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1.

A chemist was investigating the reactions of benzene, phenol and cyclohexene with
bromine. She found that they all reacted with bromine but under different conditions.
(a)

The chemist found that when benzene reacts with bromine, a halogen carrier is
required as a catalyst.
Write an equation for this reaction.
You do not need to show the halogen carrier in your equation.

[1]

(b)

The chemist also found that when phenol or cyclohexene reacts with bromine, a
halogen carrier is not required.
(i)

The chemist observed that bromine decolourises when it reacts with


phenol.
What other observation would she have made?
Draw the structure of the organic product formed.
Observation ...........................................................................................
Organic product:

[2]

(ii)

Cyclohexene also decolourises bromine.


Name the organic product formed.
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[1]

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(iii)

Explain the relative resistance to bromination of benzene compared to


phenol and compared to cyclohexene.
In your answer, you should use appropriate technical terms, spelt correctly.
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[5]
[Total 9 marks]

2.

Compound A, shown below, is being considered as an azo dye by a chemical


company. A chemist planned a two-stage synthesis of compound A starting from an
aromatic amine.
N
H 3C

O H

com pound A

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The aromatic amine is first converted into a diazonium ion.

Draw the displayed formula of the aromatic amine and of the diazonium ion.

State the reagents and conditions for each stage in the synthesis of compound A
from an aromatic amine.

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[Total 5 marks]

3.

Hydroxyethanal, HOCH2CHO, is sometimes referred to as the first sugar as it is the


simplest possible molecule that contains both an aldehyde group and an alcohol group.
A biochemist investigated some redox reactions of hydroxyethanal and found that
several different products were produced.
(a)

The biochemist reacted hydroxyethanal with Tollens reagent.


(i)

State what the biochemist would see when hydroxyethanal reacts with
Tollens reagent.
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[1]

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(ii)

Write the structural formula of the organic product formed when


hydroxyethanal reacts with Tollens reagent.

[1]

(b)

The biochemist also reacted hydroxyethanal with acidified dichromate by heating


under reflux.
Write an equation for this oxidation.
Use [O] to represent the oxidising agent.

[2]

(c)

The biochemist then reduced hydroxyethanal using aqueous NaBH4.


(i)

Write the structural formula of the organic product.


................................................................................................................
[1]

(ii)

Outline the mechanism for this reduction.


Use curly arrows and show any relevant dipoles.

[4]
[Total 9 marks]

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4.

Aspirin and paracetamol are commonly available painkillers.


O

C O O H
H 3C

H 3C

O H

H
a s p ir in

p a ra c e ta m o l

Aspirin and paracetamol can be prepared using ethanoic anhydride, (CH3CO)2O.


Some examples of the reactions of ethanoic anhydride are shown below.
reaction 1

(CH3CO)2O + CH3OH CH3COOCH3 + CH3COOH

reaction 2

(CH3CO)2O + CH3NH2 CH3CONHCH3+ CH3COOH

reaction 3

(CH3CO)2O + C6H5OH CH3COOC6H5 + CH3COOH

Draw the structure of a compound that could react with ethanoic anhydride to form
aspirin.

[Total 1 mark]

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5.

Propanal, CH3CH2CHO, can be used in the synthesis of organic compounds.


CH3CH2CHO reacts with NaBH4 in a nucleophilic addition reaction. The nucleophile
can be represented as a hydride ion, H. A mechanism for the reaction is shown below.
H +
+
H
O

O
C H 3C H

N aBH 4
s te p 1

H
H

(i)

C H 3C H

s te p 2
H

o r g a n ic p r o d u c t

Add 'curly arrows' to the mechanism to show how the intermediate reacts with the
water molecule in step 2.
[2]

(ii)

Draw the structure of the organic product in the box above.


[1]

(iii)

What is meant by the term nucleophile?


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[1]

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(iv)

Describe, in words, exactly what is happening to the electron pairs and bonds in
step 1 of the mechanism above.
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[3]
[Total 7 marks]

6.

Benzene reacts with chlorine in the presence of a halogen carrier, such as AlCl3.
(a)

(i)

Write the equation for the reaction of benzene with chlorine.

