ORGANIC WS 4 - ALCOHOLS & CARBONYLS

For
Examiners
Use

11

16

Compounds D and E are both ketones.

CH3CH2COCH2CH3

CH3CH2CH2COCH3

(a) State which one of these compound reacts with alkaline aqueous iodine, and draw the
structural formulae of the products formed during this reactions.
(i)

compound (D or E) ....................................................................................................

(ii)

products

.............................................................................................................................. [3]
(b) The reduction of D with NaBH4 produces just one alcohol, but a similar reduction of E
produces two isomers in equal amounts. Explain these observations, drawing structures
where appropriate.
..........................................................................................................................................
..........................................................................................................................................

[3]
[Total: 6]

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12

(a) The reaction producing tri-iodomethane (iodoform) can be used as a test for the
presence of certain groups within a molecule.
(i)

State the reagents and conditions used for this reaction.

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

(ii)

Write the structural formula of one functional group that would give a positive result
with this iodoform reaction.
..................................................................................................................................

(iii)

What do you observe in a positive test?

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

(iv)

In the following table place a tick ( ) in the column against each compound that
would give a positive result with this test, and a cross ( ) against each compound
that would give a negative result.
compound

result

CH3OH
CH3CH2OH
CH3CHO
CH3CO2H
CHO

COCH3
[6]

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For
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Use

13
(b) The iodoform test can be used, along with other reactions, to work out the structures of
unknown compounds.
Use the information in the table below to deduce the structures of the compounds in the
following scheme, and draw these structures in the boxes provided.
C7H12O
D

hot concentrated acidified KMnO4

Results of tests (

indicates a positive result;

For
Examiners
Use

C3H6O + C4H6O3
E
F
indicates a negative result)

results of tests with each compound

test

iodoform
Fehlings solution
2,4-dinitrophenylhydrazine reagent
Na2CO3(aq)
structures

D(C7H12O)

E(C3H6O)

F(C4H6O3)
[3]

(c) Treatment of compound F with NaBH4 gives compound G, C4H8O3. Heating G with Al2O3
gives a mixture of three isomeric unsaturated carboxylic acids H, J and K, C4H6O2, two
of which are stereoisomers of each other.
Suggest structures for G, H, J, and K, and name the type of stereoisomerism shown.

Al2O3

type of stereoisomerism ............................................................................................... [5]

[Total: 14]
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10

10

Compound C has the molecular formula C7H14O. Treating C with hot concentrated acidified
35 5Compound
C has the molecular formula C H O. Treating C with hot concentrated acidified

For

C4H8O, and E, C3H4O3. The results of four tests For

KMnO4(aq) produces two compounds, 7D, 14
Examiners
produces
compounds,
D,are
C4Hshown
E, Cfollowing
results of four tests Examiners
KMnO
Use
4(aq)out
8O, and
3H4O3. The
carried
on thesetwo
three
compounds
in the
table.
Use
carried out on these three compounds are shown in the following table.
test reagent
test reagent

result of test with

result of test with
compound C
compound D
compound E
compound C
compound D
compound E

Br2(aq)
Br2(aq)

decolourises
decolourises

no reaction
no reaction

no reaction
no reaction

Na(s)
Na(s)

fizzes
fizzes

no reaction
no reaction

fizzes
fizzes

(aq)
I2(aq) + OH
I2(aq)
+ OH(aq)

no reaction
no reaction

2,4-dinitrophenylhydrazine
2,4-dinitrophenylhydrazine

no reaction
no reaction

yellow
yellow
precipitate
precipitate
orange
orange
precipitate
precipitate

yellow
yellow
precipitate
precipitate
orange
orange
precipitate
precipitate

(a) State the functional groups which the above four reagents test for.
(a) State the functional groups which the above four reagents test for.
(i) Br2(aq)
(i) Br2(aq)
..................................................................................................................................
..................................................................................................................................
(ii) Na(s)
(ii) Na(s)
..................................................................................................................................
..................................................................................................................................
(iii) I2(aq) + OH(aq)
(iii) I2(aq) + OH(aq)
..................................................................................................................................
..................................................................................................................................
(iv) 2,4-dinitrophenylhydrazine
(iv) 2,4-dinitrophenylhydrazine
..................................................................................................................................
.................................................................................................................................. [4]
[4]
(b) Based upon the results of the above tests, suggest structures for compounds D and E.
(b) Based upon the results of the above tests, suggest structures for compounds D and E.

E, C3H4O3
E, C3H4O3

D, C4H8O
D, C4H8O

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[2]

[2]

11
(c) Compound C exists as two stereoisomers.
Draw the structural formula of each of the two isomers, and state the type of
stereoisomerism involved.

For
Examiners
Use

type of stereoisomerism .......................................................

[3]
[Total: 9]

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4 4

Ethylbenzene is an important starting material for making polystyrene (poly(phenylethene)).

