2

39
Answer all the questions in the spaces provided.
ARENES WS 1
11 (a) Complete the diagrams to show the energies of the electrons in a carbon atom, a C+ ion and a
C– ion.

2p 2p
Zp
increasing
energy
25 25
25

1s ↑↓ 1s ↑↓ 1s ↑↓

carbon atom C+ ion C– ion

[2]

(b) One of the simple molecular allotropes of carbon is buckminsterfullerene, C60.

1h20

buckminsterfullerene

(i) What is the hybridisation of the carbon atoms in C60?

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

(ii) C60 reacts with an excess of hydrogen to form a single product, C60Hx.

Using your answer to (i), suggest a suitable value for x.

60 ( as carbon can
only
make one bond
)
....................................................................................................................................... [1]

© UCLES 2016 9701/42/F/M/16

CEDAR COLLEGE ARENES WS 1

 3
40
(c) Methylbenzene can undergo different reactions to form the products shown below.

CH2 Cl CH3 CH3

Electrophilic Cl
reaction 1 reaction 2
substitution
methylbenzene

(i) Give the reagents and conditions for these two reactions.
Ck ka Uv
light
reaction 1 ............................................................................................................................
Cl z t Mcl 3 t heat
reaction 2 ............................................................................................................................
[2]

(ii) Name the mechanism of reaction 1.

free radical substitution

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

[1]

(iii) Draw the structure of the product obtained if reaction 1 is carried out using an excess of
chlorine.

443

3 It the WTH be
all the on
Utz group
-

substituted .

[1]

[Total:
[M'16 8]
P42 Q1]

© UCLES 2016 9701/42/F/M/16 [Turn over

CEDAR COLLEGE ARENES WS 1

 14
41

29 The anti-inflammatory drug ketoprofen can be synthesised from benzene via the following five
steps. °
heat A
t Akko city
'
O
an
:b
'
step 1 step 2

- -

T, (C15 H14 O)

O step 3

Br
Bht u
.V.ligh
NACH
in ethanol
Hi V. R
step 4

O
ditka
step 5 CO2 H
a ,

heat
U ketoprofen

(a) Suggest the structures of compounds T and U and draw them in the boxes above.
CHzCHzCl t
Alas to [2]
Heart

(b) Suggest reagents and conditions for steps 1-5.

colts-codkgmclzlqhe.at
-

step 1 .........................................................................................................................................

cltzcttzclqmclzlqhe.at
step 2 .........................................................................................................................................

Brztuvlight
step 3 .........................................................................................................................................
NACN in ethanol heat under reflux
step 4 .........................................................................................................................................
Ail Ha t heat
step 5 .........................................................................................................................................
[5]

(c) What types of reaction are steps 1 and 5?

Electrophilic substitution
step 1 .........................................................................................................................................

hydrolysis
step 5 .........................................................................................................................................
.

[2]

[Total:
[J'16 9]
P41 Q9]

© UCLES 2016 9701/41/M/J/16

CEDAR COLLEGE ARENES WS 1

 18
42
18
993 The
The anti-inflammatory
anti-inflammatory drug
drug ibuprofen
ibuprofen can
can be synthesised
18
be synthesised from benzene
from benzene via
via the
the following
following si
si steps
steps

9 The anti-inflammatory drug ibuprofen can be synthesised from benzene via the following si steps

step
step 11 step 22
step
step 1 step 2

H
H
OH step 33 H
OH step
step 3
CN OH
CN
CN

step
step 44
step 4

CO2 H
CO H CO2 H
CO H
step 55
stepstep 2 step 66
CO2 H step CO2 H
2
5 step 6
CN

J
J J
ibuprofen
ibuprofen
ibuprofen

(a)
(a) raw
raw circles
(a) circles around
raw circles
around any
around chiral
any any carbon
chiral
chiral atoms
carbon
carbon in in
atoms
atoms in the
the above
the five
abovefive
above formulae
fiveformulae
formulae

