ALDEHYDES AND KETONES

Assoc. Prof. Lubomir Makedonski,PhD

Medical University of Varna

Aldehydes and ketones as carbonyl compounds

Aldehydes and ketones are simple compounds which contain a carbonyl group - a
carbon-oxygen double bond. 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 - as you might find, for example, in carboxylic acids containing -
COOH.

Examples of 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.

Notice that these all have exactly the same end to the molecule. All that differs is
the complexity of the other group attached.

The name counts the total number of carbon atoms in the longest chain -
including the one in the carbonyl group. If you have side groups attached to the
chain, notice that you always count from the carbon atom in the carbonyl group
as being number 1

Names

Aldehydes

All aldehydes contain the group:

The names of aldehydes end in al.

Examples of ketones

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In ketones, the carbonyl group has two hydrocarbon groups attached . Again,
these can be either alkyl groups or ones containing benzene rings. Again, we'll
concentrated on those containing alkyl groups just to keep things simple.

Notice that ketones never have a hydrogen atom attached to the carbonyl group.

Propanone is normally written CH3COCH3. Notice the need for numbering in the
longer ketones. In pentanone, the carbonyl group could be in the middle of the
chain or next to the end - giving either pentan-3-one or pentan-2-one.

Names

Ketones

Ketones contain a carbon-oxygen double bond just like aldehydes, but this time
it's in the middle of a carbon chain. There isn't a hydrogen atom attached to the
group as there is in aldehydes.

Ketones are shown by the ending one.

Bonding and reactivity

Bonding in the carbonyl group

Oxygen is far more electronegative than carbon and so has a strong tendency to
pull electrons in a carbon-oxygen bond towards itself. One of the two pairs of
electrons that make up a carbon-oxygen double bond is even more easily pulled
towards the oxygen. That makes the carbon-oxygen double bond very highly
polar.

Important reactions of the carbonyl group

The slightly positive carbon atom in the carbonyl group can be attacked by
nucleophiles. A nucleophile is a negatively charged ion (for example, a cyanide
ion, CN-), or a slightly negatively charged part of a molecule (for example, the
lone pair on a nitrogen atom in ammonia, NH3).

During the reaction, the carbon-oxygen double bond gets broken. The net effect
of all this is that the carbonyl group undergoes addition reactions, often followed
by the loss of a water molecule. This gives a reaction known as addition-
elimination or condensation

Where aldehydes and ketones differ

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An aldehyde differs from a ketone by having a hydrogen atom attached to the
carbonyl group. This makes the aldehydes very easy to oxidizes

For example, ethanal, CH3CHO, is very easily oxidized to either ethanoic acid,
CH3COOH, or ethanoate ions, CH3COO-.

Ketones don't have that hydrogen atom and are resistant to oxidation. They are
only oxidised by powerful oxidising agents which have the ability to break
carbon-carbon bonds.

Physical properties

Boiling points

Methanal is a gas (boiling point -21°C), and ethanal has a boiling point of +21°C.
That means that ethanal boils at close to room temperature.

The other aldehydes and the ketones are liquids, with boiling points rising as the
molecules get bigger.

The size of the boiling point is governed by the strengths of the intermolecular
forces.

Solubility in water

The small aldehydes and ketones are freely soluble in water but solubility falls
with chain length. For example, methanal, ethanal and propanone - the common
small aldehydes and ketones - are miscible with water in all proportions.

The reason for the solubility is that although aldehydes and ketones can't
hydrogen bond with themselves, they can hydrogen bond with water molecules.

One of the slightly positive hydrogen atoms in a water molecule can be

sufficiently attracted to one of the lone pairs on the oxygen atom of an aldehyde
or ketone for a hydrogen bond to be formed.

There will also, of course, be dispersion forces and dipole-dipole attractions

between the aldehyde or ketone and the water molecules.

Forming these attractions releases energy which helps to supply the energy
needed to separate the water molecules and aldehyde or ketone molecules from
each other before they can mix together.

As chain lengths increase, the hydrocarbon "tails" of the molecules (all the
hydrocarbon bits apart from the carbonyl group) start to get in the way.

