CHEMISTRY A2, Chapter 12.

Compounds containing the carbonyl group (as

well as carboxylic acids, carboxylate salts, esters, acyl chlorides and acid
anhydrides ).
By the end of this topic you will be able to :

recognise and name the carbonyl compounds that are aldehydes aand
ketones.

describe the reagents and condititions for the reactions of carbonyl

compounds with NaBH4 or Li AlH4 and HCN.

understand and describe the mechanism for nucleophilic addition
reactions.
Explain the use of 2,4- dintrophenyl hydrazine and Tollens' reagent or
Fehling's solution, and the tri-iodomethane reaction, to characterise and
identify carbonyl compounds.

Dr.A.Matovu

COMPOUNDS CONTAINING THE CARBONYL GROUP

Aldehydes and Ketones, Mechanism of nucleophilic addition

Dr.A.Matovu

ALDEHYDES AND KETONES

1.

Introduction

Aldehydes and ketones are collectively known as carbonyls and represented by the general formula
CnH2nO. They have the following functional group:
O
C

In aldehydes one of the groups attached to the carbon is a hydrogen atom and the other is
a hydrogen atom or an alkyl groups. In ketones both of the groups attached to the carbon are alkyl
groups:

O
H

CH3

ethanal

methanal

butanone

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butanal

pentan-2-one

2.

Redox reactions

The redox reactions involving carbonyls have been discussed at AS level and are summarized by
the following diagram:
secondary
alcohols

primary
alcohols
[O]

aldehydes
[O]

[O]
[R]

[R]

tertiary
alcohols
X

ketones
X

carboxylic
acids

a) oxidation reactions
Carbonyls are formed by the oxidation of alcohols.
Partial oxidation of a primary alcohol results in the formation of an aldehyde.
Oxidation of a secondary alcohol results in the formation of a ketone.
Primary alcohols, secondary alcohols and aldehydes are oxidized using potassium dichromate
(K2Cr2O7) in sulphuric acid (H2SO4). Gentle warming is necessary to start the reaction.
When making an aldehyde, care must be taken to prevent further oxidation to the carboxylic acid.
This is achieved by using distillation apparatus so that the aldehyde can be distilled off as soon as it
is formed.
The orange Cr2O72- is reduced to the green Cr3+.

Dr.A.Matovu

Simplified equations for these oxidation reactions can be written using the symbol [O] as the
oxidant:
Primary alcohol aldehyde
R-CH2OH + [O] R-CHO + H2O
Secondary alcohol ketone
R1-CH(OH)-R2 + [O] R1-CO-R2 + H2O
Aldehyde carboxylic acid
R-CHO + [O] R-COOH
The most important difference in the reactions of aldehydes and ketones is the fact that aldehydes
can be readily oxidized to carboxylic acids but ketones are not readily oxidized. This is used as the
basis for two important distinguishing tests between aldehydes and ketones.
Ammoniacal silver nitrate, [Ag(NH3)2]+, is known as Tollen's reagent. It is a mild oxidising agent:
[Ag(NH3)2]+(aq) + e Ag(s) + 2NH3(aq)
It can be reduced by aldehydes, oxidising them to carboxylic acids:
R-CHO + H2O RCOOH + 2H+(aq) + 2e
The overall equation for the reaction is:
R-CHO + 2[Ag(NH3)2]+ + H2O RCOOH + 2Ag + 4NH3 + 2H+
Thus aldehydes give a grey precipitate or "silver mirror" if boiled with ammoniacal silver nitrate.
This is a standard test for an aldehyde, since ketones cannot be oxidised in this way.
Fehlings solution is an alkaline solution containing Cu2+ ions. It is a mild oxidizing agent:
2Cu2+ + 2e + 2OH- Cu2O + H2O
It is also reduced by aldehydes, and the overall equation for the reaction is:
R-CHO + 4OH- + 2Cu2+ R-COOH + Cu2O + 2H2O
The blue Cu2+ is reduced to the brick-red precipitate Cu2O on gentle warming. This is another
standard test for an aldehyde.

Dr.A.Matovu

b)

reduction reactions

Aldehydes and ketones can be reduced to primary and secondary alcohols respectively using the
reducing agent sodium tetrahydroborate (III), NaBH4.
Simplified equations for these reduction reactions can be written using the symbol [H] as the
reductant:
Aldehyde primary alcohol
R-CHO + 2[H] R-CH2OH
Ketone Secondary alcohol
R1-CO-R2 + 2[H] R1-CH(OH)-R2
Carboxylic acids cannot be reduced using NaBH4 but can be reduced to primary alcohols using the
stronger reducing agent LiAlH4.
R and R' can be any combination of hydrogen or alkyl groups.