(b)
(b) Suggest the
the structures
(b) Suggest
Suggest of
of compounds
the structures
structures H
of compounds
compounds and J and
H and
H and J and draw
J and them
drawthem
draw ininthe
themin the boxes
theboxes above.
boxes above.
above. [2]
[2]
[2]

(c) (c) Suggest

(c) Suggest
Suggest reagents
reagents
reagents and and
and conditions
conditions
conditions for for
for steps
steps
steps 1-6.
1-6.
1-6.

step
step 1 CH 3) 2 CHCH z Cl t AIC 13 and heat
step (1 .........................................................................................................................................
1 .........................................................................................................................................
.........................................................................................................................................

step 2step CH 3 CO Cl At Cb and heat

2 .........................................................................................................................................
t
.........................................................................................................................................
HCN cage KC N and heat under
in
reflux
step 3 .........................................................................................................................................
step 3 .........................................................................................................................................
step 4HCl heat
.........................................................................................................................................
cage ) and
step 4 .........................................................................................................................................
step Conc H 2504 heat
5 .........................................................................................................................................
and
step 5 .........................................................................................................................................
.

step 6 .........................................................................................................................................
Hzcg ) t Ni
Catalyst and heat ( 200°C )
step 6 .........................................................................................................................................
[6]
[6]
(d) Name the mechanism of step 1 and state the type of reaction for step 6.
(d) Name the mechanism of step 1 and state the type of reaction for step 6.
step 1 .........................................................................................................................................
Electrophilic Substitution
step 1 .........................................................................................................................................
step 6 .........................................................................................................................................
Reduction
step 6 .........................................................................................................................................
[2]

[Total: 11] [2]

[Total: 11]
[Total:
[J'16 P42 11]
Q9]
© UCLES 2016 9701/42/M/J/16

© UCLES 2016 9701/42/M/J/16

CEDAR COLLEGE ARENES WS 1

 12
43

64 (a) 4-nitromethylbenzene can be prepared via an electrophilic substitution reaction as shown.

CH3 CH3 CH3

conc. HNO3
conc. H2SO4

H NO2 NO2

methylbenzene intermediate T 4-nitromethylbenzene

(i) This reaction also forms an isomer of 4-nitromethylbenzene as a by-product.

Draw the structure of this by-product.

Cttz
I NO z
,

[1]

(ii) Write an equation for the reaction between HNO3 and H2SO4 that forms the electrophile for
this reaction.

Hzsoy NOE t Hzot

-

2 t HN Oz →
211504 t
....................................................................................................................................... [1]

(iii) Describe how the structure and bonding of the six-membered ring in intermediate T
differs from that in methylbenzene.
one carbon is
sp3 hybridized kg makes 4 bonds
.............................................................................................................................................
and has no e- delocalized the 5
remaining
.............................................................................................................................................
.

overlapping
'

carbons have one orbital each

p
.............................................................................................................................................
and deloused
sharing
4 e-
....................................................................................................................................... [3]
.

[N’17 P41 Q6]

© UCLES 2017 9701/41/O/N/17

CEDAR COLLEGE ARENES WS 1

 16
44

85 (a) Cumin is a spice used to flavour food. Two compounds responsible for its flavour are
cuminaldehyde and cuminyl alcohol.

O OH

cuminaldehyde cuminyl alcohol

17
(i) Deduce the number of peaks that17would be present in the 13C NMR spectrum of
17
cuminyl
(b) Cuminyl alcohol.
alcohol can be synthesised from benzene by the following route.
(b) (b)
Cuminyl alcohol
Cuminyl cancan
alcohol bebe
synthesised
synthesised ¥ from from benzene
benzenebyIodoform
bythe
thefollowing
followingroute.route.
Caza OCHS
number of peaks ...........................................................................................................
-
-

