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What are esters?
Esters are carboxylic acid derivatives with
the hydrogen of the hydroxyl group replaced
by an alkyl group (hydrocarbon chain)
or an aryl group (an aromatic ring).

ethyl ethanoate methyl benzoate

(contains an alkyl (contains an aryl
group) group)

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Esterification

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Naming esters

The names of esters are based on the carboxylic acid and

alcohol from which they are produced.
The first component of this ester
name, the methyl, is derived
from the alcohol methanol.
The second component of the name,
the ethanoate, is derived from the
methylethanoate
carboxylic acid ethanoic acid.

ethylmethanoate propylethanoate
ethanol + methanoic acid propanol + ethanoic acid
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Naming esters

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Hydrolysis of esters

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Uses of esters
Shorter chain esters have fruity smells and tastes, which
makes them useful as solvents in perfumes and flavourings.

For example, ethyl butanoate smells of

pineapple; pentyl ethanoate smells of pears,
and octyl ethanoate smells of oranges.

Esters are used as artificial

fragrances and flavours as
synthesizing the ester is
often cheaper than extraction
from the natural source.

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Uses of esters
Esters are also useful as
glues, such as those used for
constructing plastic model
aircraft kits, and as plasticizers
to increase the flexibility of
plastics.

Esters have low boiling points and evaporate readily. This

makes them useful as industrial solvents, for example in paints.

Ethyl ethanoate is one such common solvent, being used in

the decaffeination of tea, as well as a laboratory solvent for
chromatography.

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Esters in fats and oils

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Naming fatty acids
Fatty acids have systematic names as well as common names.
For example, the systematic name for oleic acid is octadec-9-
enoic acid. Some common fatty acids are explained below.

Common
Formula and systematic name Description
name
stearic CH3(CH2)16COOH saturated, found in
acid (octadecanoic acid) most animal fats
palmitic CH3(CH2)14COOH saturated, used for
acid (hexadecanoic acid) making soaps
oleic CH3(CH2)7CH═CH(CH2)7COOH monounsaturated, found
acid (octadec-9-enoic acid) in most fats and olive oil
linoleic CH3(CH2)4(CH═CHCH2)2(CH2)6COOH polyunsaturated, found
acid (octadec-9,12-dienoic acid) in vegetable oils

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Saturated and unsaturated

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Esters: true or false?

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Trans fats and health
Most naturally occurring isomers of unsaturated fatty acids are
the cis form, such as cis-octadec-9-enoic acid, found in olive
oil, avocados and nuts.

In the partial hydrogenation of vegetable oils, the trans form of

the fatty acid, such as trans-octadec-9-enoic acid, may be
formed.

A diet high in trans fats, along with saturated fats, can lead to
an increased risk of coronary heart disease (CHD).

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Cholesterol and lipoproteins
Cholesterol is a lipid that regulates
fluidity in cell membranes. It is
transported in lipoproteins.

Low-density lipoprotein (LDL) transports

cholesterol from the liver to body tissues,
depositing it on the walls of blood vessels.
It increases the risk of CHD.

A diet high in saturated/trans fats is the biggest cause of high

LDL cholesterol levels.

High-density lipoprotein (HDL) transports cholesterol away

from the tissues to the liver, where cholesterol is metabolized.
High HDL levels are linked to a lower risk of CHD.

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Making soap and biodiesel

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What is acylation?
Acylation is the process in which an acyl group (RCO–) is
introduced to another molecule by an acylating agent.

Acid derivatives contain an acyl group, and

are derived from carboxylic acids. They have
the general formula RCOZ and include esters,
acid chlorides and acid anhydrides.

Name of acid General

Z group Example
derivative formula
OR’ ester RCOOR’ ethyl ethanoate, CH3COOC2H5
Cl acid chloride RCOCl ethanoyl chloride, CH3COCl
OCOR’ acid anhydride RCOOCOR’ ethanoic anhydride, CH3COOCOCH3

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Acylation
Acid derivatives are important acylating agents due to
their polarized carbonyl group.
The carbonyl group
is attacked by
nucleophiles at
the Cδ+, replacing Z.
The speed of acylation depends on:
 the reactivity of the nucleophile, according to its ability to
donate its lone pair to an electron-deficient carbon
 the electron-releasing or attracting power of Z, which affects
the magnitude of the + charge on the carbonyl carbon
 how easily Z is lost.

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What are acid chlorides?
Acid chlorides, also known as acyl
chlorides, contain a chlorine atom
attached to the acyl group.

Acid chlorides are named with the suffix –oyl;

the term chloride is also added.

ethanoyl chloride propanoyl chloride

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What are acid anhydrides?
Acid anhydrides are prepared by the reaction of two
molecules of a carboxylic acid, resulting in the elimination of a
molecule of water.

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Naming acid anhydrides
The acyl group is named after the carboxylic acid with
the suffix –oic; the term anhydride is also added.

ethanoic anhydride propanoic anhydride

Acid anhydrides can only be named in this way when they

are symmetrical. Some unsymmetrical acid anhydrides
are known but they are less common.

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Ester, acid chloride or acid anhydride?

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Naming acyl compounds

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Reactivity of acid chlorides
The oxygen and chloride atoms attached δ–
to the acyl carbon are groups that both δ+
withdraw electron density.
δ–

As a result, the carbon–oxygen and carbon–chlorine bonds

are both polar, with a δ+ charge on the carbon atom.

This means the acyl carbon atom is susceptible to attack

by nucleophiles, resulting in substitution of the chloride.

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Reactivity of acid anhydrides
Both the oxygen atoms attached to the δ–
acyl carbon withdraw electron density. δ+
δ–
As a result the carbon–oxygen bonds
δ+
are polar, with δ+ charges on both the
acyl carbon atoms. δ–

This means the acyl carbon atoms are susceptible to attack

by nucleophiles, resulting in substitution of a carboxylate ion.

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The addition–elimination mechanism

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Acid chloride reactions

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Relative reactivity of nucleophiles
Nucleophiles vary in their reactivity with an acid derivative
as follows:

ammonia → amide
increasing reactivity

N-substituted
amine →
amide

alcohol → ester

water → carboxylic acid

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Relative reactivity of nucleophiles

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Applications of acylation reactions
In organic synthesis reactions, the use of acid anhydride is
favoured over the corresponding acid chloride for several
reasons:
acid chlorides (e.g. ethanoyl chloride)
 difficult to handle as they react very readily with
water so need to be used in water-free conditions
 react to produce corrosive HCl.

acid anhydrides (e.g. ethanoic anhydride)

 cheaper to produce
 not as moisture sensitive
 less corrosive
 produce carboxylic acids, which are safer than HCl.

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Production of paracetamol and aspirin

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Acid derivatives: a summary

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Glossary

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What’s the keyword?

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Multiple-choice quiz

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