[1]

(ii)

How does the halogen carrier allow the reaction to take place?
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[1]

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(iii)

Outline a mechanism for this reaction.


Include curly arrows and relevant dipoles.

[4]

(iv)

State the name of this mechanism.


...............................................................................................................
[1]

(b)

In contrast to benzene, the reaction of an alkene with bromine does not need a
halogen carrier.
Compare the different reactivities of benzene and alkenes towards chlorine.
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[3]
[Total 10 marks]

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7.

An unknown colourless liquid with molecular formula C4H8O was thought to be one of
butanal, but-3-en-1-ol, or butanone.

O
C

C
H

b u ta n a l

(a)

O H

H
H

b u t-3 -e n -1 -o l

b u ta n o n e

State a simple chemical test that would positively identify:


(i)

butanal only;
reagent .................................................................................................
observation ...........................................................................................
organic product .....................................................................................
[3]

(ii)

but-3-en-1-ol only.
reagent .................................................................................................
observation ...........................................................................................
type of reaction .....................................................................................
[3]

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(b)

Butanal and butanone both react with 2,4-dinitrophenylhydrazine to produce


mixtures containing orange precipitates.
Outline how the mixtures containing these orange precipitates can be used to
distinguish between butanal and butanone.
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[3]
[Total 9 marks]

8.

The method below can be used to make phenylamine from nitrobenzene in the
laboratory.
3.69 g of nitrobenzene and 8 g of tin (an excess) were placed into a flask. The flask
was fitted with a reflux condenser. Concentrated hydrochloric acid was then added
dropwise to the flask.
The mixture was heated for 30 minutes to complete the reaction.
Once the mixture had cooled, concentrated sodium hydroxide solution was added until
the mixture was alkaline.
Purification gave a 72.1% yield of phenylamine.

(a)

Reaction of nitrobenzene with the tin and hydrochloric acid produces


phenylammonium chloride as the organic product.
(i)

Complete the equation for this reaction.


N O

[H ]

H C l

NH

+ C l

p h e n y la m m o n iu m c h lo r id e
[2]

(ii)

State what the symbol [H] in the equation represents.

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[1]

(b)

When the sodium hydroxide was added, the phenylammonium chloride was
converted to phenylamine.
Write an equation for this reaction.

[2]

(c)

Calculate the mass of phenylamine that was produced from the 3.69 g of
nitrobenzene in this experiment. Give your answer to three significant figures.
Mr: nitrobenzene,123; phenylamine, 93.1

mass of phenylamine = . g
[4]
[Total 9 marks]

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11

9.

In this question, one mark is available for the quality of spelling, punctuation and
grammar.
Describe with the aid of suitable diagrams the bonding and structure of a benzene
molecule.

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[6]
Quality of Written Communication [1]
[Total 7 marks]

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10.

The demand for natural shampoos and detergents has led to the development of more
biodegradable detergents such as sorbitan monolaurate, which is made from plants.
O H
O

11

23

O
HO

O H
s o r b ita n m o n o la u r a te

(i)

Suggest a type of reaction that could break down sorbitan monolaurate when it is
washed into drains and rivers.
Explain your answer and state the type of organic products formed.
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[3]

(ii)

Suggest one other reason why detergents such as sorbitan monolaurate are
regarded as environmentally friendly.
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[1]
[Total 4 marks]

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13

11.

The diagram below shows some reactions of phenol.


O

O H

N a

Br

Br

Br
O H

II

phenol
IV

III
O H

NO

O H

N
N

(i)

On the diagram above, identify suitable reagents that could be used to carry out
reactions I, II and III.
[3]

(ii)

State a use for the compound formed in reaction IV.


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[1]

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(iii)

Outline how you could carry out reaction IV in the laboratory starting from phenol
and a suitable aromatic amine.
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[5]
[Total 9 marks]

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15

12.

In this question, one mark is available for the quality of spelling, punctuation and
grammar.
Phenol reacts much more readily with bromine than benzene does.

Describe, with the aid of a diagram, the bonding in benzene.

Explain why electrophiles, such as bromine, react much more readily with phenol
than with benzene.

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[7]
Quality of Written Communication [1]
[Total 8 marks]

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13.