LIAIHY OH
[1]
- CO2H
OO Iraqi - OH
OH
(ii) Identify two bonds that are responsible for the differences COCO 2H H the infra-red spectra of
2in
lot
-

cuminaldehyde
step 1 and cuminyl
step 2alcohol, and statestep their3absorption ranges. step 4
step 1 1
step step
step2 2 step
step3 3 step
step44
absorption range in the infra-red spectrum / cm–1
Ox
Reduction
benzene bond ES ES
responsible
benzene
benzenefor the difference cuminaldehyde cuminyl alcohol

cuminyl alcohol
Ahly
cuminyl
cuminylalcohol
alcohol
CHSCHCI CHS t

(i) Suggest reagents and conditions for steps 1– 4.

(i) (i)Suggest
Suggest reagents
reagents andand conditions
conditions forfor steps
steps 1–1–
4.4.
stepstep Ahly Heat
1 ..................................................................................................................................
t
1 (..................................................................................................................................
Uts ) CHU t
step 1 ..................................................................................................................................
,
[2]
step 2
step CHIOU Alclzt Heat
..................................................................................................................................
2 t
..................................................................................................................................
step 2 ..................................................................................................................................
step Naohtcaep t Izcaq, Heat
33 ..................................................................................................................................
step +
3 ..................................................................................................................................
step ..................................................................................................................................
Lint Hy in ether t heat
step
step 44 ..................................................................................................................................
step 4 ..................................................................................................................................
..................................................................................................................................
[4][4]
[4]

(ii) (ii)Name
(ii) Name
Name thethe mechanism
mechanism
mechanism ofof
of step
step
step 2and
and
22and state
state
state thetype
the
the typeofof
type reaction
ofreaction
reactioninininstep4.4.4.
step
step
mechanism of step EG
2..........................................................................................................
..........................................................................................................
mechanism step
mechanism of step 22 ..........................................................................................................
.

Reduction
type of reaction in step 4 ....................................................................................................
type
type of reaction in step
reaction in step 44 ....................................................................................................
....................................................................................................
.

[2]
[2] [2]
[Total: 9]
[Total:
[M’18 P42 9] 9]
[Total:
Q8]

© UCLES 2018 9701/42/F/M/18

CEDAR COLLEGE ARENES WS 1

 12
45

66 (a) Benzene reacts with D in the presence of a suitable catalyst to give cumene and non-organic
product E. This is an electrophilic substitution reaction.

catalyst
+ D + E

cumene

(i) Name the reactant D and the non-organic product E.

2- Chloro propane
OHHHH City
HCl
D ....................................................
Chloride
Hydrogen
E ....................................................
[2]

(ii) Give the name of the type of aromatic electrophilic substitution reaction taking place.

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

(b) Cumene undergoes substitution reactions with chlorine to give several different isomeric
products with the formula C9H11Cl. The substitution can occur in the aromatic ring or in the
side-chain of cumene.

(i) Describe the conditions that are used to ensure substitution takes place only in the
aromatic ring.
Alan t heat in darkness
....................................................................................................................................... [1]
.

(ii) Draw the structures of the two major isomeric products of the reaction, formula C9H11Cl,
when substitution takes place in the aromatic ring.

✓ I
I
it I

I
Cl

[1]

© UCLES 2018 9701/41/M/J/18

CEDAR COLLEGE ARENES WS 1

 13
46

(iii) Describe the conditions that are used to ensure substitution takes place only in the
side-chain.
Uv
light
'

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

(iv) Draw the structures of two isomeric products of the reaction, formula C9H11Cl, when
substitution takes place in the side-chain.

Ta Y

[1]

(c) Complete the following table to show the structures of the organic products formed when
cumene reacts with each reagent.

reagent structure of organic product

of
OH
It
402
hot KMnO4(aq)
OR

y
H2 + Ni, high pressure

[2]

© UCLES 2018 9701/41/M/J/18 [Turn over

CEDAR COLLEGE ARENES WS 1

 14
47

(d) Cumene can be nitrated using a mixture of concentrated nitric and sulfuric acids. The
mechanism for this reaction is similar to the mechanism for the nitration of benzene.