The product is then treated with a dilute acid (such as dilute sulphuric acid or dilute hydrochloric
acid) to release the alcohol from the complex ion.

The alcohol formed can be recovered from the mixture by fractional distillation.
Using sodium tetrahydridoborate (sodium borohydride)
Sodium tetrahydridoborate is a more gentle (and therefore safer) reagent than lithium
tetrahydridoaluminate. It can be used in solution in alcohols or even solution in water - provided the
solution is alkaline.
Solid sodium tetrahydridoborate is added to a solution of the aldehyde or ketone in an alcohol
such as methanol, ethanol or propan-2-ol. Depending on which recipe you read, it is either heated
under reflux or left for some time around room temperature. This almost certainly varies depending
on the nature of the aldehyde or ketone.
At the end of this time, a complex similar to the previous one is formed.

In the second stage of the reaction, water is added and the mixture is boiled to release the alcohol
from the complex.
Dr.A.Matovu

Again, the alcohol formed can be recovered from the mixture by fractional distillation.
REDUCTION OF ALDEHYDE AND KETONES.
Only one UK A level Exam Board (AQA) is likely to ask for these mechanisms, and they
are happy with a simplified version of what is quite a complex mechanism. Because of that
simplification, these reactions are dealt with entirely on this page - without the "talk
through" page that you will find for other mechanisms on this site.

The reduction of aldehydes and ketones by sodium tetrahydridoborate

The facts
Sodium tetrahydridoborate (previously known as sodium borohydride) has the formula NaBH4, and
contains the BH4- ion. That ion acts as the reducing agent.
The reduction of an aldehyde
For example, with ethanal you get ethanol:

Notice that this is a simplified equation - perfectly acceptable to examiners. The H in square
brackets means "hydrogen from a reducing agent".
In general terms, reduction of an aldehyde leads to a primary alcohol. A primary alcohol is one
which only has one alkyl group attached to the carbon with the -OH group on it. They all contain
the grouping -CH2OH.
Note: There is one exception to this. Methanol CH3OH is also a primary alcohol. Think of this
as H-CH2OH.

The reduction of a ketone

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

Dr.A.Matovu

Reduction of a ketone leads to a secondary alcohol. A secondary alcohol is one which has two
alkyl groups attached to the carbon with the -OH group on it. They all contain the grouping
-CHOH.

Beware! The following mechanisms are simplified for UK A level

purposes to the point that they are wrong! If you are working outside the
UK A level system, please don't read any further!
The simplified mechanisms
The BH4- ion is essentially a source of hydride ions, H-. The simplification used is to
write H- instead of BH4-.
Doing this not only makes the initial attack easier to write, but avoids you getting
involved with some quite complicated boron compounds that are formed as
intermediates.
The reduction is an example of nucleophilic addition.
The carbon-oxygen double bond is highly polar, and the slightly
positive carbon atom is attacked by the hydride ion acting as a
nucleophile. A hydride ion is a hydrogen atom with an extra
electron - hence the lone pair.

The mechanism for the reduction of ethanal

In the first stage, there is a nucleophilic attack by the hydride ion on the slightly positive carbon
atom. The lone pair of electrons on the hydride ion forms a bond with the carbon, and the electrons
in one of the carbon-oxygen bonds are repelled entirely onto the oxygen, giving it a negative
charge.

What happens now depends on whether you add an acid or water to complete the reaction.
Adding an acid:

Dr.A.Matovu

When the acid is added, the negative ion formed picks up a hydrogen ion to give an alcohol.

Note: You may find that other sources write the hydrogen ion simply as H+.
That's not good practice, because it suggests a free hydrogen ion. The hydrogen
ion is actually attached to a water molecule as H3O+. Writing that makes the
equation look more complicated. H+(aq) is a happy compromise.
Adding water:
This time, the negative ion takes a hydrogen ion from a water molecule.

The mechanism for the reduction of propanone

As before, the reaction starts with a nucleophilic attack by the hydride ion on the slightly positive
carbon atom.

Again, what happens next depends on whether you add an acid or water to complete the reaction.
Adding an acid:
The negative ion reacts with a hydrogen ion from the acid added in the second stage of the
reaction.

Adding water:

Dr.A.Matovu

This time, the negative ion takes a hydrogen ion from a water molecule.

Important!
Remember that the equations and mechanisms given on this page are not the truth - they are
merely simplifications to suit the demands of a particular A level syllabus.

