2814/01

ADVANCED GCE
CHEMISTRY
Chains, Rings and Spectroscopy
TUESDAY 29 JANUARY 2008

Afternoon
Time: 1 hour 30 minutes

*CUP/T51626*

Additional materials: Scientific calculator

Data Sheet for Chemistry (Inserted)

INSTRUCTIONS TO CANDIDATES

Write your name in capital letters, your Centre Number and Candidate Number in the boxes above.
Use blue or black ink. Pencil may be used for graphs and diagrams only.
Read each question carefully and make sure that you know what you have
FOR EXAMINERS USE
to do before starting your answer.
Answer all the questions.
Qu.
Max
Mark
Do not write in the bar codes.
Do not write outside the box bordering each page.
1
11
Write your answer to each question in the space provided.
2

12

13

13

14

TOTAL

90

INFORMATION FOR CANDIDATES

The number of marks for each question is given in brackets [ ] at the end of
each question or part question.
The total number of marks for this paper is 90.
You will be awarded marks for the quality of written communication where
this is indicated in the question.
You may use a scientific calculator.
A copy of the Data Sheet for Chemistry is provided as an insert with this
question paper.
You are advised to show all the steps in any calculations.

This document consists of 19 printed pages, 1 blank page and a Data Sheet for Chemistry.
SP (SLM/SLM) T51626/3

OCR 2008 [F/100/3426]

OCR is an exempt Charity

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2
Answer all the questions.
1

The table below gives information about some carbonyl compounds.

structural formula

boiling
point / C

melting point of the

2,4-dinitrophenylhydrazine
derivative / C

CH3CH2CH2CHO

74

123

............................

(CH3)2CHCHO

64

187

butanone

CH3COCH2CH3

80

117

pentanal

CH3CH2CH2CH2CHO

name
butanal

methylbutanone

98

(CH3)2CHCOCH3

94

120

pentan-2-one

.........................................

102

143

pentan-3-one

.........................................

102

156

hexanal

CH3CH2CH2CH2CH2CHO

131

104

(a) In the table above, complete the missing name and structural formulae.

[2]

(b) Predict the boiling point of pentanal.

...............................................................................................................................................[1]
(c) (i)

State what you would

2,4-dinitrophenylhydrazine.

observe

when

carbonyl

compound

reacts

with

.......................................................................................................................................[1]
(ii)

State why the melting points of the derivatives are more useful in the identification of
carbonyl compounds than the boiling points of the carbonyl compounds. Use the data in
the table to justify your answer.
...........................................................................................................................................
...........................................................................................................................................
.......................................................................................................................................[1]

(d) Carbonyl compounds can also be analysed by mass spectrometry.

State the m/e value of the molecular ion peak you would expect to find on the mass spectrum
of butanal.
...............................................................................................................................................[1]
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(e) The n.m.r. spectrum of one of the carbonyl compounds in the table is shown below.
6

absorption
of
energy
..............
1

10

(i)

..............
..............
1

5
/ppm

What do the relative peak areas on the spectrum represent?

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

(ii)

The peaks at = 1.0 and 9.5 ppm are both doublets.

What does this information tell you about the structure?
...........................................................................................................................................
...........................................................................................................................................
.......................................................................................................................................[1]

(iii)

Draw the displayed formula of the compound.

[1]
(iv)

Label the spectrum to show which atoms on your structure are responsible for each peak
on the spectrum.
[2]
[Total: 11]

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2

Mordant Orange 1 is an azo-dye with the structure shown below.

O2N

COOH

N
N

OH

Mordant Orange 1
(a) Draw a circle around the azo group that identifies this molecule as an azo-dye.

[1]

(b) Describe how Mordant Orange 1 can be made starting from 4-nitrophenylamine and another
suitable organic reagent.
Include in your answer:

the structure of 4-nitrophenylamine, the intermediate diazonium ion and the other organic
reagent;
essential reagents and conditions for each stage.

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(c) Mordant Orange 1 is yellow in acidic conditions, but changes to a red colour in the presence
of strong bases, such as aqueous sodium hydroxide.
Draw the structure of Mordant Orange 1 after reaction with excess aqueous sodium
hydroxide.

[2]
(d) The colour of the dye can also be changed by reducing the nitro group.
(i)

State suitable reagents to reduce a nitro group.

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

(ii)

Write an equation for the reduction of Mordant Orange 1. Use [H] to represent the
reducing agent.
You may simplify the structure of Mordant Orange 1 to O2N

[2]
[Total: 12]

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3

Glutamic acid is an amino acid, H2NCH(CH2CH2COOH)COOH.

(a) Glutamic acid has two stereoisomers.
Explain how these stereoisomers arise. Illustrate your answer with suitable diagrams.
...................................................................................................................................................
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...................................................................................................................................................

[3]
(b) Complete the table to show the structure of glutamic acid that would exist in an aqueous
solution at each pH value shown.
pH 1

pH 3
H
+

H3N

CH2CH2COOH

COO
pH 12

[2]
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(c) Glutathione is a naturally occurring molecule made from glutamic acid and two other amino
acids. The structure of glutathione is shown below.
O

H
H2N

CH2CH2

COOH

CH2

H
N

COOH

SH
glutathione
(i)

Show the structures of the other two amino acids used to make glutathione.

[2]
(ii)

State the type of reaction that takes place when glutathione is made from its three
constituent amino acids.
.......................................................................................................................................[1]

(iii)

Glutathione can be hydrolysed by enzymes. Describe one other way that this reaction
can be carried out in the laboratory.
...........................................................................................................................................
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.......................................................................................................................................[1]
[Total: 9]

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4

Thymol is a phenol that is used in mouthwashes.