Complete the mechanism for this reaction.

nclude all relevant c ar es and curl arrows s owin t e movement of electron pairs.
raw t e structure of t e intermediate.
ou do not need to draw t e products.

¥
A student calculates the areas underneath the three peaks in the chromatogram.
products
peak J K L

↳ NOE area / mm2 46

ANNE
18 28

(ii) The area underneath each peak is proportional to the mass of the respective compound.
cumeneCalculate the percentage by mass inintermediate
the original mixture of the compound responsible for
peak K.
[4]

[Total:
[J’18 P4113]
Q6]
% of mixture responsible for peak K = .............................. [1]

8 (b) Chlorobenzene can be prepared from benzene as shown.

Cl 2
Cl
Al Cl 3

Aluminium chloride, Al Cl 3, catalyses this reaction.

(i) Write an equation to show how Al Cl 3 generates the electrophile needed in this reaction.
Ck at
Maz
-

t →
may t
....................................................................................................................................... [1]

(ii) Draw the mechanism of the reaction between this electrophile and benzene to form
chlorobenzene. Include all relevant curly arrows and charges.

fat
a
Ht
a
I
→
↳ → t Ht

[4]

(iii) Write an equation to show how the catalyst is regenerated.

Ht Aidy Ha Mag
-

t → t
....................................................................................................................................... [1]

[N’18 P42 Q1]

© UCLES 2018 9701/41/M/J/18

CEDAR COLLEGE ARENES WS 1

 48

CEDAR COLLEGE ARENES WS 1

 49

ARENES WS 2
For
1010
SECTION A For
Examiner’s
Examiner’s
Use
Use
15 5BothBoth ethene
ethene andand benzene
benzene react
react with
with bromine,
bromine, butbut
thethe mechanisms
mechanisms andthe
and thetypes
typesofofproducts
products
of the two reactions are different.
of the two reactions are different.

reaction I
H2C CH2 + Br2 reaction I BrCH2CH2Br
H2C CH2 + Br2 no heat, no light, no catalyst needed BrCH2CH2Br
no heat, no light, no catalyst needed

Br
reaction II Br
+ Br2 reaction II + HBr
+ Br2 heat and catalyst needed + HBr
heat and catalyst needed

(a) State the type of reaction undergone in each of reactions I and II.
(a) State the type of reaction undergone in each of reactions I and II.
reaction I

Electrophilic Addition
reaction I
..........................................................................................................................................
..........................................................................................................................................
reaction II
reaction II Electrophilic Substitution
..........................................................................................................................................
[2]
..........................................................................................................................................
[2]

CEDAR COLLEGE
© UCLES 2008 9701/04/M/J/08 ARENES WS 2
 50 11 For
Examiner’s
Use
(b) In each of reactions I and II, the intermediate is a bromine-containing cation. In each
of the following boxes, draw the intermediate and use curly arrows to show how it is
converted into the product.

H H It H

reaction I
H C C H H C C H product

Br
-

H H t .

intermediate

H Br H Br

reaction II dodged
⇐ product

intermediate

[4]

(c) Why do ethene and benzene differ in their reaction with bromine?
The delocalized
ring of electrons in benzene is stable so
it is
reformed
..........................................................................................................................................
in second
the
in
step benzene The electrons in the ethene
.

.................................................................................................................................... [1]IT
bond
and available
are localized more
for reaction with
electrophiles
[J'08 P4 Q5]
[Total: 7]
.

© UCLES 2008 9701/04/M/J/08 [Turn over

CEDAR COLLEGE ARENES WS 2

 For
5110 Examiner’s
Use
27 The nitration of benzene occurs in the following steps.