But-2-enal, CH3CH=CHCHO, is a pale yellow, flammable liquid with an irritating odour.


(a)

(i)

Describe a simple chemical test that would show that but-2-enal is an


aldehyde.
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[2]

(ii)

Explain why this test gives a different result with aldehydes than it does with
ketones.
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[1]

(b)

But-2-enal also reacts with sodium borohydride, NaBH4.


(i)

Identify the organic compound formed in this reaction.

...............................................................................................................
[1]

(ii)

State the type of chemical reaction occurring.


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[1]

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(c)

Precautions must be taken to prevent but-2-enal catching fire.


Construct a balanced equation for the complete combustion of but-2-enal,
C4H6O.

[1]
[Total 6 marks]

14.

(a)

The reaction of trichloroethanal with water is a nucleophilic addition reaction. It


can be catalysed by small amounts of hydroxide ions, OH.
Complete the diagram below to suggest a mechanism for this reaction. Show all
the relevant dipoles and curly arrows.
H
Cl
Cl

Cl

C
H

Cl

Cl

Cl

O
H

[5]

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18

(b)

The recommended adult dose of chloral hydrate as a sedative is 250 mg, three
times a day.
Calculate the mass of trichloroethanal you would need to react with water to
make one weeks supply of chloral hydrate for an adult, assuming a 60% yield.
Mr: chloral hydrate, 165.5; trichloroethanal, 147.5

mass of trichloroethanal = g
[3]
[Total 8 marks]

15.

Chloral hydrate is broken down in the body after several hours. One reaction is
oxidation to trichloroethanoic acid.
Complete the equation for this reaction below.
Cl3CCH(OH)2

[O]

[Total 1 mark]

16.

An ester D with the formula, CH3CH2COOCH2CH(CH3)2, is used in rum flavouring.


(a)

Draw a displayed formula of ester D.

[2]

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(b)

Outline how you could obtain a sample of ester D, starting with a named
carboxylic acid and a named alcohol.
Include any essential reaction conditions and write an equation for the reaction.
You do not need to include any details of the separation or purification of the
ester.

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[6]

(c)

State a spectroscopic method that could be used to confirm that a sample of


ester D has a molecular mass of 130.
Explain how you would obtain the molecular mass of D from the spectrum.
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[2]
[Total 10 marks]

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20

17.

Linoleic acid, C17H31COOH, is an unsaturated fatty acid found in triglycerides from


sunflower oil.
(i)

Draw the structure of the triglyceride made from linoleic acid, C17H31COOH, and
propane-1,2,3-triol. Show clearly all the bonds in the ester groups.

[2]

(ii)

Deduce the number of carbon to carbon double bonds in a molecule of the


triglyceride.
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[1]
[Total 3 marks]

18.

Explain why triglycerides are soluble in non-polar solvents and not in water.
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[Total 3 marks]

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21

19.

Compound A is used to add the flavour of mushrooms to foods.


O
C

H 3C
C
H

C H

C
CH

com pound A

(a)

(i)

Apart from the benzene ring, name the two functional groups in
compound A.
.....................................................

.....................................................
[2]

(ii)

Draw the skeletal formula of compound A.

[1]

(iii)

Deduce the molecular formula of compound A.


...............................................................................................................
[1]

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(b)

Compound B is a stereoisomer of compound A.


Explain what is meant by the term stereoisomerism. Use compounds A and B to
illustrate your answer.
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[2]

(c)

If the food is cooked for a long time, naturally occurring acids catalyse the
hydrolysis of compound A.
Draw structures to show the two organic compounds formed by the acid
hydrolysis of compound A.

[2]

(d)

The hydrolysis of compound A can be monitored by sampling the mixture at


regular intervals, separating the components, and recording their infra-red
spectra.
(i)

State two absorptions that would be expected in the infra-red spectrum of


compound A, and identify the parts of the molecule responsible for each.
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[2]

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(ii)

Suggest a wavenumber range within the spectrum that could be used to


clearly distinguish compound A from the products formed by the hydrolysis
reaction.
Explain your answer.
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[2]
[Total 12 marks]

20.

