PMT

Oxford Cambridge and RSA

Tuesday 11 June 2019 – Afternoon

A Level Chemistry A
H432/02 Synthesis and analytical techniques
Time allowed: 2 hours 15 minutes

You must have:

* 7 6 7 3 7 2 9 2 0 4 *

• the Data Sheet for Chemistry A

(sent with general stationery)
You may use:
• a scientific or graphical calculator

* H 4 3 2 0 2 *

Please write clearly in black ink. Do not write in the barcodes.

Centre number Candidate number

First name(s) �

Last name �

INSTRUCTIONS
• Use black ink. You may use an HB pencil for graphs and diagrams.
• Answer all the questions.
• Where appropriate, your answers should be supported with working. Marks may be
given for a correct method even if the answer is incorrect.
• Write your answer to each question in the space provided. If additional space is
required, use the lined page(s) at the end of this booklet. The question number(s) must
be clearly shown.

INFORMATION
• The total mark for this paper is 100.
• The marks for each question are shown in brackets [ ].
• Quality of extended responses will be assessed in questions marked with an
asterisk (*).
• This document consists of 32 pages.

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SECTION A

You should spend a maximum of 20 minutes on this section.

Write your answer to each question in the box provided.

Answer all the questions.

1 Which alkane has the highest boiling point?

A CH3(CH2)5CH3

B (CH3)3CCH(CH3)2

C CH3(CH2)3CH(CH3)2

D (CH3)2CHCH2CH(CH3)2

Your answer
[1]

2 Butane reacts with chlorine in the presence of ultraviolet radiation to form a mixture of organic
products.

Which equation shows a propagation step in the mechanism for this reaction?

A Cl 2 → •Cl + •Cl

B •Cl + •C4H8Cl → C4H8Cl 2

C C4H9Cl + •Cl → C4H8Cl 2 + •H

D •Cl + C4H9Cl → •C4H8Cl + HCl

Your answer
[1]

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3 What is the name of the compound below?

H CH3
C

C
H 3C CH2 CH2 CH2 CH3

A 3-Propylpent-2-ene

B 3-Propylpent-3-ene

C 3-Ethylhex-2-ene

D 4-Ethylhex-4-ene

Your answer
[1]

4 The structure of a stereoisomer is shown below.

H3C CH(CH3)2

C C

CH3CH2 CH2CH2CH3

Which term correctly describes this stereoisomer?

A cis-

B trans-

C E-

D Z-

Your answer
[1]

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5 Which types of bonds are broken and formed in the reaction of ethene and bromine?

Types of bond broken Types of bond formed

A σ π
B π σ
C σ and π π
D σ and π σ

Your answer
[1]

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6 What is the organic product of the reaction below?

CH2Cl

KOH(aq)

Cl

CH2OH

Cl

CH2Cl

OH

CH2OH

OH

HO CH2Cl

Cl

Your answer
[1]

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7 What is the number of chiral carbon atoms in the steroid molecule below?

OH

A 5

B 6

C 7

D 8

Your answer
[1]

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8 Phenol reacts with bromine.

Which is the least likely organic product?

OH

Br

Br

OH

Br Br
B

OH

Br
C

Br

OH

Br Br

Br

Your answer
[1]

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9 The repeat unit of a polymer is shown below.

H H H H O

O C C O C C C C

H H O H H

Which monomers could form this polymer?

OH HO
A
HO OH

OH
HO OH
B
HO

O O
HO OH
C

HO OH

O O

D HO
HO OH OH

Your answer
[1]

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10 Which compound shows 4 peaks in its carbon-13 NMR spectrum?

Your answer
[1]

11 A student reacts 4.50 g of C6H5NH2 with excess CH3COCl in the reaction below.

C6H5NH2 + CH3COCl → C6H5NHCOCH3 + HCl

Mr = 93.0 Mr = 135.0

The reaction produces 3.25 g of C6H5NHCOCH3.

What is the percentage yield of C6H5NHCOCH3?

A 49.8

B 68.9

C 72.2

D 95.4

Your answer
[1]

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12 A compound produces the 13C NMR spectrum below.

80 70 60 50 40 30 20 10 0
chemical shift, d / ppm

Which compound could have produced this spectrum?

A Propane

B 2-Methylbutane

C 2-Methylpropan-1-ol

D 2-Methylpropan-2-ol

Your answer
[1]

13 A carbonyl compound is reacted with NaBH4.

Which compound(s) could be formed?

1 2-Methylpentan-2-ol

2 2-Methylpentan-1-ol

3 3-Methylpentan-2-ol

A 1, 2 and 3

B Only 1 and 2

C Only 2 and 3

D Only 1

Your answer
[1]

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14 Which chemical(s) can react with phenol?