OH
CH3
CH

H3C

CH3
thymol
(a) Suggest why phenols are often used in mouthwashes.
...............................................................................................................................................[1]
(b) Thymol can be manufactured from 3-methylphenol by a FriedelCrafts reaction.
(i)

Complete the equation for this reaction below.

OH

OH

CH3
+

H3C

H3C

CH

..............

CH3
[2]
(ii)

State a suitable catalyst for this reaction.

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

(c) In a typical mouthwash, the concentration of thymol is 3.0 103 mol dm3.
Calculate the mass of thymol that would be contained in a bottle containing 400 cm3 of
mouthwash. Show all your working clearly.

mass of thymol = .......................................................g [3]

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(d) Esters of thymol are used in some cosmetics.
An ester can be obtained by reacting thymol with ethanoyl chloride.
(i)

Draw the displayed formula of ethanoyl chloride.

[1]
(ii)

Ethanoyl chloride can be made from ethanoic acid.

State a suitable reagent and write a balanced equation for this reaction.
reagent ..............................................................................................................................
equation

[2]
(iii)

Draw the structure of the ester formed from thymol and ethanoyl chloride.

[1]
(iv)

State how you would expect the infra-red spectrum of the thymol ester to differ from the
spectrum of thymol.
...........................................................................................................................................
...........................................................................................................................................
.......................................................................................................................................[2]
[Total: 13]

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5

Poly(propene) is used in the manufacture of ropes.

(a) Write a balanced equation for the formation of poly(propene) from propene.

[1]
(b) The strength of the rope can be improved by using the stereochemical form of poly(propene)
which is described as isotactic.
Describe and explain with the aid of suitably labelled 3-D diagrams the three different
stereochemical forms of poly(propene).

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(c) Ropes can also be made from polymers such as Terylene.
Terylene is made from benzene-1,4-dicarboxylic acid and ethane-1,2-diol.
(i)

Draw the structures of the two monomers used to make Terylene.

[2]
(ii)

Draw the structure of a section of Terylene, showing one repeat unit.

[2]
[Total: 9]

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6

2-Phenylethylamine, C6H5CH2CH2NH2, is a compound that is found in chocolate.

(a) 2-Phenylethylamine can be synthesised by the two reactions shown below.
H

H
Cl

reaction 1

reaction 2
H

H
NH2

2-phenylethylamine
(i)

State the reagent for reaction 1.

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

(ii)

What type of reaction is reaction 1?

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

(iii)

State the reagent for reaction 2.

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

(iv)

What type of reaction is reaction 2?

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

(b) 2-Phenylethylamine can be converted into C6H5CH2CH2NHCOCH3 by reaction with a suitable

reagent.
Write a balanced equation for the reaction.

[2]

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(c) In this question, one mark is available for the quality of spelling, punctuation and grammar.

Phenylamine and 2-phenylethylamine are both bases.

However, phenylamine is a weaker base than 2-phenylethylamine.

Explain these two statements.

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Quality of Written Communication [1]
[Total: 13]

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7

(a) In this question, one mark is available for the quality of use and organisation of scientific
terms.
Describe the bonding in benzene.
Illustrate your answer with a suitable diagram.

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Quality of Written Communication [1]

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(b) Benzene reacts with reagent A to produce a hydrocarbon, B, containing 90.57% carbon by
mass. The relative molecular mass of B is between 100 and 150.

Deduce the empirical formula of B.

Suggest a possible structure for B.
Suggest the identity of reagent A.

Show all your working.

[4]
[Total: 9]

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8

There are many isomers with the molecular formula C6H12O2.

(a) Ester C, CH3CH2CH2COOC2H5, is used in the manufacture of a variety of foods and drinks.
When heated, ester C can be hydrolysed by aqueous hydrochloric acid or aqueous sodium
hydroxide.
(i)

State the name of this ester.

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

(ii)

Write a balanced equation for the hydrolysis of ester C with aqueous hydrochloric acid.
.......................................................................................................................................[1]

(iii)

The hydrolysis of ester C is carried out with aqueous sodium hydroxide.

Identify the products.
...........................................................................................................................................
.......................................................................................................................................[1]

(b) Part of the mechanism for the reaction of ester C with aqueous sodium hydroxide is shown
below.
O

O
C3H7

step 1

C
OC2H5

C
C3H7

OC2H5
OH

O
step 2

C3H7

OC

2H5

OH

OH

intermediate 1
(i)

Add curly arrows to intermediate 1 to show how the products of step 2 are formed. [2]

(ii)

State what the curly arrows represent.

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

(iii)

Why is the OH ion acting as a nucleophile?

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

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(c) The structural isomers D, E and F are all carboxylic acids with the molecular formula
C6H12O2.
Each structural isomer has one chiral carbon atom.
Draw the structural formulae of the structural isomers D, E and F.

[3]

TURN OVER FOR QUESTION 8(d) AND (e)

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(d) Compound G is another carboxylic acid with the molecular formula C6H12O2.
In its n.m.r. spectrum, isomer G has three singlet peaks.
Draw the structural formula of isomer G.

[1]
(e) Cyclohexane-1,4-diol has the molecular formula C6H12O2.
(i)

Draw the skeletal formula of cyclohexane-1,4-diol.

[1]
(ii)

Predict the number of peaks, and the relative peak areas, that would be observed in the
n.m.r. spectrum of cyclohexane-1,4-diol.
...........................................................................................................................................
...........................................................................................................................................
.......................................................................................................................................[2]
[Total: 14]
END OF QUESTION PAPER

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Copyright Acknowledgements:
Q.1e spectrum

SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, accessed
2 October 2007)

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