Benzene

1.
The following passage gives a method for the preparation of nitrobenzene.

Place 35 cm3 of concentrated nitric acid in a 500 cm3 flask, and add slowly 40 cm3 of
concentrated sulphuric acid, keeping the mixture cool during the addition by immersing the flask
in cold water. Place a thermometer in the nitrating mixture, and add very slowly 29 cm 3 of
benzene. The benzene should be added about 3 cm3 at a time, and the contents of the flask
thoroughly mixed after each addition; the temperature of the mixture must not be allowed to rise
above 40 C, and the flask must be cooled in cold water if necessary.
When all the benzene has been added, fit a reflux condenser to the flask, and heat the latter in a
water bath at 60 C for 45 minutes. During this period the flask should be removed from the
water bath from time to time and vigorously shaken.
After this heating period, pour the contents of the flask into a large excess of cold water (about
300 cm3), and stir the mixture vigorously. Decant off as much of the upper aqueous layer as
possible, and transfer the residue to a separating funnel. Run off the lower nitrobenzene layer
into a beaker, and reject the aqueous layer. Then wash the nitrobenzene successively first with an
equal volume of cold water and then with dilute sodium carbonate solution.
Transfer the nitrobenzene to a small flask, add some granular calcium chloride, and leave until
the liquid is quite clear. Filter the nitrobenzene into a small, dry flask, and distil, collecting the
fraction which boils between 207 C and 211 C.
(Adapted from Mann FG & Saunders BC, Practical Organic Chemistry, 4th ed:
Longman, 1960.)
(a)
Suggest reasons for each of the following:

(i)
the use of a mixture of concentrated nitric and sulphuric acids.
(2)
(ii)
the slow addition of the benzene to the nitrating mixture.
(1)
(iii)
the need to keep the temperature below 40 C during the addition.
(1)
(iv)
the need to keep the reaction temperature at 60 C.
Gateway International School (PVT) Limited
(1)
(v)
the necessity to shake the mixture from time to time.
(2)
(vi)
the addition of the reaction mixture to an excess of cold water.
(1)
(vii) the need to wash with water and then with sodium carbonate solution.
(1)
(viii) the distillation between 207 C and 211 C.
(1)
(b)
Nitrobenzene can be nitrated further to give 1,3-dinitrobenzene:

N O
N O
By analogy with the reduction of nitrobenzene to phenylamine, suggest reagents and

conditions by which 1,3-dinitrobenzene can be converted to 1,3-diaminobenzene.
..
..
..
(3)
(c)
Nomex is a du Pont fibre, used for flame-retardant clothing, which can resist temperatures
of 1000 C for 12 seconds, enough to have enabled the Benetton Formula 1 team to have
survived a serious fire during the 1994 Grand Prix season. Nomex is a polymer which
could in principle be made from 1,3-diaminobenzene and benzene-1,3-dicarboxylic acid:
N H
C O 2H
N H
CO 2H
(i)
Draw a representative length of the Nomex polymer chain.

(2)
(ii)
What type of polymer is Nomex?
(1)
(iii)
Dicarboxylic acids are not usually used in making this type of polymer. They are
generally made from acid chlorides. Suggest why this is so.
(2)
(iv)
Suggest how benzene-1,3-dicarboxylic acid could be converted to its diacid

chloride, and draw its structure.
(2)
(Total 20 marks)
2.
An active ingredient in many sunscreen creams is 4-aminobenzoic acid.
C O O H
N H
It can be prepared as described below.

To 15 g of 4-nitrobenzoic acid, in a flask fitted with a reflux condenser, add 35 g of powdered tin
3
and 75 cm of concentrated hydrochloric acid. Heat the mixture until the reaction commences,
remove the flame and shake the flask gently from time to time. After about 20 minutes cool and
3
decant the liquid into a beaker, wash the residual tin with 15 cm of water and add the washings
to the beaker. Add concentrated ammonia solution until the solution is just alkaline, filter off the
precipitate of hydrated tin oxide, wash it well with water and add these washings to the filtrate.
Acidify the filtrate with concentrated ethanoic acid and evaporate on a water bath until crystals
commence to separate. Cool in ice, filter the crystals at the pump and dry in a steam oven. The
yield of 4-aminobenzoic acid, melting temperature 192 C, is 12 g.
(After A Textbook of Practical Organic Chemistry by A. E. Vogel)
(a)
Suggest reasons for each of the following:

(i)
the use of a mixture of tin and hydrochloric acid;
......................................................................................................................
(1)
(ii)
heating the mixture but then taking the flame away;

......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(iii)
the use of a reflux condenser;

......................................................................................................................
......................................................................................................................
(1)
(iv)
adding ammonia;
......................................................................................................................
......................................................................................................................
(1)
(v)
collecting all the washings;

......................................................................................................................
......................................................................................................................
(1)
(vi)
adding ethanoic acid.