H NO2 NO2

+
+ NO2 + + H+

(a) What reagents and conditions are needed for this reaction?
Conc
......................................................................................................................................[2]

(b) .su/furicAcidandConc.NitricAcid.gheatto5OoC.2HzSO4tHN03
+
Write an equation showing how the electrophile NO 2 is formed from the reagents.

2h59 Hzott NOT

-

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

(c) The nitration of methylbenzene produces mainly 2-nitromethylbenzene, whereas the

nitration of benzoic acid produces mainly 3-nitrobenzoic acid.

CH3 CO2H
NO2

NO2

2-nitromethylbenzene 3-nitrobenzoic acid

Use this information to suggest suitable intermediates G and H in the following two
2-stage syntheses of chlorobenzoic acids, and suggest suitable reagents for reactions
I to IV.

CH 's CO2H
Ct Cl
.

II
CH3
I
G

III CAH
CO2H

.
IV

Cl
H

reagents:
C 12+1-103
reaction I ................................................ Htlkmnoy
reaction II ................................................
Ht/KMn04
reaction III .............................................. Cht Alds
reaction IV ...............................................
[4]
[Total:
[N'07 P47]
Q7]

© UCLES 2007 9701/04/O/N/07

CEDAR COLLEGE ARENES WS 2

 5210

35 (a) All the carbon atoms in benzene lie in the same plane. This means that they are coplanar, For
but this is not the case with cyclohexane. Examiner’s
Use

benzene cyclohexane

By rotating the molecule around its several C–C bonds, all the carbon atoms in butane
can be made to lie in the same plane, but this is not the case with methylpropane.
H3C H
H3C CH2

CH2 CH3 H3C CH3

butane methylpropane

By considering the 3-dimensional geometry of the following five molecules, and allowing
rotations around C–C bonds, decide whether or not the carbon atoms in each molecule
can be arranged in a coplanar fashion. Then place a tick in the appropriate column in
the table below.

H3C O CH3

C C
H3C CH3
O

A B C

H2N NO2
C C
CH3CH(OH)CO2H CH3
O H

D E

all carbon atoms not all carbon atoms

compound
can be coplanar can be coplanar
A

E
[3]

© UCLES 2009 9701/42/O/N/09

CEDAR COLLEGE ARENES WS 2

 5311

(b) Methylbenzene can react with chlorine under different conditions to give the monochloro For
derivatives F and G. Examiner’s
Use

CH3 CH3 CH2Cl

I II

Cl

F G

Suggest reagents and conditions for each reaction.

reaction I
C Kt Alds
..........................................................................................................................................

reaction II
Ck -1 UV
light
...................................................................................................................................... [2]

© UCLES 2009 9701/42/O/N/09 [Turn over

CEDAR COLLEGE ARENES WS 2

 5412

(c) Benzyl benzoate is a constituent of many perfumery products, and has also been For
used in the treatment of the skin condition known as scabies. It can be made from Examiner’s
methylbenzene by the following route, which uses one of the chlorination reactions Use

from (b).

CH3 CHZCI

IV

H
III

CO2H CH2OH

VI
O

C CH2
O

benzyl benzoate

(i) Draw the structural formula of the intermediate H in the box above.

© UCLES 2009 9701/42/O/N/09

CEDAR COLLEGE ARENES WS 2

 13
55

(ii) Suggest reagents and conditions for each reaction. For

Examiner’s
reaction Ill Use

K Mn
acidified 04 t heat
..................................................................................................................................

reaction V
NaOH heat under reflux
Cag ) t
..................................................................................................................................

reaction VI
Conc . H 2504 + heat
..................................................................................................................................

(iii) State the type of reaction occurring during

reaction Ill,
Oxidation
..................................................................................................................................

reaction V.
Nucleophilic
Substitution
..................................................................................................................................
[6]
[N'09 P42 Q5]
[Total: 11]

CEDAR
© UCLES COLLEGE
2009 9701/42/O/N/09 ARENES WSover
[Turn 2
 56 8 For
Examiner’s
Use
45 Benzene can be converted into nitrobenzene by a nitration reaction.