3.

Nucleophilic addition

Carbonyls are unsaturated and can thus undergo addition reactions.

The C=O bond is polar so the carbon is a positive centre. Thus carbonyls can react with
nucleophiles:
-

O
+
C

Nu:
Carbonyls therefore tend to undergo nucleophilic addition.

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10

Mechanism of nucleophilic addition:

Example 1: addition of HCN to make hydroxynitriles
NB

HCN is a very poisonous gas. It is not safe to carry out this reaction in the laboratory.
HCN is not stored, but made in situ by mixing KCN and HCl.
KCN is also very poisonous but it is safer to store as it is a solid.

Hydrogen cyanide, HCN, is a nucleophile. It reacts with carbonyls as follows:

R1-CO-R2 + HCN R1-C(CN)(OH)-R2
OH

R1

HCN

R1

R2

R2

CN

HCN is a very toxic gas, so is generated in situ:

KCN(s) + HCl(aq) HCN(g) + KCl(aq)
The mechanism consists of three steps:
Step 1: the HCN is a weak acid and dissociates:
HCN H+ + CNThe CN- behaves as a nucleophile.
Step 2: The nucleophile attacks the carbonyl:
+
R1

R2
:CN-

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11

Step 3: The O atom picks up the H+ ion:

H

..

OC

R2

CN

R1

Eg propanal + HCN 2-hydoxybutanenitrile

+

CN

CH3CH2

C
CH3CH2

OH

H+

..-

CH3CH2

CN

CN

H
H

:CN-

Example 2: reduction by NaBH4 to make alcohols

The reduction of aldehydes and ketones as described above is another example of a nucleophilic
addition reaction.
R1-CO-R2 + 2[H] R1-CH(OH)-R2
OH

R1

R1

2[H]

R2

R2

NaBH4 contains hydrogen in a negative oxidation state, which can therefore behave as a
nucleophile.
Step 1: the H- ion attacks the + carbon atom:
-

O-

O
+

R1

H:

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R2

R2

R1

12

Step 2: the O- pulls a H atom off a water molecule

..-

O
R2

OH

O
R2

OH

R1

R1

eg propanone + 2[H] propan-2-ol

-

..

O
+
CH3

H:

Dr.A.Matovu

CH3
CH3

OC
CH3

OH
CH3

OH

CH3

13

4.

Summary of reactions of aldehydes and ketones

Type of reaction

Mechanism

1. oxidation (aldehydes only): aldehyde carboxylic acid

n/a

reagents: potassium dichromate (K2Cr2O7) in sulphuric acid (H2SO4)

conditions: warm under reflux
equation: R-CHO + [O] R-COOH
observation: orange to green
to distinguish between aldehydes and ketones:
either:
add Fehlings solution and heat
observation: blue solution to brick red precipitate
equation: R-CHO + 4OH- + 2Cu2+ R-COOH + Cu2O + 2H2O
or:
add Tollens reagent and heat
observation: colourless solution to silver mirror
equation: R-CHO + 2[Ag(NH3)2]+ + H2O RCOOH + 2Ag + 4NH3 + 2H+
2. reduction: carbonyl alcohol
reagents: NaBH4(aq)
conditions: room temperature
equation: R1-CO-R2 + 2[H] R1-CH(OH)-R2
3. addition of HCN: carbonyl hydroxynitrile
reagents: KCN and HCl(aq)
conditions: room temperature
equation: R1-CO-R2 + HCN R1-C(CN)(OH)-R2

Dr.A.Matovu

Nucleophilic
addition
(required)

Nucleophilic
addition
(required)

14

CARBOXYLIC ACIDS AND CARBOXYLATE SALTS, ESTERS

ACYL CHLORIDES AND ACID ANHYDRIDES

By the end of this topic you will be able to :

recognise and name carboxylic acids, esters, acid chlorides and amides.
give equations and conditions for the reactions of carboxylicacids with
alcohols, LiAlH4, phosphrous pentachloride, sodium carbonate and
sodium hydrogen carbonate.
describe the hydrolysis of esters in the presence of acids and alkalis
(including the hydrolysis of fats or vegetable oils to make soap and
gycerol.
give equations and conditions for the reactions of acylchlorides and acid
anhydrides with water, alcohol, ammonia and primary amides.
understand the mechanism of the nucleophilic addition-elimination
reactions of acyl chlorides.
Carboxylic acids have the general formula C2H2nO2 and contain the following functional
group:
O
C