Phenol reacts readily with dilute nitric acid at room temperature in a nitration reaction to
produce a mixture of products as shown below.
O H

O H
d ilu t e H N O
ro o m te m p

O H
N O

and

N O

(a)

Suggest the structure of another organic product that is likely to be formed in the
nitration of phenol.

[1]

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24

(b)

Assuming a yield by mass of 27% for 4-nitrophenol, calculate the mass of 4nitrophenol that would be produced from 100 g of phenol. Show your working.
Give your answer to an appropriate number of significant figures.

mass of 4-nitrophenol = g
[4]

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(c)

In this question, one mark is available for the quality of spelling, punctuation and
grammar.
Compare the reagents and conditions for the nitration of phenol with those used
for the nitration of benzene.
State and explain the effect of the OH group on the reactivity of the benzene
ring in phenol.
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[7]
Quality of Written Communication [1]
[Total 13 marks]

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26

21.

4-Nitrophenol can be converted into a range of useful organic chemicals. Draw the
structures of the organic products formed in the following reactions.

N a O H (a q )

B r2(a q )

S n (s )
conc.
H C l(a q )

O H

NO

C H 3 C O C l(I)

[Total 4 marks]

22.

The reducing agent, NaBH4, is used widely in organic chemistry. One example is for
the reduction of diphenylethanedione, C14H10O2, shown below.
O
C
C
O
d ip h e n y le th a n e d io n e

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(i)

Draw a displayed formula to show the structure of the organic product that would
be formed by reducing diphenylethanedione with excess NaBH4.

[1]

(ii)

Complete and balance the equation for this reaction, using [H] to represent the
reducing agent.
C14H10O2

[1]
[Total 2 marks]

23.

Diphenylethanedione is a pale yellow colour, which disappears when it is reduced.


The colour results from the arrangement of the delocalised -bond electrons.
Explain what is meant by the term delocalised -bond electrons.
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[Total 2 marks]

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24.

Coloured organic compounds also include azo dyes.


Describe how an azo dye can be made from phenylamine. Show the structure of the
azo dye and the organic intermediate in your answer.
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[Total 6 marks]

25.

(a)

In this question, one mark is available for the quality of use and organisation of
technical terms.
Bromine is used in organic chemistry to carry out a variety of electrophilic
reactions.
(i)

Describe and explain how a molecule of bromine acts as an electrophile.


Illustrate your answer with a diagram showing relevant dipoles and curly
arrows.

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(ii)

Use your answer to (i) to explain why bromine reacts much more readily
with cyclohexene than it does with benzene.

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[7]
Quality of Written Communication [1]

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(b)

The compound iodine monobromide, IBr, also reacts with benzene in an


electrophilic reaction.
(i)

Which compound would be the main product of this reaction, iodobenzene


or bromobenzene? Explain your answer.
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[2]

(ii)

Deduce an equation for the reaction of iodine monobromide with benzene.

[1]
[Total 11 marks]

26.

Glyceryl trihexanoate is a triglyceride that can be made from glycerol


(propane-1,2,3-triol) and hexanoic acid, C5H11COOH.
Draw the structure of glyceryl trihexanoate. Show every bond in the functional groups.

[Total 2 marks]

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31

27.

As a wine ages, some of the acids slowly react with ethanol in the wine to produce
esters.
(i)

Draw a displayed formula to show the structure of the ester formed when lactic
acid reacts with ethanol.

[1]

(ii)

Suggest what effect this process might have on the flavour of the wine. Explain
your reasoning.
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[1]
[Total 2 marks]

28.

Salicylic acid is used in the manufacture of aspirin tablets. In the UK around 3500
tonnes of salicylic acid are manufactured per year.
O
HO

O H

s a lic y lic a c id
Salicylic acid is manufactured from phenol in three stages.

(a)

Phenol is first converted to sodium phenoxide, C6H5ONa+.


(i)

State a reagent that could be used for this reaction.


...............................................................................................................
[1]

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(ii)

Write a balanced equation for this reaction.