1 Potassium hydroxide

2 Ethanoyl chloride

3 Nitric acid

A 1, 2 and 3

B Only 1 and 2

C Only 2 and 3

D Only 1

Your answer
[1]

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15 The structure of a compound used to treat influenza is shown below.

O
O

HN

NH2
O

Which functional group(s) is/are in a molecule of the compound?

1 Ester

2 Secondary amide

3 Ketone

A 1, 2 and 3

B Only 1 and 2

C Only 2 and 3

D Only 1

Your answer
[1]

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SECTION B

Answer all the questions.

16 This question is about unsaturated aldehydes and alcohols.

(a) 3-Methylbut-2-enal, shown below, is used as a food flavouring.

H3C CHO

C C

H3C H
3-methylbut-2-enal

3-Methylbut-2-enal is reacted with hydrogen bromide, forming a mixture of two organic

products.

One of the organic products forms in a much greater quantity than the other organic product.

(i) Outline the reaction mechanism for the formation of one of the organic products.

Include curly arrows and relevant dipoles.

[4]

(ii) Explain why one of the organic products forms in a much greater quantity than the other
organic product.

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(b) Geraniol and citronellal, shown below, are isomers present in ‘citronella oil’, used as an insect
repellent.

OH O
Geraniol Citronellal

• Geraniol and citronellal are structural isomers of each other.

• They also show stereoisomerism.

(i) Describe how the observations from a chemical test would distinguish between geraniol
and citronellal.

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(ii) What is the molecular formula of geraniol?

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(iii) Explain why geraniol and citronellal are structural isomers of each other.

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(iv) Explain the term stereoisomerism.

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(v) The structures of geraniol and citronellal are repeated below with the carbon atoms
numbered.

7 1 7 1
5 4 3 5 4 3 2
8 6 2 OH 8 O
6
Geraniol Citronellal

Explain the types of stereoisomerism shown by geraniol and citronellal.

In your answer,
• refer to the numbered carbon atoms in the structures above
• draw diagrams clearly showing any stereoisomers.

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Geraniol stereoisomers

Citronellal stereoisomers

[4]

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17 This question is about α-amino acids, RCH(NH2)COOH.

(a) Table 17.1 shows the R groups in four amino acids.

Amino acid R group

alanine (ala) CH3–
serine (ser) HOCH2–
leucine (leu) (CH3)2CHCH2–
glycine (gly) H–

Table 17.1

(i) In the boxes, draw the organic products for the reactions of serine shown below.

(CH3)2CHOH / H2SO4
H+(aq)

H O
excess CH3COCl
H 2N C C

CH2 OH

OH
serine

[4]

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(ii) A student is provided with one of the four amino acids in Table 17.1.

A student carries out a titration with a standard solution of hydrochloric acid to identify
the amino acid. The student’s method is outlined below.

• The student dissolves 5.766 g of the amino acid in water and makes the solution up
to 250.0 cm3 in a volumetric flask.

• The student titrates this solution with 25.0 cm3 of 0.150 mol dm−3 hydrochloric acid.

• 21.30 cm3 of the amino acid solution were required for complete neutralisation of the
hydrochloric acid.

Determine which amino acid the student used.

[4]

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(b) The student is provided with another amino acid.

The student attempts to identify the unknown amino acid using chromatography.

The student obtains two TLC chromatograms of the unknown amino acid and the four amino
acids in Table 17.1, using two different solvents, W and X.

solvent front

origin

unknown ala ser leu gly unknown ala ser leu gly
amino amino
acid acid
Solvent W Solvent X

(i) What is the Rf value of serine (ser) in solvent W?

Rf = ......................................................... [1]

(ii) Analyse the chromatograms to identify the unknown amino acid.

Explain your reasoning.

Name of unknown amino acid ...........................................................................................

Explanation .......................................................................................................................

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BLANK PAGE

PLEASE DO NOT WRITE ON THIS PAGE

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18 This question is about esters.

(a) The structure of ester A is shown below.

Br O
Ester A

(i) What is the systematic name of ester A?

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

(ii) In the boxes, draw the organic products for the reactions of the functional groups in
ester A shown below.

Each reaction forms two organic products.

H+(aq)

Br O
Ester A

excess OH–(aq)

[5]

(iii) Name the type of reactions of ester A shown in (ii).

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(b) The protons in ester A are in four different environments, labelled 1– 4 on the structure below.