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By forcing themselves between water molecules, they break the relatively strong
hydrogen bonds between water molecules without replacing them by anything as
good. This makes the process energetically less profitable, and so solubility
decreases.

MAKING ALDEHYDES AND KETONES

Oxidising alcohols to make aldehydes and ketones

If you now think about where they are coming from, you will get an aldehyde if
your starting molecule looks like this:

In other words, if you start from a primary alcohol, you will get an aldehyde.

You will get a ketone if your starting molecule looks like this:

. . . where R and R' are both alkyl groups.

Secondary alcohols oxidise to give ketones.

Making aldehydes

Aldehydes are made by oxidising primary alcohols. There is, however, a problem.

The aldehyde produced can be oxidised further to a carboxylic acid by the

acidified potassium dichromate(VI) solution used as the oxidising agent. In order
to stop at the aldehyde, you have to prevent this from happening.

To stop the oxidation at the aldehyde, you . . .

 use an excess of the alcohol. That means that there isn't enough oxidising
agent present to carry out the second stage and oxidise the aldehyde
formed to a carboxylic acid.
 distil off the aldehyde as soon as it forms. Removing the aldehyde as soon
as it is formed means that it doesn't stay in the mixture to be oxidised
further.

 If you used ethanol as a typical primary alcohol, you would produce the
aldehyde ethanal, CH3CHO.

The full equation for this reaction is fairly complicated, and you need to
understand about electron-half-equations in order to work it out.

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 Secondary alcohols

Secondary alcohols are oxidised to ketones. There is no further reaction which

might complicate things. For example, if you heat the secondary alcohol propan-
2-ol with sodium or potassium dichromate(VI) solution acidified with dilute
sulphuric acid, you get propanone formed.

Playing around with the reaction conditions makes no difference whatsoever to

the product.

Using the simple version of the equation:

SIMPLE ADDITION TO ALDEHYDES AND KETONES

This page looks at the addition of hydrogen cyanide and sodium hydrogensulphite
(sodium bisulphite) to aldehydes and ketones.

Addition of hydrogen cyanide to aldehydes and ketones

The reactions

Hydrogen cyanide adds across the carbon-oxygen double bond in aldehydes and
ketones to produce compounds known as hydroxynitriles. These used to be
known as cyanohydrins.

For example, with ethanal (an aldehyde) you get 2-hydroxypropanenitrile:

With propanone (a ketone) you get 2-hydroxy-2-methylpropanenitrile:

The reaction isn't normally done using hydrogen cyanide itself, because this is an
extremely poisonous gas. Instead, the aldehyde or ketone is mixed with a
solution of sodium or potassium cyanide in water to which a little sulphuric acid
has been added. The pH of the solution is adjusted to about 4 - 5, because this
gives the fastest reaction. The reaction happens at room temperature.

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The solution will contain hydrogen cyanide (from the reaction between the
sodium or potassium cyanide and the sulphuric acid), but still contains some free
cyanide ions. This is important for the mechanism.

THE NUCLEOPHILIC ADDITION OF HYDROGEN CYANIDE TO ALDEHYDES AND

KETONES

This page gives you the facts and simple, uncluttered mechanisms for the
nucleophilic addition reactions between carbonyl compounds (specifically
aldehydes and ketones) and hydrogen cyanide, HCN. If you want the mechanisms
explained to you in detail, there is a link at the bottom of the page.

Aldehydes and ketones behave identically in their reaction with hydrogen

cyanide, and so will be considered together - although equations and mechanisms
will be given for both types of compounds for the sake of completeness.

The reaction of aldehydes and ketones with hydrogen cyanide

The facts

Hydrogen cyanide adds across the carbon-oxygen double bond in aldehydes and
ketones to produce compounds known as hydroxynitriles.

For example, with ethanal (an aldehyde) you get 2-hydroxypropanenitrile:

With propanone (a ketone) you get 2-hydroxy-2-methylpropanenitrile:

The reaction isn't normally done using hydrogen cyanide itself, because this is an
extremely poisonous gas. Instead, the aldehyde or ketone is mixed with a
solution of sodium or potassium cyanide in water to which a little sulphuric acid
has been added. The pH of the solution is adjusted to about 4 - 5, because this
gives the fastest reaction.

