Exercise

18.1 Carbonyl compounds: Synthesis and

reduction
This exercise will familiarise you with the formulae of aldehydes as it revises the practical procedure for
making these compounds. You will also revise the use of LiAlH4 and NaBH4 in reducing carbonyl
compounds.

TIP
When naming ketones, remember that the CO group is given the
smallest number counting from either end of the molecule.

a Name these carbonyl compounds.

i HCHO

ii CH3CH2COCH2CH2CH3

iii CH3CH2CH2CHO

b Write the structural formulae for:

i butan-2-one

ii pentanal

iii pentan-2,4-dione (this has two CO carbonyl groups).

c Read the paragraph below about the preparation of carbonyl compounds then answer the questions
that follow.

To make propanal, propan-1-ol is heated gently with acidified potassium dichromate, K2Cr2O7. The
acidified dichromate is added a drop at a time to the alcohol and the propanal is distilled off
immediately, leaving unreacted propan-1-ol in the flask. The mixture turns green as the orange
dichromate ions are reduced to chromium(III) ions. Further heating oxidises the alcohol in the flask to
propanoic acid. Propan-2-ol can be oxidised in a similar way but the product need not be distilled off
immediately.

i Identify the oxidising agent in these reactions.

ii Write formulae for the dichromate ion and the chromium(III) ion.

iii How do you know from the information in the passage that propanal has a lower boiling point than
propan-1-ol?

iv Why is the propanal distilled off straight away and not refluxed?

v What is the name of the organic product formed when propan-2-ol is oxidised?

vi Why does the product of the oxidation of propan-2-ol not need to be distilled off immediately?

d Write equations for the following reactions using structural formulae.

i The reduction of butan-2-one by LiAlH4.

ii The reduction of propanal by NaBH4.

iii The reduction of hexan-2,4-dione by LiAlH4.

e Give the name of each of the products in part d.

Exercise 18.2 Distinguishing carbonyl compounds
This exercise will familiarise you with the use of Tollens’ reagent and Fehling’s solution to distinguish
aldehydes from ketones. It also revises the use of 2,4-dinitrophenylhydrazine (2,4-DNPH) to identify
particular carbonyl compounds.

a Copy and complete these statements.

When propanal is warmed gently with Tollens’ reagent the colour changes from __________ to a
__________ mirror. Propanal is oxidised to __________ __________. Silver ions are __________ to silver. When
propanal is warmed gently with Fehling’s solution, the colour changes from __________ to __________.
Propanal is oxidised to __________. Copper(II) ions are __________ to __________ ions. When a ketone is
heated with Tollens’ reagent __________.

Particular aldehydes and ketones can be identified by reacting them with 2,4-DNPH in a condensation
reaction. Yellow or orange crystalline precipitates are formed which have specific melting points.

TIPS

Tollens’ reagent and Fehling’s solution both oxidise aldehydes but

not ketones.

You need to know the colour changes that occur when these
reagents oxidise reducing agents.

b Copy and complete these statements.

A solution of 2,4-DNPH is added to a carbonyl compound. An __________ coloured __________ of a

dinitrophenylhydrazone is formed. The precipitate is purified by __________ and the __________ point is
measured. Each dinitrophenylhydrazone derivative of an aldehyde or __________ has a characteristic
melting point which can be compared with known data book values.

c The reaction between 2,4-DNPH and ethanal, CH3CHO, is shown.

RNH2 + CH3CHO → RN=CHCH3 + H2O

where R is the rest of 2,4-DNPH molecule.

Explain why this is a condensation reaction.

d The table gives the melting points of some dinitrophenylhydrazones.

Dinitrophenylhdyrazone Melting point / °C

propanal 150

butanal 126

hexanal 104

propanone 126

butan-2-one 117

pentan-2-one 144

Table 18.1: Melting points of some dinitrophenylhydrazones.

The melting point of the dinitrophenylhydrazone derivative of an unknown carbonyl compound, X, is

126 °C.

i How does the table of melting points help in the identification of X?

ii Describe one other experiment you could do to confirm the identity of X.