[1]

(b)

The phenoxide ion is then combined with carbon dioxide under high pressure to
form the salicylate ion.
O

C O

O H

This reaction is an electrophilic substitution reaction, which occurs by the


incomplete mechanism shown below. Carbon dioxide acts as the electrophile.
H
O
C

s te p 1

H
C

s te p 2

O
in te r m e d ia te

(i)

Add partial charges + and to show the polarisation of the C=O bonds in
the carbon dioxide molecule above.
[1]

(ii)

Complete the mechanism by adding curly arrows to show the movement of


electron pairs in step 1 to give the intermediate shown.
[2]

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(iii)

Carbon dioxide is normally a very poor electrophile. However, this reaction


does occur because the benzene ring in the phenoxide ion is activated.
Explain how the benzene ring in the phenoxide ion is activated.
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[3]

(c)

In the final stage of this process, the salicylate ion is acidified to give salicylic
acid.
Assuming an overall yield by mass of 45% for this three stage process, calculate
the mass of phenol that is needed to produce the annual UK output of
3500 tonnes of salicylic acid.
Mr of phenol = 94.0; 1 tonne = 106 g

mass of phenol = ....................... tonnes


[4]
[Total 12 marks]

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34

29.

A dye can be made from 4-methylphenylamine and 2,6-dimethylphenol, shown below.


O H
H 3C
H 3C

N H

C H

4 -m e th y lp h e n y la m in e

2 ,6 -d im e th y lp h e n o l

4-Methylphenylamine is dissolved in ice-cold hydrochloric acid and sodium nitrite is


added.
This mixture is then slowly added to an alkaline solution of the phenol to form the dye.

(i)

Identify the inorganic nitrogen-containing compound formed by the mixture of


hydrochloric acid and sodium nitrite.
........................................................................................................................
[1]

(ii)

Draw the structure of the organic compound formed in the ice-cold acidic mixture,
showing a displayed formula of the nitrogen-containing group.

[1]

(iii)

State the name of the type of organic compound drawn in (ii).


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[1]

(iv)

Suggest why the mixture must be kept at a low temperature.


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[1]

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(v)

Suggest the structure of the dye.

[2]
[Total 6 marks]

30.

In this question, one mark is available for the quality of use and organisation of
scientific terms.
4-Methylphenylamine can be manufactured from benzene in three stages.

s ta g e 1

benzene

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s ta g e 2

N H

C H

s ta g e 3

4 - m e th y lp h e n y la m in e

36

Describe how benzene could be converted by these three stages into 4methylphenylamine.
Include the structures of the intermediate compounds A and B. State the reagents and
conditions. Give a balanced equation for each stage.
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[11]
Quality of Written Communication [1]
[Total 12 marks]

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31.
O H

geraniol
Mild oxidation of geraniol gives an aldehyde Y.
(i)

Draw the skeletal formula of aldehyde Y below.

aldehyde Y
[2]

(ii)

Complete the equation for the oxidation of geraniol to aldehyde Y.


C9H15CH2OH +

[O]

[2]
[Total 4 marks]

32.

Reaction of geraniol with ethanoic acid can be used to make ester Z, which is used in
chewing gum and desserts.
(i)

Suggest why esters are used in the manufacture of foods.


........................................................................................................................
[1]

(ii)

State the conditions needed to make ester Z from geraniol and ethanoic acid.
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[2]

(iii)

Complete the equation for the formation of ester Z.


+ C9H15CH2OH

[3]
[Total 6 marks]

33.

The nitration of benzene is a very important industrial reaction.


(a)

Name two types of commercially important material whose manufacture involves


the nitration of benzene.
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[2]

(b)

State the conditions required for the nitration of benzene using nitric acid and
sulphuric acid.
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[2]

(c)

Write a balanced equation for the nitration of benzene.

[2]

The Ravensbourne School

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(d)

The mechanism for the reaction is given below.


Step 1: formation of the electrophile, NO2+, from HNO3 and H2SO4
HNO3 + H2SO4 H2O + NO2+ + HSO4
Steps 2 and 3: substitution of NO2+ into the benzene ring
+
NO

H
s te p 2

NO

NO
2

s te p 3

+
in te r m e d ia te

Step 4: protonation of the HSO4


H+ + HSO4 H2SO4
(i)

Explain what a curly arrow

represents in this type of mechanism.

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[2]

(ii)

State why the NO2+ is described as an electrophile in this mechanism.


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[1]

(iii)

State why this mechanism is described as substitution.