NO2

(a) State the reagents and conditions necessary to carry out this reaction.
Concentrated Nitric Acid and Concentrated
..........................................................................................................................................

Sulfuric Acid at 55°C .

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

(b) What type of reaction mechanism is this?

Electrophilic Substitution
......................................................................................................................................[1]

(c) The reaction proceeds via two steps:

N Oz

+ X+ NO2 + Z+
H

(i) Draw the structure of the intermediate Y in the box.

(ii)
NOT
Identify the cation X+..................................................................................................

(iii)
Ht
Identify the cation Z+ ..................................................................................................

(iv) Write an equation to show how X+ is produced from the reagents.

NOI 't H 30++2 HS 04
-

211-2504 t HN Oz
...................................................................................................................................
[5]

9701/4 O/N/02

CEDAR COLLEGE ARENES WS 2

 57 9 For
Examiner’s
Use
(d) Some aromatic poly-nitro compounds are used in perfumes as artificial musks. An
example is ‘Baur musk’.

CH3
O2N NO2

C(CH3 )3
NO2

Baur musk

(i) Draw the structural formula of the hydrocarbon that could be nitrated in order to
produce Baur musk.
CHS

C C CH 3) 3

(ii) Suggest the structural formula of the compound formed by reacting Baur musk with
an excess of tin and concentrated hydrochloric acid.

CH 's

Hz N N H2

[2]

CC CH 3) 3 [N'02 P4 Q5]
[Total: 10]

N Hz

9701/4 O/N/02 [Turn over

CEDAR COLLEGE ARENES WS 2
 5812
12
57 Predict the products of the following reactions and draw their structures in the boxes provided. For
7
NotePredict themolecular
that the products of the following
formula of the reactions and draw
final product theirinstructures
is given each case.in the boxes provided. For
Examiner’s
Note that the molecular formula of the final product is given in each case. Examiner’s
Use
Use

CHZOH
CH 2 Cl
C 2 +C light
2 + light
NaOH
NaOH

heat
heat

C8H
C H10O
8 10O

C2+AC3 HNO3 +
C2+AC3 HNO3 +
H2SO4 Cl
SO4
H255˚C
N 02
55˚C
Cl C8H8C O2N
C8H8C O2N

KMnO4 COOCH 3
+ OH– C 02h CH3OH +
KMnO
+ heat
4 conc. H2SO4 Hz COCO
+ OH– HOI CH3OH +
then H+
+ heat conc. heat
H2SO4

then H+ heat
C10H10O4

C10H10O4
[6]
[J'10 P41 Q7]
[Total: 6]
[6]

[Total: 6]

© UCLES 2010 9701/41/M/J/10

© UCLES 2010 9701/41/M/J/10

CEDAR COLLEGE ARENES WS 2
 591010

65 5(a) (a)
There are are
There several ways
several of introducing
ways chlorine
of introducing chlorineatoms
atomsinto
intoorganic
organicmolecules.
molecules.State
State the
the For
For
reagents and conditions necessary to carry out the following transformations.
reagents and conditions necessary to carry out the following transformations. Examiner’s
Examiner’s
Use
Use

transformation
transformation reagents
reagents++conditions
conditions

C2HC42H4 C2H
C52Cl
H5Cl HCl ,
no light or
catalyst
2H5OH
C2HC5OH C2Cl
C2H H Cl
5 5 P45
C2HC62H6 C2Cl
C2H H Cl
5 5 Clztuvlight
C2HC42H4 C2Cl
C2H H4Cl2 Ck , no
light
4 2

