18

15.1 Alkanes

18.1 Aldehydes and Ketones

18.1 Aldehydes and Ketones

 Both aldehydes and ketones contain the carbonyl group:

 The functional group is unsaturated and the carbon atom attracts nucleophiles. Hence aldehydes and
ketones undergo nucleophilic addition reactions. The carbonyl group does not participate in hydrogen-
bonding.

 In aldehydes, the carbonyl group is at the terminal position of the carbon chain. Examples of aldehydes
are:

 In ketones, the carbonyl group is in the middle of the carbon chain:

Preparation of Aldehydes
 Aldehydes are prepared by the
oxidation of primary alcohols
using hot acidified sodium or
potassium dichromate (VI).

 The alcohols must be in excess,

and the aldehyde must be
distilled off as it forms, before it
oxidises to carboxylic acid. (An
electric heater is preferred to the
Bunsen burner, as the ethanol
could catch a fire!)

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 53 | P a g e
Preparation of Ketones
acidified potasium dichromate
 Ketones are prepared by the oxidation of secondary alcohols by acidified. A distillation apparatus is
preferred since the ketone is volatile and so can be distilled off as it forms.

Chemical Reactions of Carbonyl Compounds

 Reactions of aldehydes and ketones are similar, except for oxidation. Aldehydes can oxidise to carboxylic
acids; ketones resist oxidation.

i) With Reducing Agents

 The reducing agents lithium tetrahydridoaluminate (III), 𝐿𝑖𝐴𝑙𝐻4 and sodium tetrahydridoborate
(III), 𝑁𝑎𝐵𝐻4 , reduce aldehydes to primary alcohols and ketones to secondary alcohols. Hydrogen in the
presence of a nickel catalyst can also reduce carbonyl compounds to alcohols.

 𝐿𝑖𝐴𝑙𝐻4 is a much stronger reducing agent, reducing even water and carboxylic acids, hence the conditions
must be dry. A suitable solvent is dry ether. 𝑁𝑎𝐵𝐻4 is a milder reducing agent and may be used in the
presence of water, provided the solution is alkaline.

Method 1
Reagents: carbonyl compound and 𝑁𝑎𝐵𝐻4
Conditions: dry ether
Mechanism: reduction/nucleophilic addition

𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝑯𝑶 + 𝟐[𝑯] 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝑯𝟐 𝑶𝑯

propanal propan-1-ol

𝑪𝑯𝟑 𝑪𝑶𝑪𝑯𝟑 + 𝟐[𝑯] 𝑪𝑯𝟑 𝑪𝑯(𝑶𝑯)𝑪𝑯𝟑

propanone propan-2-ol

Note that 𝑁𝑎𝐵𝐻4 does not reduce the alkene group, C=C:

𝑪𝑯𝟑 𝑪𝑯 = 𝑪𝑯𝑪𝑯𝑶 + 𝟐[𝑯] 𝑪𝑯𝟑 𝑪𝑯 = 𝑪𝑯𝑪𝑯𝟐 𝑶𝑯

Method 2
Reagents: carbonyl compound and hydrogen
Conditions: nickel , heat
Mechanism: reduction/hydrogenation

𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝑯𝑶 + 𝑯𝟐 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝑯𝟐 𝑶𝑯

𝑪𝑯𝟑 𝑪𝑶𝑪𝑯𝟑 + 𝑯𝟐 𝑪𝑯𝟑 𝑪𝑯(𝑶𝑯)𝑪𝑯𝟑

Note that 𝐻2 does reduce the alkene group to alkane:

𝑪𝑯𝟑 𝑪𝑯 = 𝑪𝑯𝑪𝑯𝑶 + 𝟐𝑯𝟐 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝑯𝟐 𝑪𝑯𝟐 𝑶𝑯

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 54 | P a g e
ii) Nucleophilic Addition Reactions
 Hydrogen cyanide, 𝐻𝐶𝑁, rapidly adds across the –C=O double bond to form cyanohydrins. 𝐻𝐶𝑁 is an
extremely poisonous gas and is not directly used as the reagent; instead 𝐾𝐶𝑁 or 𝑁𝑎𝐶𝑁 is added together
with dilute sulphuric acid. These react to form 𝐻𝐶𝑁 in situ which then reacts with the carbonyl compound.