......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b)
Calculate the percentage yield of 4-aminobenzoic acid from 4-nitrobenzoic acid,

(NO2)C6H4COOH.
(3)
(c)
Suggest a two step synthetic route for the preparation of 4-nitrobenzoic acid from
methylbenzene, giving reagents and conditions for each step.
(4)
(d)
4-aminobenzoic acid can be converted into benzocaine,

O
O C H 2C H
N H
a local anaesthetic which is used to relieve the pain of sunburn.

(i)
Suggest reagents and conditions for carrying out this conversion.

......................................................................................................................
......................................................................................................................
(2)
(ii)
Name the type of reaction involved in this step.

......................................................................................................................
(1)
(e)
A better local anaesthetic than benzocaine is novocaine,
H
O
CH
C H
C H 2C H
C H 2C H
C l
N H
10
which can be injected into tissues.

State with a reason what feature of novocaine, absent in benzocaine, might be responsible
for its solubility in non-fatty tissue.
................................................................................................................................
................................................................................................................................
(2)
(Total 20 marks)
3.
Benzene is stable to all but the strongest of oxidising agents, although carbon-containing sidechains can be oxidised to the COOH group. Mono-substituted benzene derivatives give
benzoic acid.
3
The side-chain oxidation can be performed by heating under reflux 2.00 cm (1.73 g) of
methylbenzene, 7.00 g of potassium manganate(VII), 2.00 g of potassium hydroxide and
3
150 cm of water. After two hours of heating under reflux, sulphur dioxide is blown through the
hot solution to remove the dark brown precipitate and leave a very pale pink solution. On
cooling, benzoic acid crystallises out and can be filtered off, washed and dried.
The overall reaction is:
2MnO4 + C6H5CH3 2MnO2 + H2O + C6H5COO + OH

(a)
The amount of potassium manganate(VII) added to the mixture is intended to be an

excess. Calculate whether this is so.
1
[Molar masses/g mol : C6H5CH3 = 92, KMnO4 = 158]
(3)
(b)
The following half-equations are needed in this part of the question.

2
SO2 + 2H2O
Mn
SO4 + 4H + 2e
MnO2 + 4H + 2e
(i)
2+
+ 2H2O
Derive the equation for the reaction that occurs when sulphur dioxide is blown into
the aqueous suspension of the dark brown solid.
(1)
(ii)
Give the formula of the very pale pink ion remaining in the solution after the
sulphur dioxide has been passed through.
(1)
(c)
Give details of how you would purify benzoic acid by recrystallization.

(5)
(Total 10 marks)
11
12

Benzene

Uploaded by

Copyright:

Available Formats

Benzene

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Benzene

Uploaded by

Copyright:

Available Formats

1.

The following passage gives a method for the preparation of nitrobenzene.

Suggest reasons for each of the following:

the use of a mixture of concentrated nitric and sulphuric acids.

the slow addition of the benzene to the nitrating mixture.

the need to keep the temperature below 40 C during the addition.

the need to keep the reaction temperature at 60 C.

Gateway International School (PVT) Limited

Gateway International School (PVT) Limited

the necessity to shake the mixture from time to time.

the addition of the reaction mixture to an excess of cold water.

(viii) the distillation between 207 C and 211 C.

Nitrobenzene can be nitrated further to give 1,3-dinitrobenzene:

By analogy with the reduction of nitrobenzene to phenylamine, suggest reagents and

Gateway International School (PVT) Limited

Gateway International School (PVT) Limited

Draw a representative length of the Nomex polymer chain.

What type of polymer is Nomex?

Suggest how benzene-1,3-dicarboxylic acid could be converted to its diacid

An active ingredient in many sunscreen creams is 4-aminobenzoic acid.

It can be prepared as described below.

Suggest reasons for each of the following:

the use of a mixture of tin and hydrochloric acid;

Gateway International School (PVT) Limited

Gateway International School (PVT) Limited

heating the mixture but then taking the flame away;

the use of a reflux condenser;

collecting all the washings;

adding ethanoic acid.

Calculate the percentage yield of 4-aminobenzoic acid from 4-nitrobenzoic acid,

Gateway International School (PVT) Limited

Gateway International School (PVT) Limited

4-aminobenzoic acid can be converted into benzocaine,

a local anaesthetic which is used to relieve the pain of sunburn.

Suggest reagents and conditions for carrying out this conversion.

Name the type of reaction involved in this step.

A better local anaesthetic than benzocaine is novocaine,

Gateway International School (PVT) Limited

Gateway International School (PVT) Limited

which can be injected into tissues.

2MnO4 + C6H5CH3 2MnO2 + H2O + C6H5COO + OH

The amount of potassium manganate(VII) added to the mixture is intended to be an

The following half-equations are needed in this part of the question.

Give details of how you would purify benzoic acid by recrystallization.

Gateway International School (PVT) Limited

Gateway International School (PVT) Limited

You might also like