CH CO H
CH3CO32H 2
CH3COCl
CH3COCl P45
CH3
CH3 Cl
Cl CH3
CH3 C Kt Alds

CH3
CH3
CH2Cl
CH2Cl Clztuvlight
[6]
[6]
(b) (i) When treated with concentrated HNO3 + H2SO4 at 55 °C, benzene produces
(b) (i) When nitrobenzene.
treated with concentrated HNO3 + H2SO4 at 55 °C, benzene produces
Outline
nitrobenzene.the mechanism of this reaction. You should include all charges, and use
curly arrows to represent
Outline the mechanism the movement
of this of electron
reaction. You should pairs.
include all charges, and use
curly arrows to represent the movement of electron pairs.

production of NOT :

2HzS04tHN0z 2HS0ItH3O+t NOT

NOZ
"
Y
H NOZ

f-
'

nozt
L
+ At
→
→
t

© UCLES 2011 9701/41/M/J/11

© UCLES 2011 9701/41/M/J/11

CEDAR COLLEGE ARENES WS 2

 6011
In aromatic substitution of monosubstituted benzenes, the orientation of an incoming For
group depends on the nature of the group already attached to the ring. Examiner’s
For example, using the same reagents and conditions as in (i), methylbenzene and Use

benzoic acid produce the following nitro compounds.

CH3 CH3 CO2H CO2H

NO2
NO2 methylbenzene benzoic acid

(ii) Using this information as an aid, suggest a structure for compound C in the following
synthesis of 3-bromobenzoic acid.

CH3 CO2H
Todt
step 1 step 2

Br

(iii) Suggest reagents and conditions for steps 1 and 2.

step 1 step 2

heat
'
heat
acidified Koun Te Bros
I
04 g Brat g

[6]
[J'11 P41 Q5]
[Total: 12]

© UCLES 2011 9701/41/M/J/11 [Turn over

CEDAR COLLEGE ARENES WS 2

 10
61

74 Both ethene and benzene react with bromine.

room
temperature
H2C CH2 + Br2 BrCH2CH2Br

Br
Al Br3 + heat
+ Br2 + HBr

(a) What type of reaction is the reaction of bromine with

(i) ethene,
Addition
.............................................................................................................................................

(ii) benzene?
Substitution
.............................................................................................................................................
[1]

(b) Write an equation to show the formation of the electrophile during the reaction between bromine
and benzene.

Brat At Bros Brt t At Bry

-

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

(c) Each of these reactions involves an intermediate.

(i) Draw the structure of the intermediate in each reaction.

H H

H 2C CH2 + Br2 → It C C H
Br

Br
+ Br2

(ii) Suggest why the product of the reaction between bromine and benzene, bromobenzene,
is still unsaturated.
The
of IT electrons in benzene is stable
configuration and
ring
a
.............................................................................................................................................
the reaction [3]
remains
unchanged after
.

© UCLES 2014 9701/42/M/J/14

CEDAR COLLEGE ARENES WS 2

 11
62

(d) When methylbenzene is nitrated, 4-nitromethylbenzene is formed, but when benzoic acid is
nitrated, 3-nitrobenzoic acid is produced.

Consider the following synthesis of 3-chlorobenzoic acid, F, from methylbenzene.

Use the information given above to suggest

the structure of the intermediate E,

the reagents and conditions needed for reactions 1 and 2.

CH3 CO2 H CO2H

reaction 1 reaction 2

Cl

E F

reagents and conditions for reaction 1

H 'T K Mn Ou and heat
....................................................................................................................................................

reagents and conditions for reaction 2

Ck and At Cho and heat
....................................................................................................................................................
[3]

(e) Consider the following synthesis of 3-chlorophenylmethylamine, H, from F.

Suggest

the structure of the intermediate G,

the reagents for reactions 3 and 4.

