ORGANIC WS 2 - BENZENE10& METHYL BENZENE

10

Both ethene and benzene react with bromine, but the mechanisms and the types of products
1 5 5 Both
ethene and benzene react with bromine, but the mechanisms and the types of products
of the two reactions are different.
of the two reactions are different.

H C
H2C2

CH
CH2 2

Br
Br2 2

Br
Br2 2

reaction I
reaction I
BrCH2CH2Br
no heat, no light, no catalyst needed BrCH2CH2Br
no heat, no light, no catalyst needed

reaction II
reaction II
heat and catalyst needed
heat and catalyst needed

Br
Br
+
+

HBr
HBr

(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
reaction I
..........................................................................................................................................
..........................................................................................................................................
reaction II
reaction II
..........................................................................................................................................
..........................................................................................................................................
[2]
[2]

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Use
Use

11
(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.

For
Examiners
Use

reaction I
product

intermediate

reaction II
product

intermediate
[4]
(c) Why do ethene and benzene differ in their reaction with bromine?
..........................................................................................................................................
.................................................................................................................................... [1]
[Total: 7]

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For
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10

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?
......................................................................................................................................[2]
+

(b) Write an equation showing how the electrophile NO 2 is formed from the reagents.
......................................................................................................................................[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
3-nitrobenzoic acid

2-nitromethylbenzene

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.
CO2H
Cl

II
CH3

I
G
III

CO2H
IV
Cl

H
reagents:
reaction I ................................................

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

reaction III ..............................................

reaction IV ...............................................
[4]
[Total: 7]

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10

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

benzene

cyclohexane

By rotating the molecule around its several CC 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

CH2

H3C

CH3

CH2

CH3

H3C

butane

methylpropane

By considering the 3-dimensional geometry of the following five molecules, and allowing
rotations around CC 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
C
H3C
A

CH3

O
C

CH3

H2N
CH3CH(OH)CO2H

NO2
C

CH3

compound

all carbon atoms

can be coplanar

not all carbon atoms

can be coplanar

A
B
C
D
E
[3]
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11
(b) Methylbenzene can react with chlorine under different conditions to give the monochloro
derivatives F and G.
CH3

CH3
I

For
Examiners
Use

CH2Cl
II

Cl
F

Suggest reagents and conditions for each reaction.

reaction I
..........................................................................................................................................
reaction II
...................................................................................................................................... [2]

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12
(c) Benzyl benzoate is a constituent of many perfumery products, and has also been
used in the treatment of the skin condition known as scabies. It can be made from
methylbenzene by the following route, which uses one of the chlorination reactions
from (b).

CH3
IV

III

V
CO2H

CH2OH

VI
O
C

CH2
O

benzyl benzoate
(i)

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Draw the structural formula of the intermediate H in the box above.

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13
(ii)

Suggest reagents and conditions for each reaction.

For
Examiners
Use

reaction Ill
..................................................................................................................................
reaction V
..................................................................................................................................
reaction VI
..................................................................................................................................
(iii)

State the type of reaction occurring during

reaction Ill,
..................................................................................................................................
reaction V.
..................................................................................................................................
[6]
[Total: 11]

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45

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Benzene can be converted into nitrobenzene by a nitration reaction.

NO2

(a) State the reagents and conditions necessary to carry out this reaction.
..........................................................................................................................................
......................................................................................................................................[2]
(b) What type of reaction mechanism is this?
......................................................................................................................................[1]
(c) The reaction proceeds via two steps:

+ X+

NO2 + Z+

Y
(i)

Draw the structure of the intermediate Y in the box.

(ii)

Identify the cation X+..................................................................................................

(iii)

Identify the cation Z+ ..................................................................................................

(iv)

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

...................................................................................................................................
[5]

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9
(d) Some aromatic poly-nitro compounds are used in perfumes as artificial musks. An
example is Baur musk.

For
Examiners
Use

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.

(ii)

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

[2]
[Total: 10]

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12 12

57

Predict
the products
of the
reactions
andand
draw
their
structures
in the
boxes
provided.
7
Predict
the products
of following
the following
reactions
draw
their
structures
in the
boxes
provided. ForFor
NoteNote
that that
the molecular
formula
of
the
final
product
is
given
in
each
case.
Examiners
the molecular formula of the final product is given in each case.
Examiners
Use
Use

C 2 +Clight
+ light
2

NaOH
NaOH
heat
heat

O
C8H
C10
8H10O

C 2 +CA2 C
+A
3 C 3

HNO
HNO
3 +3 +
H2SO
H2SO
4
4
55C
55C
C88C
H8O
C2O
C8H
N2N

KMnO
KMnO
4
4
+ OH+OH
+ heat
+ heat

CHCH
+ +
3OH
3OH
conc.
H
conc. H2SO2SO
4 4

+
thenthen
H+ H

heat
heat

C10CH1010HO104O4
[6][6]
[Total:
[Total:
6] 6]

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13
(c) When heated with concentrated, acidified KMnO4(aq), one of the two alkenes L or M
produces the dicarboxylic acid N.

For
Examiners
Use

CO2H CO2H

N
(i)

Give the letter of the alkene that produced N by this reaction.

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

(ii)

Suggest the structure of the product, P, of the reaction between the other alkene
you have drawn and hot concentrated acidified KMnO4.

P
(iii)

Suggest one chemical test that would enable you to distinguish between N and P.
reagent(s) ..................................................................................................................
observation ................................................................................................................
[3]

(d) Chlorocyclohexane can be prepared by bubbling HCl(g) through a solution of

cyclohexene.
C
+ HC

Suggest the mechanism of this 2-stage reaction by means of a diagram. Include all whole
or partial charges, and represent the movements of electron pairs by curly arrows.

[3]

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[Total: 12]
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10 10

65

There
are are
several
ways
of introducing
chlorine
atoms
into
organic
molecules.
State
5(a) (a)
There
several
ways
of introducing
chlorine
atoms
into
organic
molecules.
Statethe
the ForFor
Examiners
Examiners
reagents
andand
conditions
necessary
to carry
outout
thethe
following
transformations.
reagents
conditions
necessary
to carry
following
transformations.
Use
Use

transformation
transformation

C2HC4 2H4

H5Cl
C2HC52Cl

C2HC
2H5OH
5OH

H5Cl
C2HC52Cl

C2HC6 2H6

H5Cl
C2HC52Cl

C H
C2H4 2 4

C H Cl
C2H42Cl42 2

CH CO H
CH3CO32H 2
CH3
CH3
CH3
CH3

reagents
+ conditions
reagents
+ conditions

CH3COCl
CH3COCl

Cl

Cl

CH3
CH3
CH2Cl
CH2Cl

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

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11
In aromatic substitution of monosubstituted benzenes, the orientation of an incoming
group depends on the nature of the group already attached to the ring.
For example, using the same reagents and conditions as in (i), methylbenzene and
benzoic acid produce the following nitro compounds.
CH3

CH3

CO2H

For
Examiners
Use

CO2H

NO2
NO2
(ii)

methylbenzene

benzoic acid

Using this information as an aid, suggest a structure for compound C in the following
synthesis of 3-bromobenzoic acid.
CO2H

CH3
step 1

step 2
Br
C

(iii)
step 1

Suggest reagents and conditions for steps 1 and 2.

step 2

[6]
[Total: 12]

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