The solution will contain hydrogen cyanide (from the reaction between the
sodium or potassium cyanide and the sulphuric acid), but still contains some free
cyanide ions. This is important for the mechanism.

The mechanisms

These are examples of nucleophilic addition.

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The carbon-oxygen double bond is highly polar, and the slightly positive carbon
atom is attacked by the cyanide ion acting as a nucleophile.

The mechanism for the addition of HCN to propanone

In the first stage, there is a nucleophilic attack by the cyanide ion on the slightly
positive carbon atom.

The negative ion formed then picks up a hydrogen ion from somewhere - for
example, from a hydrogen cyanide molecule.

The hydrogen ion could also come from the water or the H3O+ ions present in the
slightly acidic solution. You don't need to remember all of these. One equation is
perfectly adequate.

Uses of the reaction

The product molecules contain two functional groups:

 the -OH group which behaves like a simple alcohol and can be replaced by
other things like chlorine, which can in turn be replaced to give, for
example, an -NH2 group;

 the -CN group which is easily converted into a carboxylic acid group -COOH.

For example, starting from a hydroxynitrile made from an aldehyde, you can quite
easily produce relatively complicated molecules like 2-amino acids - the amino
acids which are used to construct proteins.

Addition of sodium hydrogensulphite to aldehydes and ketones

Sodium hydrogensulphite used to be known as sodium bisulphite, and you might

well still come across it in organic textbooks under this name - or using the
bisulfite spelling.

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The reactions

This reaction only works well for aldehydes. In the case of ketones, one of the
hydrocarbon groups attached to the carbonyl group needs to be a methyl group.
Bulky groups attached to the carbonyl group get in the way of the reaction
happening.

The aldehyde or ketone is shaken with a saturated solution of sodium

hydrogensulphite in water. Where the product is formed, it separates as white
crystals.

In the case of ethanal, the equation is:

. . . and with propanone, the equation is:

These compounds are rarely named systematically, and are usually known as
"hydrogensulphite (or bisulphite) addition compounds".

Uses of the reaction

The reaction is usually used during the purification of aldehydes (and any ketones
that it works for). The addition compound can be split easily to regenerate the
aldehyde or ketone by treating it with either dilute acid or dilute alkali.

If you have an impure aldehyde, for example, you could shake it with a saturated
solution of sodium hydrogensulphite to produce the crystals. These crystals could
easily be filtered and washed to remove any other impurities. Addition of dilute
acid, for example, would then regenerate the original aldehyde.

It would, of course, still need to be separated from the excess acid and assorted
inorganic products of the reaction - but that is beyond the scope of this page!

REDUCTION OF ALDEHYDES AND KETONES

The reducing agents

Despite the fearsome names, the structures of the two reducing agents are very
simple. In each case, there are four hydrogens ("tetrahydido") around either
aluminium or boron in a negative ion (shown by the "ate" ending).

The "(III)" shows the oxidation state of the aluminium or boron, and is often left
out because these elements only ever show the +3 oxidation state in their

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compounds. To make the names shorter, that's what I shall do for the rest of this
page.

The formulae of the two compounds are LiAlH4 and NaBH4.

Their structures are:

In each of the negative ions, one of the bonds is a co-ordinate covalent (dative
covalent) bond using the lone pair on a hydride ion (H-) to form a bond with an
empty orbital on the aluminium or boron.

The overall reactions

The reduction of an aldehyde

You get exactly the same organic product whether you use lithium
tetrahydridoaluminate or sodium tetrahydridoborate.

For example, with ethanal you get ethanol:

Notice that this is a simplified equation - perfectly acceptable to UK A level

examiners. [H] means "hydrogen from a reducing agent".

In general terms, reduction of an aldehyde leads to a primary alcohol.

The reduction of a ketone

Again the product is the same whichever of the two reducing agents you use.

For example, with propanone you get propan-2-ol:

Reduction of a ketone leads to a secondary alcohol.

OXIDATION OF ALDEHYDES AND KETONES

Why do aldehydes and ketones behave differently?

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You will remember that the difference between an aldehyde and a ketone is the
presence of a hydrogen atom attached to the carbon-oxygen double bond in the
aldehyde. Ketones don't have that hydrogen.

