4.8 Further Organic Chemistry

1 of 38 © Boardworks Ltd 2010

The carbonyl group
The carbonyl group (>C=O) is the
functional group found in
compounds such as aldehydes,
ketones, and carboxylic acids.
 In aldehydes the carbonyl group is at

the end of the carbon chain and so has
at least one hydrogen attached to it.
 In ketones the carbonyl group is in the

middle of a carbon chain and so has
two alkyl groups attached to it.

Representing aldehydes and ketones
Aldehydes and ketones cannot be distinguished by their
molecular formula because they have the same functional
group.
What is the molecular formula of the aldehyde and ketone

below?
an aldehyde a ketone
Both have the molecular formula C3H6O

Representing aldehydes and ketones
Aldehydes and ketones are therefore represented either
using displayed or structural formulae.
CH3CHO CH3CH2CH2CHO
CH3COCH2CH3 CH3CH2COCH2CH3

Naming aldehydes
Aldehydes are named using the suffix –al, and follow the
same conventions as for naming alkanes.
ethanal propanal
2-methylbutanal
Naming ketones
Ketones are named using the suffix –one.
propanone hexan-3-one
Like alkenes, ketones with four or more carbon atoms display

positional isomerism because the carbonyl group may
appear between different carbon atoms. In these cases, a
number is used before the –one to indicate the first carbon
involved.

Naming aldehydes and ketones activity

Synthesis of aldehydes and ketones

Properties of aldehydes and ketones
The carbonyl group is polar due to the
greater electronegativity of oxygen (3.4) than δ+ δ-
carbon (2.6). This influences the properties
of aldehydes and ketones, such as solubility.
Small aldehydes and ketones are soluble

in water due to hydrogen bonding between
a lone pair on the oxygen of the carbonyl
group and the hydrogen of the water.
As size increases, solubility decreases

due to interference in hydrogen
bonding by the hydrocarbon ‘tails’ of
the aldehydes/ketones.

Boiling points: a comparison

Boiling points and intermolecular forces
The general increase in boiling points from alkanes to
aldehydes/ketones and alcohols is due to the intermolecular
forces between each type of molecule.
 Alkanes are only held together by van der Waals forces.

These forces increase with the size/length of a molecule.
 The polar carbonyl group in aldehydes and ketones means

that as well as van der Waals forces, these molecules are
also held together by dipole–dipole interactions.
 Alcohols are held together by van der Waals forces and

dipole–dipole interactions. In addition, these molecules can
form hydrogen bonds with each other, due to the slightly
positive hydrogen atom of the hydroxyl group.

Reactivity of the carbonyl group
Although double bonds require more energy to break than
single bonds, compounds with double bonds tend to be
more reactive as addition reactions are possible.
Some of the chemical properties of δ+ δ-

aldehydes and ketones result from the
polar nature of the C=O bond.
 The positive charge on the carbon atom makes it open

to attack by nucleophiles.
 Aldehydes and ketones can be reduced, forming

primary and secondary alcohols respectively.
 Aldehydes may also be oxidized to carboxylic acids.

Nucleophilic addition using cyanide

Dangers of HCN
Hydrogen cyanide (HCN) is highly volatile liquid (boiling point
26 °C), which has a faint bitter almond smell.
In solution, hydrogen cyanide partially dissociates:
HCN(aq) H+(aq) + CN-(aq)
Hydrogen cyanide is highly toxic because it inhibits a

mitochondrial enzyme that is essential for respiration. Being
so volatile and flammable, it is difficult to handle safely.
A safer alternative is potassium cyanide, which is a solid at

room temperature and is therefore easier to handle. An
acidified solution contains both the H+ and CN- ions.

Reduction of aldehydes and ketones

Distinguishing aldehydes & ketones

Detecting a carbonyl group

Reactions of aldehydes and ketones

Aldehydes and ketones: true or false?

Carboxylic acids
Carboxylic acids have a carboxyl group
(-COOH) consisting of a carbonyl group
and a hydroxyl group attached to the
terminal carbonyl carbon.
Carboxylic acids are named using the suffix –oic acid.
Methanoic acid is the simplest carboxylic

acid and is found in bee and ant stings.
Ethanoic acid is the acid that gives vinegar

its sharp taste and smell. It is also important
in the chemical industry and about 6.5
million tonnes are used worldwide each year

Naming carboxylic acids

Boiling points of carboxylic acids

Synthesis of carboxylic acids

Oxidation of 1° alcohols and aldehydes
Carboxylic acids can be created by the oxidation of aldehydes
by oxidizing agents such as potassium dichromate(VI).
They can also be created by the oxidation of primary alcohols,

again using potassium dichromate(VI).