OH

Eg

methanoic acid

ethanoic acid
H

O
H

OH

butanoic acid

OH
H

O
C
OH

They can form hydrogen bonds with water, so most carboxylic acids with relatively short
chains are highly soluble in water. They are often less soluble in non-polar solvents.
a)

Reactions of carboxylic acids with bases

Carboxylic acids are weak acids; they dissociate partially in water to form carboxylate (or
alkanoate) salts.
R-COOH(aq) + H2O(l) == RCOO-(aq) + H3O+(aq)
The ability of carboxylic acids to behave as acids is due to the relatively high stability of the
R-COO- anion. These anions are known as carboxylate or alkanoate ions and have the
following structure:
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15

The ion has a delocalised system which accounts for its relatively high stability.
Nevertheless these acids are weak acids and will only dissociate partially in water.
In the presence of stronger bases such as carbonate ions or hydroxide ions, the acid will
dissociate completely:
i)

with sodium hydroxide

Carboxylic acids react with sodium hydroxide to produce the sodium salt and water:
R-COOH(aq) + NaOH(aq) R-COO-Na+(aq) + H2O(l)
Eg ethanoic acid + sodium hydroxide sodium ethanoate + water
H
H

O
C

+
Na OH

OH
H

ii)

C
H

O
C

+
-

+
O Na

H2O

with sodium carbonate

Carboxylic acids react with sodium carbonate to produce the sodium salt, carbon
dioxide and water:
2R-COOH(aq) + Na2CO3(aq) 2R-COO-Na+(aq) + CO2(g) + H2O(l)
eg 2C2H5COOH(aq) + Na2CO3(aq) 2 C2H5COO-Na+(aq) + CO2(g) + H2O(l)
Thus when carboxylic acids are treated with sodium carbonate, a colourless gas is evolved
which turns limewater milky. This is the standard test for a carboxylic acid.
b)

Reaction of carboxylate salts with acids

Since these salts are the salts of weak acids, they have basic properties. Most have a pH of
between 8 and 9:
R-COO-(aq) + H2O(l) == R-COOH(aq) + OH-(aq)
They react completely with strong acids to form the original carboxylic acid:

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16

R-COO-(aq) + H+(aq) R-COOH(aq)

CH3COO-Na+(aq) + HCl(aq) CH3COOH(aq) + NaCl(l)
sodium ethanoate
ethanoic acid

Eg

Carboxylate salts can readily be converted into carboxylic acids by addition of a strong
acid such as hydrochloric acid.
c)

Reaction of carboxylic acids with alcohols

If a carboxylic acid and an alcohol are heated under reflux with concentrated H 2SO4, a
condensation reaction takes place and an ester is formed:
Carboxylic acid + alcohol == ester + H2O
R1-COOH + R2OH == R1-COOR2 + H2O
This reaction is known as esterification. Esterifcation is an example of condensation; a
reaction in which two or more organic molecules join together to form a single large
molecule, and in so doing give off a small molecule such as HCl or H2O.
Eg
ethanoic acid + ethanol
H
H

ethyl ethanoate + water

O

CH3

OH

CH2

CH3

OH

CH2

methanoic acid + propan-2-ol

methylethyl methanoate + water

OH

O
H

C
OH

CH3

CH3

C
O

Dr.A.Matovu

H2O

methyl propanoate + water

O

O
C

+
OH

CH3

H
C

CH

CH3

propanoic acid + methanol

H

H2O

CH3

OH

CH3

CH2

+ H2O

C
O

CH3

17

The H2SO4 acts as a catalyst. The alcohol behaves as a nucleophile, and the lone pair on the
O attacks the positive centre on the carboxylic acid:
O

R1

C
OH

R2

O
H

This reaction is reversible and reaches an equilibrium. The equilibrium constant for the
reaction has a value of approximately 4, indicating that about 70% of the reactants are
converted into products at equilibrium.
d) Reduction of carboxylic acids
This page looks at the reduction of carboxylic acids to primary alcohols using lithium
tetrahydridoaluminate(III) (lithium aluminium hydride), LiAlH4.
The "(III)" is the oxidation state of the aluminium. Since aluminium only ever shows the +3
oxidation state in its compounds, the "(III)" is actually unnecessary.

The reaction
The reducing agent
Lithium tetrahydridoaluminate has the structure:

In the negative ion, 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.