The presence of that hydrogen atom makes aldehydes very easy to oxidise. Or,
put another way, they are strong reducing agents.

Because ketones don't have that particular hydrogen atom, they are resistant to
oxidation. Only very strong oxidising agents like potassium manganate(VII)
solution (potassium permanganate solution) oxidise ketones - and they do it in a
destructive way, breaking carbon-carbon bonds.

Provided you avoid using these powerful oxidising agents, you can easily tell the
difference between an aldehyde and a ketone. Aldehydes are easily oxidised by
all sorts of different oxidising agents: ketones aren't.

What is formed when aldehydes are oxidised?

It depends on whether the reaction is done under acidic or alkaline conditions.

Under acidic conditions, the aldehyde is oxidised to a carboxylic acid. Under
alkaline conditions, this couldn't form because it would react with the alkali. A
salt is formed instead.

Building equations for the oxidation reactions

If you need to work out the equations for these reactions, the only reliable way of
building them is to use electron-half-equations.

The half-equation for the oxidation of the aldehyde obviously varies depending on
whether you are doing the reaction under acidic or alkaline conditions.

Under acidic conditions it is:

. . . and under alkaline conditions:

These half-equations are then combined with the half-equations from whatever
oxidising agent you are using. Examples are given in detail below.

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Specific examples

In each of the following examples, we are assuming that you know that you have
either an aldehyde or a ketone. There are lots of other things which could also
give positive results.

Assuming that you know it has to be one or the other, in each case, a ketone
does nothing. Only an aldehyde gives a positive result.

Using acidified potassium dichromate(VI) solution

A small amount of potassium dichromate(VI) solution is acidified with dilute

sulphuric acid and a few drops of the aldehyde or ketone are added. If nothing
happens in the cold, the mixture is warmed gently for a couple of minutes - for
example, in a beaker of hot water.

The orange dichromate(VI) ions have been reduced to green chromium(III) ions by
the aldehyde. In turn the aldehyde is oxidised to the corresponding carboxylic
acid.

The electron-half-equation for the reduction of dichromate(VI) ions is:

Combining that with the half-equation for the oxidation of an aldehyde under
acidic conditions:

. . . gives the overall equation:

Using Tollens' reagent (the silver mirror test)

Tollens' reagent contains the diamminesilver(I) ion, [Ag(NH 3)2]+.

This is made from silver(I) nitrate solution. You add a drop of sodium hydroxide
solution to give a precipitate of silver(I) oxide, and then add just enough dilute
ammonia solution to redissolve the precipitate.

To carry out the test, you add a few drops of the aldehyde or ketone to the freshly
prepared reagent, and warm gently in a hot water bath for a few minutes.

Aldehydes reduce the diamminesilver(I) ion to metallic silver. Because the

solution is alkaline, the aldehyde itself is oxidised to a salt of the corresponding
carboxylic acid.

The electron-half-equation for the reduction of of the diamminesilver(I) ions to

silver is:
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Combining that with the half-equation for the oxidation of an aldehyde under
alkaline conditions:

. . . gives the overall equation:

Using Fehling's solution or Benedict's solution

Fehling's solution and Benedict's solution are variants of essentially the same
thing. Both contain complexed copper(II) ions in an alkaline solution.

Fehling's solution contains copper(II) ions complexed with tartrate ions in sodium
hydroxide solution. Complexing the copper(II) ions with tartrate ions prevents
precipitation of copper(II) hydroxide.

Benedict's solution contains copper(II) ions complexed with citrate ions in

sodium carbonate solution. Again, complexing the copper(II) ions prevents the
formation of a precipitate - this time of copper(II) carbonate.

Both solutions are used in the same way. A few drops of the aldehyde or ketone
are added to the reagent, and the mixture is warmed gently in a hot water bath
for a few minutes.

Aldehydes reduce the complexed copper(II) ion to copper(I) oxide. Because the
solution is alkaline, the aldehyde itself is oxidised to a salt of the corresponding
carboxylic acid.