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[1]

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(iv)

How does the mechanism show that the sulphuric acid is acting as a
catalyst?
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[1]

(e)

In this question, one mark is available for the quality of spelling, punctuation and
grammar.
The benzene ring and the ring in the intermediate formed after step 2 have
different structures shown below. Both structures have -bonds.

+
b e n z e n e r in g

r in g in t h e in te r m e d ia te

Deduce how many electrons are involved in the -bonding in each structure and
describe how their arrangements are different.
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[5]
Quality of Written Communication [1]
[Total 17 marks]

The Ravensbourne School

41

34.

E110 is a yellow colouring agent that is commonly added to a variety of foods.


E110 contains an azo dye made from an amine and a phenol.
(a)

Describe how you would prepare a sample of an azo dye in the laboratory from
an amine, a phenol and any other necessary reagents.

Include in your answer

essential reagents and conditions for each stage

names of any functional groups formed during the process.


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[7]

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(b)

The structure of E110 is shown below.


O H
N
SO

SO

(i)

Na

N a

E 11 0

On the structure above, draw a circle around the functional group that
identifies this molecule as an azo dye.
[1]

(ii)

Deduce how many carbon and hydrogen atoms are in a molecule of E110.
..................... carbon atoms and ..................... hydrogen atoms.
[2]

(c)

The solubility of E110 in water can be improved by converting the phenolic OH


group into a charged O group.
Suggest a suitable reagent that will convert the OH group in E110 into an O
group.
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[1]

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(d)

In the boxes below, draw the structures of a phenol and an amine that could be
used to make E110 by the method in part (a).
Assume that the SO3Na+ groups do not change during the process.

phenol

amine
[2]
[Total 13 marks]

35.

Benzoic acid and phenylmethanol will react with each other in the presence of a
suitable catalyst.
(i)

State a suitable catalyst for this reaction.


........................................................................................................................
[1]

(ii)

Draw the displayed formula of the organic product.

[2]
[Total 3 marks]

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44

36.

Cinnamaldehyde can be reduced using sodium borohydride, NaBH4.


(i)

State which functional group reacts with the sodium borohydride.


........................................................................................................................
[1]

(ii)

Complete and balance the equation for this reaction.


C6H5CH=CHCHO

[H]

[1]
[Total 2 marks]

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45

37.

In this question, one mark is available for spelling, punctuation and grammar.
Tollens reagent can be used to identify the aldehyde group in cinnamaldehyde.

Describe how you would make Tollens reagent and carry out this test in the
laboratory.

Explain what happens to both the Tollens reagent and the cinnamaldehyde in
this reaction. Identify the organic product.

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[7]
Quality of Written Communication. [1]
[Total 8 marks]

The Ravensbourne School

46

38.

1,4-Diaminobenzene is used in the manufacture of a variety of materials including dyes


and polymers.
H 2N

NH

1 ,4 -d ia m in o b e n z e n e

(a)

Explain what is meant by the term 1,4-diamino in the name of this compound.

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[2]

(b)

1,4-diaminobenzene can be manufactured from 1,4-dinitrobenzene.


O 2N

N O

1 , 4 - d in it r o b e n z e n e

(i)

H 2N

N H

1 , 4 - d ia m in o b e n z e n e

What type of reaction is this?


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[1]

(ii)

State reagents and conditions that could be used to carry out this reaction.
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[2]

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(iii)

Complete and balance the equation below for this reaction.

O 2N

NO

[H ]

H 2N

NH

+
[2]

(c)

1,4-Diaminobenzene is used to make permanent black dye for hair.


1,4-Diaminobenzene can irritate the skin because it is basic. Therefore, it is
sometimes neutralised with excess hydrochloric acid to give the salt.
(i)

Explain how the amino groups in a primary amine such as


1,4-diaminobenzene allow the molecule to act as a base.
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[2]

(ii)

Draw the structure of the salt formed in this reaction.

[2]

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(iii)

State whether you would expect hexane-1,6-diamine to be a stronger or


weaker base than 1,4-diaminobenzene. Explain your reasoning.
N H

H 2N

h e x a n e -1 ,6 -d ia m in e
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[3]
[Total 14 marks]

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