( I refer to the reduction of aldehydes and ketones using either Lithium

tetrahydridoaluminate - LiAlH4 , above) .
The reduction of a carboxylic acid
The reaction happens in two stages - first to form an aldehyde and then a primary alcohol.
Because lithium tetrahydridoaluminate reacts rapidly with aldehydes, it is impossible to stop
at the halfway stage.
Equations for these reactions are usually written in a simplified form for UK A level
purposes. The "[H]" in the equations represents hydrogen from a reducing agent.
Because of the impossibility of stopping at the aldehyde, there isn't much point in giving an
equation for the two separate stages. The overall reaction is:

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18

"R" is hydrogen or a hydrocarbon group. For example, ethanoic acid will reduce to the
primary alcohol, ethanol.

"R" is hydrogen or a hydrocarbon group. For example, ethanoic acid will reduce to
the primary alcohol, ethanol.

Sodium tetrahydridoborate (sodium borohydride) won't work!

If you are familiar with the reduction of aldehydes and ketones using lithium tetrahydridoaluminate,
you are probably aware that sodium tetrahydridoborate is often used as a safer alternative.
It CAN'T be used with carboxylic acids. The sodium tetrahydridoborate isn't reactive enough to
reduce carboxylic acids.
Reaction conditions
Lithium tetrahydridoaluminate reacts violently with water and so the reactions are carried out in
solution in dry ethoxyethane (diethyl ether or just "ether"). The reaction happens at room
temperature.
At the end of the reaction, the product is a complex aluminium salt. This is converted into the
alcohol by treatment with dilute sulphuric acid.

Summary of reactions of carboxylic acids and their salts

Type of reaction

Mechanism

1. acid-base

n/a

a) carboxylic acids with sodium hydroxide

reagent: NaOH
conditions: room temperature
equation: R-COOH(aq) + NaOH(aq) R-COO-Na+(aq) + H2O(l)
b) carboxylic acids with sodium carbonate
reagent: Na2CO3
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19

conditions: room temperature

equation: 2R-COOH(aq) + Na2CO3(aq) 2R-COO-Na+(aq) +
CO2(g) + H2O(l)
observations: colourless gas evolved which turns limewater milky
c) carboxylate salts with acids
reagent: HCl(aq)
conditions: room temperature
equation: R-COO-(aq) + H+(aq) R-COOH(aq)
d) Reduction of carboxylic acids.

2. esterification
reagents: any alcohol, concentrated sulphuric acid catalyst
conditions: heat and reflux
equation: R1-COOH + R2OH == R1-COOR2 + H2O

Dr.A.Matovu

Nucleophilic
addition/
Elimination
(not required)

20

ESTERS
Esters are made when carboxylic acids and alcohols are heated together under reflux in the
presence of a strong acid catalyst as described above. They have the same general formula
(CHO) as carboxylic acids and contain the following functional group:
O
C
O

Eg
O
H

C
O

CH3

CH2

a)

C
O

C
O

methyl methanoate

ethyl propanoate

CH2

CH3

CH

CH3

CH3

methylethyl methanoate

Properties and uses of esters

Esters have pleasant, often sweet smells. They are widely used as food flavourings for this
reason (eg ethyl methanoate gives raspberry flavour and ethyl butanoate gives pear flavour).
This sweet smell can also be used to test for the presence of carboxylic acids and alcohols; a
carboxylic acid will give a sweet smell if heated with ethanol and a strong acid, and an
alcohol will give a sweet smell if heated with ethanoic acid and a strong acid.
Esters are also used as plasticizers. They can be added to polymers to make them less rigid
and more flexible. Plasticiser molecules weaken the intermolecular forces between the
polymer chains.
Esters are also used as solvents for organic compounds such as nail varnish. The ester
evaporates easily, leaving the solute behind.

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21

b)

Hydrolysis of esters

i) acid hydrolysis
Since the esterification reaction is reversible, it follows that if an ester is heated under reflux
with concentrated H2SO4, a carboxylic acid and an alcohol will be formed in a reversible
reaction:
R1-COOR2 + H2O == R1-COOH + R2OH
Eg ethyl ethanoate + H2O == ethanoic acid + ethanol
H

CH3

C
O

CH2

H2O

CH3

CH2

OH

OH

CH3

Eg methyl propanoate + H2O == propanoic acid + methanol

O

CH3

CH2

C
O

H2O

CH2

CH3

CH3

OH

OH

CH3

Eg propyl methanoate + H2O == methanoic acid + propan-1-ol

O

C
O

CH2

CH2

CH3

H2O

C
O

CH3

CH2

CH2

OH

This reaction is known as ester hydrolysis. It does not go to completion but reaches
equilibrium with only approximately 30% of the ester hydrolysed. It does not therefore give
a very good yield of the carboxylic acid or the alcohol.