Reagents: carbonyl compound, 𝐾𝐶𝑁 and 𝐻2 𝑆𝑂4

Conditions: warm
Mechanism: nucleophilic addition

𝑪𝑯𝟑 𝑪𝑯𝑶 + 𝑯𝑪𝑵 𝑪𝑯𝟑 𝑪𝑯𝟐 (𝑶𝑯)𝑪𝑵

ethanal 2-hydroxypropanenitrile

𝑪𝑯𝟑 𝑪𝑶𝑪𝑯𝟑 + 𝑯𝑪𝑵 𝑪𝑯𝟑 𝑪(𝑶𝑯)(𝑪𝑵)𝑪𝑯𝟑

propanone 2-hydroxy-2-methylpropanenitrile

 The reaction occurs via a two-step mechanism:

Step 1: the –CN nucleophile attacks the carbon atom of the carbonyl group, and the C=O bond
undergoes heterolytic fission.
Step 2: the oppositely charged ions attract and react readily

 Note that step 1 is the rate-determining step with a much higher activation energy than the fast step 2,
as step 2 involves oppositely charged particle which should react more readily.

 Ketones undergo similar reaction:

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 55 | P a g e
 This reaction increases the number of carbon atoms in the molecule.

 The nitrile group formed undergoes two important reactions: hydrolysis to carboxylic group by boiling
in aqueous acid, and reduction to amine group by heating in the presence of hydrogen and nickel
catalyst:

iii) With Mild Oxidising Agents

 Mild oxidising agents provide a way of distinguishing ketones from aldehydes. Ketones resist oxidation;
aldehydes oxidise to carboxylic acids.
Typical mild oxidising agents are silver (I) ions and copper (II) ions, both in alkaline conditions.

1. Tollens’ Reagent (Silver Mirror Test)

This solution contains the diammine silver (I) complex, [𝐴𝑔(𝑁𝐻3 )2 ]+ . It oxidises aldehydes while the silver
ions are reduced to silver metal.

Reagents: any aldehyde and Tollens reagent

Conditions: warm
Mechanism: oxidation (mild)
Observation: silver precipitate

𝑪𝑯𝟑 𝑪𝑯𝑶 + 𝟐[𝑨𝒈(𝑵𝑯𝟑 )𝟐 ]+ + 𝑯𝟐 𝑶 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝟐𝑵𝑯𝟑 + 𝟐𝑵𝑯𝟒+ + 𝟐𝑨𝒈

ethanal
𝑪𝟔 𝑯𝟓 𝑪𝑯𝑶 + 𝟐[𝑨𝒈(𝑵𝑯𝟑 )𝟐 ]+ + 𝑯𝟐 𝑶 𝑪𝟔 𝑯𝟓 𝑪𝑶𝑶𝑯 + 𝟐𝑵𝑯𝟑 + 𝟐𝑵𝑯+
𝟒 + 𝟐𝑨𝒈
benzaldehyde

Fehling’s Solution
This solution contains copper (II) ions complexed with tartrate ions. It oxidises only aliphatic aldehydes
to carboxylic acids, while the copper (II) ions are reduced to copper (I) oxide.