1 O 3
4
CH2 C CH2
Br CH2 O CH3

Complete the table to predict the proton NMR spectrum of ester A.

Proton environment Chemical shift Splitting pattern

[4]

(c) Compound B is a structural isomer of ester A.

• Compound B reacts with aqueous sodium carbonate.

• The 13C NMR spectrum of B has 4 peaks.

Draw a possible structure for compound B.

[1]

(d) A polyester is formed from 200 molecules of 4-hydroxybenzoic acid.

What is the relative molecular mass, Mr, of the polyester?

Mr = ............................................. g mol−1 [2]

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(e)* A student intends to synthesise ester C.

H O

H3C C C

CH3 O CH3

Ester C

(i) Plan a two-stage synthesis to prepare 12.75 g of ester C starting from 2-methylpropanal,
(CH3)2CHCHO. Assume the overall percentage yield of ester C from 2-methylpropanal is
40%.

In your answer include the mass of 2-methylpropanal required, reagents, conditions and
equations where appropriate.

Purification details are not required. [6]

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(ii) The mass spectrum of ester C is shown below.

100
Y
80

60
Relative
intensity
40
Z

20

0
10 20 30 40 50 60 70 80 90 100
m/z

Suggest possible structures for the species responsible for peaks Y and Z in the mass
spectrum.

Y Z
[2]

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19 This question is about benzene.

(a) Over time, the Kekulé and delocalised models have been used to describe the bonding and
structure of a benzene molecule.

(i) Describe, in terms of orbital overlap, the similarities and differences between the bonding
in the Kekulé model and the delocalised model of benzene.

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(ii) Experimental evidence led to the general acceptance of the delocalised model over the
Kekulé model.

Describe two pieces of evidence to support the delocalised model of benzene.

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(b) Benzene can be used as the starting material for the synthesis of compounds D and E, shown
below.

In the diagrams C6H5 is a phenyl group.

CH3
H H

C C H2N C COOH

C6H5 H
C 6H 5

compound D compound E

Compounds D and E can be converted into polymers.

(i) Draw two repeat units of these polymers.

Two repeat units of polymer formed from D

Two repeat units of polymer formed from E

[3]

(ii) State the type of polymer formed from compounds D and E.

From compound D ............................................................................................................

From compound E .............................................................................................................

[1]

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(iii) In the synthesis of compounds D and E, benzene is first reacted with ethanoyl chloride,
CH3COCl, to form phenylethanone, shown below.

H3 C O
C

phenylethanone

The reaction takes place in the presence of aluminium chloride, Al Cl 3, which acts as a
catalyst.

In the mechanism for this reaction,

• ethanoyl chloride first reacts with aluminium chloride to form the CH3–C+=O cation
• the CH3–C+=O cation then behaves as an electrophile.
Complete the mechanism for the reaction.

Include equations to show the role of the Al Cl 3 catalyst, relevant curly arrows and the
structure of the intermediate.

Formation of electrophile ...................................................................................................

+
H 3C C O

Intermediate

H 3C O
C
+ H+

Regeneration of catalyst ...................................................................................................

[5]
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(iv) Complete the flowchart for the synthesis of compounds D and E from phenylethanone.

H3 C O
C

NaBH4

phenylethanone

NaCN(aq) / H+(aq)

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

H C
C H

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

CH3

compound D
Br C CN

.................................................. CH3

H 2N C COOH
....................................

compound E [7]
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20 This question is about reaction mechanisms.

(a) Chemists use curly arrows in reaction mechanisms.

(i) What does a curly arrow show in a reaction mechanism?

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

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

(ii) Draw structures to show the products in the reaction mechanism below.

H + H
O

[2]

(iii) Use the mechanism in (ii) to explain what is meant by heterolytic fission.

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(b) An incomplete reaction mechanism is shown below.

(i) Complete the mechanism by adding curly arrows and any missing species.

–
O O

H 3C C H 3C C Cl

Cl OH
–
OH

H3C C + …………

OH
[4]

(ii) What is the role of OH− in this mechanism?

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

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21* Analysis of an unknown organic compound produced the following results.

Elemental analysis by mass

C: 73.17%; H: 7.32%; O: 19.51%

Mass spectrum
Molecular ion peak at m / z = 164.0

Infrared spectrum
100

Transmittance
(%) 50

0
4000 3000 2000 1500 1000 500
Wavenumber / cm–1
1H NMR spectrum in D2O

4 3
1

8 7 6 5 4 3 2 1 0
Chemical shift, d / ppm

The numbers by the peaks are the relative peak areas.

Use the results to suggest one possible structure for the unknown compound.

Show all your reasoning. [6]

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