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22

ii) alkaline hydrolysis (saponification)

If an ester is heated under reflux with a strong alkali such as NaOH, a carboxylate salt and
an alcohol are formed:
R1-COOR2 + NaOH == R1-COO-Na+ + R2OH
Eg ethyl ethanoate + NaOH(aq) sodium ethanoate + ethanol
H

CH3

C
O

CH2

NaOH

CH3

CH3

O- Na+

CH2

OH

Eg methyl propanoate + NaOH(aq) sodium propanoate + methanol

O

CH3

CH2

C
O

NaOH

CH2

CH3

O- Na+

OH

CH3

CH3

Eg propyl methanoate + NaOH(aq) sodium methanoate + propan-1-ol

O

C
O

CH2

CH2

CH3

NaOH

- +

O Na

CH3

CH2

CH2

OH

This reaction is known as alkaline hydrolysis. It is also known as saponification.

It is not readily reversible, so results in a better yield of the alcohol and carboxylate than the
acid hydrolysis of the same ester.
The NaOH in this reaction is not a catalyst; it is a reactant. The equilibrium can thus be
moved further to the right by using the NaOH in excess.
Saponification is thus a more efficient way of hydrolysing an ester than acid hydrolysis,
since it results in a much better yield.
After the mixture is cooled, the carboxylate salt can be readily converted to the carboxylic
acid by acidifying the mixture.
R-COO-(aq) + H+(aq) R-COOH(aq)
This means that even if you want a carboxylic acid as your final product, it is better to
hydrolyse the ester in alkaline conditions first and then acidify the mixture afterwards.

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23

c)

naturally occurring fats and oils

Naturally occurring fats and oils are in fact esters. They have the general formula:
H
O

C
O
C

R1

R2

R3

R = C13H27, C15H31, C17H35 , or C19H39

They contain three ester groups. These esters are hydrolysed in the acidic conditions of the
stomach and can be broken down into the constituent acid and alcohol. They can also be
hydrolysed artificially in alkaline conditions.
i) acid hydrolysis of fats
During digestion, some fats are broken down into the constituent parts. The reaction is
catalysed by an enzyme called lipase and the acidic conditions of the stomach:
H

O
O

H
H

C
C

C
O

H
R1

R2

3H2O

R3

HO

OH

OH

OH

R1

+
O

HO

R2

+
O

H
HO

R3

The products of this hydrolysis are propan-1,2,3tri-ol (more commonly known as glycerol)
and three long-chain carboxylic acids (generally known as fatty acids).
So the hydrolysis of a fat or oil molecule in the stomach produces glycerol and three fatty
acid molecules. The formula for a typical fatty acid molecule would be C17H35COOH.
Glycerol is used by the body to make glucose for respiration (which is why fats are good
energy sources) and fatty acids are used to make cell membranes (which is why fats are
essential for healthy tissue growth).

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24

ii) alkaline hydrolysis of fats (saponification)

Fats and oils are hydrolysed commercially in alkaline conditions. The products are glycerol
and the salts of the fatty acids:
H

C
O
C

H
R1

OH

OH

OH

R1

+
O

R2

+ 3NaOH

Na + O

R3

Na + O

+
-

Na + O

R2

O
C

R3

The salts of the long-chain fatty acids are known as soaps. They are extremely useful as
they help oil and water mix together. Glycerol is a useful by-product of this reaction as it
can be used to make pharmaceuticals and cosmetics.
So the alkaline hydrolysis of fats and oils produces soap, which usually has the formula
C17H35COO-Na+. Glycerol is also formed as a useful by-product.
Soap molecules have a polar end, which is the carboxylate end, which attracts water and
other hydrophilic groups. They also have a non-polar end, which is the long-chain
hydrocarbon end, which attracts oils and other hydrophobic groups. The same molecule is
thus attracted to aqueous species and oily species, thus enabling them to mix. This means
that oil will come off skin (or cooking utensils) into water which contains soap.
hydrophobic end (attracts fats and oils)
hydrophilic end (attracts water,
ionic and polar groups)

O
C
O-

Dr.A.Matovu

Na+

25

iii) making biodiesel

Biodiesel is a mixture of methyl esters of long chain fatty acids.
It is made by hydrolysing naturally occurring fats or oils (as described above) to make fatty
acids.
The fatty acids can then be mixed with methanol in the presence of a suitable catalyst to
make a methyl ester. This is an esterification reaction.
Eg C17H35COOH + CH3OH == C17H35COOCH3 + H2O
Biodiesel is a renewable fuel because it is made from vegetable oil, which can be produced
quickly by growing crops such as rape.
d)

summary of reactions of esters

Type of reaction

Mechanism

hydrolysis

n/a

a) acid hydrolysis
reagent: concentrated H2SO4
conditions: heat under reflux
equation: R1-COOR2 + H2O == R1-COOH + R2OH
b) alkaline hydrolysis (saponification)
reagent: NaOH(aq)
conditions: heat under reflux
equation: R1-COOR2 + NaOH == R1-COO-Na+ + R2OH