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 56 | P a g e
 Reagents: aliphatic aldehyde and Fehling’s solution
Conditions: warm
Mechanism: oxidation (mild)
Observation: blue solution to red ppt of copper (I) oxide

𝑪𝑯𝟑 𝑪𝑯𝑶 + 𝟐𝑪𝒖𝟐+ + 𝟐𝑯𝟐 𝑶 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝟒𝑯+ + 𝑪𝒖𝟐 𝑶

ethanal
𝑪𝟔 𝑯𝟓 𝑪𝑯𝑶 + + 𝟐𝑪𝒖𝟐+ + 𝟐𝑯𝟐 𝑶 𝒏𝒐 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏
benzaldehyde

iv) Addition-Elimination using 2,4-DNPH

 2,4-dinitrophenylhydrazine (also called Brady’s Reagent) is an orange solution. It reacts with any aldehyde
and any ketone at room conditions to form a bright orange-yellow crystalline precipitate called a
hydrazone.

Reagents: any carbonyl compound and the 2,4-DNPH reagent

Conditions: room
Mechanism: addition-elimination, or condensation
Observation: orange solution to bright orange-yellow precipitate

 A water molecule is eliminated in the process, hence the reaction can be referred to as a condensation
reaction.

 The hydrazone precipitate, when washed and dried, is found to have a well-defined melting point.

v) The Tri-iodomethane Test

 Carbonyl ketones which have the group below give a positive tri-iodomethane test, i.e., they form the
pale yellow precipitate of tri-iodomethane.

 The general reaction is given below:

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 57 | P a g e
 Section A

1. Which of the following can be distinguished by making 2,4-dinitrophenylhydrazone derivatives?

A Ethanal and propanal
B Propan-1-ol and propan-2-ol
C Ethanoic acid and benzoic acid
D Ethanol and ethanoic acid

2. Which of the following could be the molecular formula for a ketone?

3. Which of the following statements is true about the carboxyl group?

A C=O and —OH each retain their own properties, unaffected by the other.
B The properties of the C=O are changed but the —OH is unaffected.
C The properties of the —OH are changed but the C=O is unaffected.
D The properties of the C=O and the —OH are each affected by the other.

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 58 | P a g e
 4. Which of the following reagents can be used directly to distinguish between an aldehyde and a ketone?

A Fehling’s solution
B Bromine solution
C 2,4-Dinitrophenylhydrazine
D Lithium aluminium hydride

1. A
2. B
3. D
4. A

SECTION B
1. Cinnamaldehyde is an aromatic compound found in cinnamon. It can also be prepared by the reaction
of benzaldehyde and ethanal.

(a) What type of reaction is this? [1]

(b) Draw a full structural formula for cinnamaldehyde. [1]
(c) All three of the carbonyl compounds shown above react with 2,4-dinitrophenylhydrazine,
(Brady’s reagent), forming solid derivatives.
The structure of 2,4-dinitrophenylhydrazine is

(i) Draw a structural formula of the compound formed when ethanal reacts with 2,4-
dinitrophenylhydrazine. [1]
(ii) The compound formed is impure. How would this compound be purified? [1]
(iii) How would the purified compound be used to show that the original carbonyl compound
was ethanal? [1]
(iv) 2,4-Dinitrophenylhydrazone derivatives have distinctive colours. What colour is the 2,4-
dinitrophenylhydrazone derivative of propanone? [1]
[TOTAL: 6]

2. The structure of lactic acid is

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 59 | P a g e
 (a) What is the systematic name of lactic acid? [1]
(b) Lactic acid contains an asymmetric carbon atom. Identify, and explain, which one of the numbered
carbon atoms is asymmetric. [1]
(c) Lactic acid can be produced from ethanal by the reaction sequence below.

(i) Which reagent could be used in step 1 ? [1]

(ii) What type of reaction takes place in step 2 ? [1]
(iii) Draw a structure for compound A. [5]
[TOTAL: 5]

1. a) Condensation
b)

c) i)

ii) Crystallisation/recrystallisation
iii) Measure melting point and compare to known data/value
iv) yellow/orange/gold

2 a) 2-hydroxypropanoic acid
b) Carbon atom because it has 4 different groups attached
c) i) KCN or NaCN

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 60 | P a g e
 ii) Hydrolysis/acid hydrolysis
iii)

Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 61 | P a g e