Hydrolysis of nitriles
Carboxylic acids can also be prepared by the hydrolysis of
nitriles.
The nitrile is refluxed with water and hydrochloric acid. The

carboxylic acid can then be distilled from the reaction mixture.

Reactivity of carboxylic acids
The reactivity of carboxylic δ-
acids results, in part, from
δ+
the polarization of its bonds.
δ- δ+
The reactions of carboxylic acids include:

 neutralisation – the carboxylic acid loses a proton to
form a carboxylate salt
 nucleophilic substitution – the positively-charged carbon
is attacked by a nucleophile, resulting in substitution of the
OH group
 esterification – reaction with an alcohol to form an ester.

Forming the carboxylate ion
Carboxylic acids are weak acids and partially dissociate in
aqueous solution:
carboxylate ion
The negative charge is delocalized across the

carboxylate group, resulting in a more stable
ion. The delocalization is represented by
adding a second dotted line to the carbon
oxygen bonds, which are both equivalent.

Reactions with carbonates
Carboxylic acids are the only organic compounds that are
strong enough acids to react with either sodium carbonate or
sodium hydrogencarbonate.
Reaction of ethanoic acid and sodium carbonate:
2CH3COOH + Na2CO3 → 2CH3COONa + CO2 + H2O

sodium ethanoate
Reaction of methanoic acid and sodium hydrogencarbonate:
HCOOH + NaHCO3 → HCOONa + CO2 + H2O

sodium methanoate
The formation of bubbles of carbon dioxide gas makes these

reactions useful as a test for carboxylic acids.

Reactions with alkalis
Carboxylic acids will react with alkalis, such as sodium
hydroxide, in a neutralization reaction:
RCOOH + NaOH → RCOONa + H2O
Reaction of propanoic acid and sodium hydroxide:
CH3CH2COOH + NaOH → CH3CH2COONa + H2O

sodium propanoate
Reaction of butanoic acid and potassium hydroxide:
CH3CH2CH2COOH + KOH → CH3CH2CH2COOK + H2O

potassium butanoate

Carboxylic acids: a summary

Glossary

What’s the keyword?

Multiple-choice quiz

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)

Esterification

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
Naming esters

Hydrolysis of esters

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.

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.

Esters in fats and oils

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
name
Formula and systematic name Description
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

Saturated and unsaturated

Esters: true or false?

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).

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.

Making soap and biodiesel

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

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.

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

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.

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.

Ester, acid chloride or acid anhydride?

Naming acyl compounds

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.

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.

The addition–elimination mechanism

Acid chloride reactions

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

Relative reactivity of nucleophiles

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.

Production of paracetamol and aspirin

Acid derivatives: a summary

Glossary

What’s the keyword?

Multiple-choice quiz

4.8 Further Organic Chemistry

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4.8 Further Organic Chemistry

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1 of 38 © Boardworks Ltd 2010

2 of 38 © Boardworks Ltd 2010

 In aldehydes the carbonyl group is at

 In ketones the carbonyl group is in the

3 of 38 © Boardworks Ltd 2010

What is the molecular formula of the aldehyde and ketone

Both have the molecular formula C3H6O

4 of 38 © Boardworks Ltd 2010

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Like alkenes, ketones with four or more carbon atoms display

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Small aldehydes and ketones are soluble

As size increases, solubility decreases

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 Alkanes are only held together by van der Waals forces.

 The polar carbonyl group in aldehydes and ketones means

 Alcohols are held together by van der Waals forces and

12 of 38 © Boardworks Ltd 2010

Some of the chemical properties of δ+ δ-

 The positive charge on the carbon atom makes it open

 Aldehydes and ketones can be reduced, forming

 Aldehydes may also be oxidized to carboxylic acids.

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In solution, hydrogen cyanide partially dissociates:

HCN(aq) H+(aq) + CN-(aq)

Hydrogen cyanide is highly toxic because it inhibits a

A safer alternative is potassium cyanide, which is a solid at

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Methanoic acid is the simplest carboxylic

Ethanoic acid is the acid that gives vinegar

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They can also be created by the oxidation of primary alcohols,

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The nitrile is refluxed with water and hydrochloric acid. The

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The reactions of carboxylic acids include:

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The negative charge is delocalized across the

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2CH3COOH + Na2CO3 → 2CH3COONa + CO2 + H2O

Reaction of methanoic acid and sodium hydrogencarbonate:

HCOOH + NaHCO3 → HCOONa + CO2 + H2O

The formation of bubbles of carbon dioxide gas makes these

32 of 38 © Boardworks Ltd 2010

RCOOH + NaOH → RCOONa + H2O

Reaction of propanoic acid and sodium hydroxide:

CH3CH2COOH + NaOH → CH3CH2COONa + H2O

Reaction of butanoic acid and potassium hydroxide:

CH3CH2CH2COOH + KOH → CH3CH2CH2COOK + H2O

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