The equations for these reactions are always simplified to avoid having to write
in the formulae for the tartrate or citrate ions in the copper complexes. The
electron-half-equations for both Fehling's solution and Benedict's solution can be
written as:

Combining that with the half-equation for the oxidation of an aldehyde under
alkaline conditions:

. . . gives the overall equation:

ADDITION-ELIMINATION REACTIONS OF ALDEHYDES AND KETONES

The reaction with 2,4-dinitrophenylhydrazine

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2,4-dinitrophenylhydrazine is often abbreviated to 2,4-DNP or 2,4-DNPH. A solution
of 2,4-dinitrophenylhydrazine in a mixture of methanol and sulphuric acid is
known as Brady's reagent.

What is 2,4-dinitrophenylhydrazine?

Although the name sounds complicated, and the structure looks quite
complicated, it is actually very easy to work out.

Start with the formula of hydrazine. That's almost all you need to remember!

Hydrazine is:

In phenylhydrazine, one of the hydrogens is replaced by a phenyl group, C 6H5. This

is based on a benzene ring.

attached to the phenyl group in the 2- and 4- positions. The corner with the
nitrogen attached is counted as the number 1 position, and you just number
clockwise around the ring.

Doing the reaction

Details vary slightly depending on the nature of the aldehyde or ketone, and the
solvent that the 2,4-dinitrophenylhydrazine is dissolved in. Assuming you are
using Brady's reagent (a solution of the 2,4-dinitrophenylhydrazine in methanol
and sulphuric acid):

Add either a few drops of the aldehyde or ketone, or possibly a solution of the
aldehyde or ketone in methanol, to the Brady's reagent. A bright orange or yellow
precipitate shows the presence of the carbon-oxygen double bond in an aldehyde
or ketone.

This is the simplest test for an aldehyde or ketone.

The chemistry of the reaction

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The overall reaction is given by the equation:

R and R' can be any combination of hydrogen or hydrocarbon groups (such as

alkyl groups). If at least one of them is a hydrogen, then the original compound is
an aldehyde. If both are hydrocarbon groups, then it is a ketone.

Look carefully at what has happened.

Provided you take care to draw the two starting molecules lined up right, working
out the structure of the product is easy.

The product is known as a "2,4-dinitrophenylhydrazone". Notice that all that has

changed is the ending from "-ine" to "-one". That's possibly confusing!

The product from the reaction with ethanal would be called ethanal 2,4-
dinitrophenylhydrazone; from propanone, you would get propanone 2,4-
dinitrophenylhydrazone - and so on. That's not too difficult!

The reaction is known as a condensation reaction. A condensation reaction is

one in which two molecules join together with the loss of a small molecule in the
process. In this case, that small molecule is water.

In terms of mechanisms, this is a nucleophilic addition-elimination reaction. The

2,4-dinitrophenylhydrazine first adds across the carbon-oxygen double bond (the
addition stage) to give an intermediate compound which then loses a molecule of
water (the elimination stage).

Using the reaction

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The reaction has two uses in testing for aldehydes and ketones.

 First, you can just use it to test for the presence of the carbon-oxygen
double bond. You only get an orange or yellow precipitate from a carbon-
oxygen double bond in an aldehyde or ketone.
 Secondly, you can use it to help to identify the specific aldehyde or ketone.

The precipitate is filtered and washed with, for example, methanol and then
recrystallised from a suitable solvent which will vary depending on the
nature of the aldehyde or ketone. For example, you can recrystallise the
products from the small aldehydes and ketones from a mixture of ethanol
and water.

The crystals are dissolved in the minimum quantity of hot solvent. When the
solution cools, the crystals are re-precipitated and can be filtered, washed
with a small amount of solvent and dried. They should then be pure.

If you then find the melting point of the crystals, you can compare it with
tables of the melting points of 2,4-dinitrophenylhydrazones of all the
common aldehydes and ketones to find out which one you are likely to have
got.

Some other similar reactions

If you go back and look at the equations, nothing in the 2,4-

dinitrophenylhydrazine changes during the reaction apart from the -NH 2 group.
You can get a similar reaction if the -NH2 group is attached to other things.

In each case, the reaction would look like this:

In what follows, all that changes is the nature of the "X".

with hydrazine

The product is a "hydrazone". If you started from propanone, it would be

propanone hydrazone.

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