the widespread
use of carbonyl compounds in synthesis
There is the p-bond itself (don’t forget the
anti-bonding p* orbital) and the lone pair of
electrons on the oxygen

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 Polarisable p-bond...
As shown, the carbonyl group has an easily
polarisable p-bond with an electrophilic
carbon atom at one end that is easily
attacked by nucleophiles
In addition to the electrophilic carbon centre
of the carbonyl group, there is a special
reactivity associated with the carbon-
hydrogen bonds in the position adjacent (a)
to the carbon-oxygen double bond

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 Positions on a carbon chain...
Other positions in a molecule in relation to
the carbonyl group may be referred to by
Greek letters
The carbon adjacent to the C=O group is
called the alpha (a) carbon. The next carbon
is beta (b), then gamma (g), delta (d) and so
forth.
The groups (or atoms) attached to an a
carbon are called a groups, those on b carbon
are b groups etc.
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Positions on a carbon chain...

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Reactions of aldehydes and ketones
For this course we will concentrate on the
reaction that takes place at the electrophilic
carbonyl carbon atom
The most common reaction these
compounds undergo is addition reactions of
nucleophiles to form a tetrahedral carbonyl
addition intermediate
 The following represents a general reaction
showing the addition of the nucleophile to
the electrophilic carbonyl carbon
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Reactions of aldehydes and ketones

 The following represents a general reaction

showing the addition of the nucleophile to
the electrophilic carbonyl carbon
From a synthetic viewpoint, the addition of
carbon nucleophiles is the most important
type of nucleophile addition to the C=O
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Reactions of aldehydes and ketones
This is because these reactions form new
carbon-carbon bonds which mean that the
molecule can be made larger
The main carbon nucleophile discussed here
is the Grignard reagent (R-MgX)
When Grignard reagents are added to
aldehydes, secondary alcohols are formed
upon acidification of the tetrahedral
intermediate

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Reactions of aldehydes and ketones

When ketones are reacted with Grignard

reagents, tertiary alcohols are formed upon
acidification of the tetrahedral intermediate

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Reactions of aldehydes and ketones
When methanal is reacted with Grignard
reagents, primary alcohols are formed upon
acidification of the tetrahedral intermediate

Another useful reaction is the addition of

oxygen nucleophiles to the electrophilic
carbonyl carbon to form several products
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Reactions of aldehydes and ketones
The main source of oxygen nucleophiles is the
alcohol
When a molecule of alcohol is added to the
carbonyl group of an aldehyde or ketone, a
hemiacetal is formed

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Reactions of aldehydes and ketones
The functional group of a hemiacetal is a
carbon atom vicinally bonded to a –OH and an
–OR or –OAr group

These hemiacetals are relatively unstable and

can react further to produce acetals plus a
molecule of water. These reactions are
generally acid-catalyzed
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Reactions of aldehydes and ketones

As with hemiacetals, the functional group of

an acetal is a carbon atom bonded vicinally to
two –OR or –OAr groups

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Reactions of aldehydes and ketones
Addition of nitrogen nucleophiles
Ammonia (NH3), primary aliphatic amine (R-
NH2) and primary aromatic amines (Ar-NH2)
react with the carbonyl group of aldehydes
and ketones in the presence of an acid
catalyst to give a product containing a
carbon-nitrogen (C=N) double bond
These compounds are called imines

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Reactions of aldehydes and ketones

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Synthesis of aldehydes and ketones
The most common way of preparing
aldehydes and ketones is through the
oxidation of alcohols
When primary alcohols are oxidized, they are
initially converted to aldehydes and then on
to carboxylic acids

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Synthesis of aldehydes and ketones
But when secondary alcohols are oxidized,
they are converted to ketones only
Further oxidation of the ketone involves the
cleavage of the carbon-carbon bond to yield a
carboxylic acid

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Synthesis of aldehydes and ketones
When attempting to prepare an aldehyde
from a primary alcohol by oxidation, it is not
a very good strategy to use chromic acid
(H2CrO4), potassium dichromate (K2Cr2O7),
and potassium permanganate (KMnO4)
This is because the oxidation conditions do
not allow for the reaction to stop at the
aldehyde stage
It always over-oxidizes it to the carboxylic
acid stage
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Synthesis of aldehydes and ketones
A milder variant of the chromium-based
oxidant, which selectively oxidizes primary
alcohols to aldehydes is called pyridinium
chlorochromate (PCC)

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Synthesis of aldehydes and ketones
When used in the oxidation of primary
alcohols like ethanol, it will stop only at the
aldehyde stage and not over-oxidize to the
carboxylic acid stage

PCC can also be used to oxidize secondary

alcohols to the ketone stage
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