Dr.A.Matovu

26

ACYL CHLORIDES AND ACID ANHYDRIDES

Carboxlyic acids will react with bases and with alcohols, but are generally unreactive
otherwise. Although the +ve C atom can attract nucleophiles, the stability of the COOH
group means that these reactions do not take place readily.
Nucleophilic attack at the C atom will take place if the carboxylic acid is first converted into
a more reactive derivative. Two such derivatives are acyl chlorides and acid anhydrides.
a)

structure of acyl chlorides and acid anhydrides

Acyl chlorides contain the following functional group:

O
C
Cl

Eg
H

O
H

O
H

Cl

ethanoyl chloride

C
Cl

propanoyl chloride

The carbon atom is attached to two electronegative atoms and so is very +ve. It attracts
nucleophiles readily:

C
Cl

Nu :

Dr.A.Matovu

27

Acid anhydrides contain the following functional group:

O
C
O
C
O

Eg
O

O
CH3

C
O

O
CH3

CH3

C
O

ethanoic anhydride methanoic ethanoic anhydride

CH3

CH2

CH3

CH2

O
O

propanoic anhydride

Again, the carbon atom is attached to two electronegative atoms, is very +ve and attracts
nucleophiles readily:

+
C
Nu:

O
O

C
O

Acyl chlorides and acid anhydrides both react readily with nucleophiles.

Dr.A.Matovu

28

b)

mechanism: nucleophilic addition-elimination

Acyl chlorides react by a mechanism called nucleophilic addition-elimination.

When an acyl chloride is attacked by a nucleophile, addition occurs and the bond is
broken:

O-

Cl

Cl

Nu+

..
Nu

However, the C-Cl bond then breaks and the bond is reformed. The extra H on the
nucleophile is also lost:
O:
R

O
Cl

Cl

+
H

Nu
Nu+
H

The chloride ion, or another nucleophile may combine with the free proton.
Acyl chlorides and acid anhydrides react with water, ammonia, alcohols and primary amines
by this mechanism. This reaction is also known as acylation.

Dr.A.Matovu

29

c)

acylation reactions of acyl chlorides

i) with water
Acyl chlorides react with water violently. White fumes of HCl can be clearly seen:
R-COCl + H2O R-COOH + HCl
The organic product is a carboxylic acid.
The mechanism is nucleophilic addition-elimination:

O:

C
Cl

..
O

Cl

O+

HCl

C
O

O
H

example:

Dr.A.Matovu

C
H

C
Cl

H2O

HCl

OH
H

30

ii) with ammonia

Acyl chlorides also react with ammonia violently. White fumes of HCl can be clearly seen:
R-COCl + NH3 R-CONH2 + HCl
In excess ammonia, the left-over NH3 and the HCl may react:
R-COCl + 2NH3 R-CONH2 + NH4Cl
The organic product is an amide.
The mechanism is nucleophilic addition-elimination:
O

O:

Cl

..
N
H

O
Cl

+ HCl

+
N

example:
H

O
H

C
H

O
H

NH3

Cl

NH2

HCl

or in

excess ammonia:
H

O
H

Dr.A.Matovu

C
Cl

2NH3

NH2

NH4Cl

31

iii) with alcohols

Acyl chlorides react violently with alcohols. White fumes of HCl can be seen:
R1-COCl + R2-OH R1-COOR2 + HCl
The organic product is an ester.
The mechanism is nucleophilic addition-elimination:

R1

O:

R1

Cl

..
O

R2

Cl
R1

+
O

+ HCl

R2

O
H

R2

example:
H
H

C
H

Cl

Dr.A.Matovu

CH3

CH2

OH

CH3

C
O

CH2

HCl

CH3

32

iv) with primary amines

Acyl chlorides react vigorously with primary amines. White fumes of HCl can be seen:
R1-COCl + R2-NH2 R1-CONHR2 + HCl
In excess amine, the left-over amine can react with the HCl:
R1-COCl + 2R2-NH2 R1-CONHR2 + R2-NH3Cl
The organic product is an N-substituted amide.
The mechanism is nucleophilic addition-elimination:

O:

R1

Cl

..
N
R2

Cl

C
+
N

R2

R2

+ HCl

R1

example:
H

O
H

O
CH3

CH2

CH3

NH2

Cl

HCl

or, in excess amine:

H

O
H

Dr.A.Matovu

Cl

2 CH3

CH2

NH2

CH3

+ CH

CH2

NH3Cl

33

d)

acylation reactions of acid anhydrides

Acid anhydrides react in the same way as acyl chlorides. They react with water, ammonia,
alcohols and primary amines. The mechanism is also nucleophilic addition-elimination.
The reactions are much slower than the acyl chloride reactions, and do not produce the toxic
gas HCl but produce a carboxylic acid instead.
Commercially, acid anhydrides are therefore used preferentially to acyl chlorides in
acylation reactions; the reactions are easier to control and they do not produce a toxic
gas.
i) with water
Acid anhydrides react with water slowly when the mixture is warmed. Two carboxylic
molecules are produced.
R1-COOCO-R2 + H2O R1-COOH + R2-COOH
Example:
H

O
H

C
O

CH3

H2O

OH

OH

ii) with ammonia

Acid anhydrides react with ammonia slowly when the mixture is warmed. An amide and a
carboxylic acid are produced.
R1-COOCO-R2 + NH3 R1-CONH2 + R2-COOH
Example:
C
O
CH3

O
CH3

C
O

Dr.A.Matovu

NH3

C
H

NH2

O
C
OH

34

iii) with alcohols

Acid anhydrides react with alcohols on gentle heating to produce esters. A carboxylic acid is
also produced.
R1-COOCO-R2 + R3-OH R1-COO-R3 + R2-COOH
Example:
H

O
CH3

O
CH3

H
H

OH

C
OH

iv) with primary amines

Acid anhydrides react with primary amines on gentle heating to produce N-substituted
amides. A carboxylic acid is also produced.
R1-COOCO-R2 + R3-NH2 R1-CONH-R3 + R2-COOH
Example:
O
CH3

C
O

CH3

C
O

Dr.A.Matovu

CH3

CH2

O
CH3

N
H

O
C
OH

35

e)

preparation of aspirin

Aspirin is an ester with the following formula:

O

OH
C
O

It is made be reacting the -OH group on 2-hydroxybenzoic acid with either ethanoic acid,
ethanoyl chloride or ethanoic anhydride.
The reaction with ethanoic acid needs strongly acidic conditions, heat and reflux and only
goes to equilibrium.
The reaction with ethanoyl chloride is violent, difficult to control and produces the toxic gas
hydrogen chloride.
The reaction with ethanoic anhydride is reasonably fast when heated gently and does not
produce toxic by-products. It is therefore the chosen method for the preparation of aspirin.
O

OH

O
O

C
O

CH3

CH3

C
O

O
C
OH

Dr.A.Matovu

OH

36

f)

summary of reactions of acyl chlorides and acid anhydrides

Type of reaction

Mechanism

1. acylation using acyl chlorides

Nucleophilic
additionelimination
(required)

a) with water (to make carboxylic acids)

conditions: room temperature
equation: R-COCl + H2O R-COOH + HCl
observation: white misty fumes
b) with ammonia (to make amides)
conditions: room temperature
equation: R-COCl + 2NH3 R-CONH2 + NH4Cl
observation: white misty fumes
c) with alcohols (to make esters)
conditions: room temperature
equation: R1-COCl + R2-OH R1-COOR2 + HCl
observation: white misty fumes
d) with primary amines (to make N-substituted amides)
conditions: room temperature
equation: R1-COCl + 2R2-NH2 R1-CONHR2 + R2-NH3Cl
observation: white misty fumes
2. acylation using acid anhydrides
a) with water (to make carboxylic acids)
conditions: room temperature
equation: R1-COOCO-R2 + H2O R1-COOH + R2-COOH
observation: white misty fumes

Nucleophilic
additionelimination
(not required)

b) with ammonia (to make amides)

conditions: room temperature
equation: R1-COOCO-R2 + NH3 R1-CONH2 + R2-COOH
observation: white misty fumes
c) with alcohols (to make esters)
conditions: room temperature
equation: R1-COOCO-R2 + R3-OH R1-COO-R3 + R2-COOH
observation: white misty fumes

Dr.A.Matovu

37

d) with primary amines (to make N-substituted amides)

conditions: room temperature
equation: R1-COOCO-R2 + R3-NH2 R1-CONH-R3 + R2-COOH
observation: white misty fumes

Dr.A.Matovu

38