CO2H cool CONH2 CH2NH2

reaction 3 NH3 reaction 4

Cl Cl Cl
Cl
F G H

reagents for reaction 3

Pds
....................................................................................................................................................

reagents for reaction 4

Li At Ha
....................................................................................................................................................
[3]
[J'14 P42 Q4]
[Total: 11]

© UCLES 2014 9701/42/M/J/14 [Turn over

CEDAR COLLEGE ARENES WS 2

 9

(d) Predict the organic products of the following 9

63 9 reactions and draw their structures in the For
boxes below. You may use structural or skeletal formulae as you wish. Examiner’s
8 (d) Predict
(d) Predict the organic
the organic products
products of the
of the following
following reactions
reactions anddraw
and drawtheir
theirstructures
structures in
in the
the Use
For
boxes below. You may use structural or skeletal formulae as you wish. For
Examiner’s
boxes below. You may use structural or skeletal formulae as you wish. Examiner’s
Use
Use
hot conc. O

y
– +
4+ H
MnOhot conc.
hot conc.
MnO –
+ H+
-

– 4+
MnO4 + H
O
HO
=

( CH 3 CAH )

hot conc.
MnOhot
– conc.
4 + H–
+
MnO4 + H+
hot conc.
MnO4– + H+
H 02C CO2 H

hot hot
OH OH 2– + 2–+
Cr2OCr H + O
7 2O7 + H
hot CO2 H
OH Cr2O72– + H+
It 3C
OH OH
[4]
[4]
OH
(e) KMnO
(e) KMnO 4 and K2Cr2O7 are the reagents that can be used to carry out the following
[4]
4 and K2Cr2O7 are the reagents that can be used to carry out the following
transformation.
transformation.
(e) KMnO4 and K2Cr2O7 are the CC reagents
Hdz CCOthat
It ) can be used to carry out the following
CHIH
transformation.

¥1-
CHO
I II CHO
I II
CHO
I II OH
ok
OH
E
E OH

(i)
E
Draw the structure of intermediate E in the box above.
(i) Draw the structure of intermediate E in the box above.
(ii) Suggest reagents and conditions for the following.
(i) Suggest
(ii) Draw thereagents
structureand conditions forE the
of intermediate in the box above.
following.
reaction I ...................................................................................................................
(ii) reaction
SuggestI reagents cold dilute foralkaline
and conditions the following. K Mn 04
...................................................................................................................
.

reaction II ..................................................................................................................

acidified Kzcrzoi 4 heat and distill off aldehyde as it

[3]
reactionIII ...................................................................................................................
reaction ..................................................................................................................
forms [3]
[Total: 17]
reaction II ..................................................................................................................
.

[J'10 P43 Q4]

© UCLES 2010 9701/42/M/J/10
[3] over
[Total:[Turn
17]
[Total: 17]
© UCLES 2010 9701/42/M/J/10 [Turn over
© UCLES 2010 9701/42/M/J/10 [Turn over

CEDAR COLLEGE ARENES WS 2

 [1]
64

9 (d) Benzene, C6H6, and borazine, B3N3H6, have planar, cyclic structures.

(i) Describe the structure of and bonding in benzene, C6H6.

6 with
Benzene has carbon
bonds
atoms
making Sigma
.............................................................................................................................................
each other of equal length Ig strength The carbon
.............................................................................................................................................
.

atoms are sped hybridise kg make

angles of
120
.............................................................................................................................................
.

Benzene has all 6 carbons in the same plane

.............................................................................................................................................
The 3rd e-oh each carbon is involved in a bond with
.............................................................................................................................................
It The 4th e -

g each carbon is de localised wi

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

a six Carbon pi bond .

....................................................................................................................................... [3]

(ii) In borazine, B3N3H6, the boron and nitrogen atoms alternate around the ring. Each ring
atom has a single hydrogen atom bonded to it.
All boron-nitrogen bonds in borazine are 0.144 nm in length, whereas in simple compounds
B–N and B=N bond lengths are 0.154 nm and 0.136 nm respectively.

Suggest and draw the structure of borazine.

It
It
it

rB\
I
N

INT
N
I I
B 13 [1]
t
tf H
[Total: 10]
[N'15 P41 Q6]

It
© UCLES 2015 9701/41/O/N/15 [Turn over

CEDAR COLLEGE ARENES WS 2