CH2CH3

CHCl CH3
reaction I

CH

CH2

reaction II

polystyrene

+ Cl 2
B

ethylbenzene
(a) (i)

phenylethene

State the conditions needed to carry out reaction I in the laboratory.

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

(ii)

State the reagent and conditions needed for reaction II.

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

(iii)

Draw the structure of the repeat unit of polystyrene.

(iv)

There are several polymers that consist of phenylethene co-polymerised with other
monomers. The following formula shows part of the chain of one such co-polymer.
CH2

CH

CH2

CH

CH2

CN

CH

CH2

CN

Deduce the structural formula of the other monomer.

[5]

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For
Examiners
Use

For
For
Examiners
Examiners
Use
Use

9
9
(b) Compound B undergoes the following series of reactions.
(b) Compound B undergoes the following series of reactions.
CHCl CH
CHCl CH3 3

CH(OH)CH
CH(OH)CH3 3

reaction III
reaction III

reaction IV
reaction IV

+
+

I2 + NaOH
I2 + NaOH
B
B

C
C

D
D

(i) Suggest reagents and conditions for reaction III.

(i) Suggest reagents and conditions for reaction III.
...................................................................................................................................
...................................................................................................................................
(ii) What would you see when reaction IV was carried out?
(ii) What would you see when reaction IV was carried out?
...................................................................................................................................
...................................................................................................................................
(iii) Draw structures for C and D in the boxes above.
(iii) Draw structures for C and D in the boxes above.
[4]
[4]
(c) Ethylbenzene can react with chlorine under a different set of conditions to give
(c) Ethylbenzene
chlorine under
a different Esetundergoes
of conditions
to give
compound E,can
an react
isomerwith
of compound
B. Compound
the following
compound
reaction. E, an isomer of compound B. Compound E undergoes the following
reaction.
CH2CH3
CH2CH3
reaction V
reaction V
+ Cl2
+ Cl2

reaction VI
reaction VI

CO2H
CO2H

Cl
Cl

E
E
(i) Draw a structure for E in the box above.
(i) Draw a structure for E in the box above.
(ii) Describe the conditions used for reaction V.
(ii) Describe the conditions used for reaction V.
...................................................................................................................................
...................................................................................................................................
(iii) State the reagents used for reaction VI.
(iii) State the reagents used for reaction VI.
...................................................................................................................................
[3]
...................................................................................................................................

[3]
[Total: 12]
[Total: 12]

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9701/04/O/N/06

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Chloroacetophenone (compound D, below) was formerly the most widely used tear gas,
For
8
For
under the codename CN. It was used in warfare
Examiners
8 and in riot control. It can be synthesised
Examiners
Use
from
ethylbenzene,
A,
by
the
following
route.
4
Chloroacetophenone (compound D, below) was formerly the most widely used tear gas,
Use
5 4 Chloroacetophenone
D, below)
was
the most
used tear gas,
under the codename (compound
CN. It was used
in warfare
andformerly
in riot control.
It canwidely
be synthesised
fromthe
ethylbenzene,
by the
following
route.
under
codenameA,CN.
It was
used
in warfare and in riot control. It can be synthesised
I
II
III
IV
from ethylbenzene, A, by the following route.
CH2CH3
CHClCH3
CH(OH)CH3
COCH3
COCH2Cl
I

CH2CH3

A
CH2CH3

II

CHClCH3

B
CHClCH3

III

CH(OH)CH3

II

CH(OH)CH3

(a) Suggest
reagents andBconditions for step I.
A
(a) Suggest reagents and conditions for step I.

IV

III

COCH3
C

C
COCH3

IV COCH2Cl
D
COCH2Cl
D

......................................................................................................................................[1]
......................................................................................................................................[1]
(a) Suggest
reagents and conditions for step I.
(b) Suggest
reagents
forconverting
converting
ethylbenzene
into compound
(b) Suggest
reagentsand
and conditions
conditions for
ethylbenzene
into compound
E, an E, an
......................................................................................................................................[1]
isomer
of B.
isomer
of B.
(b) Suggest reagents and conditions for converting ethylbenzene into compound E, an
isomer of B.
Cl
CH2CH3
Cl
CH2CH3
E

E CH2CH3

Cl

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

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

(c) Draw the structure of the product obtained by heating ethylbenzene with KMnO4.

(c) Draw
the structure of the product obtained by heating ethylbenzene with KMnO4.
......................................................................................................................................[1]
(c) Draw the structure of the product obtained by heating ethylbenzene with KMnO4.
[1]

(d) Describe a test (reagents and observations) that would distinguish compound C from
compound F.

[1]

(d) Describe a test (reagents and observations) that would distinguish compound C from
[1]
compound F.
COCH2CH3
(d) Describe a test (reagents and observations) that would distinguish compound C from
F
compound F.
COCH2CH3
reagents

F COCH2CH3

..........................................................................................................................................
observation with C
reagents

..........................................................................................................................................
reagents
..........................................................................................................................................
observation with F

..........................................................................................................................................
observation
with C
..........................................................................................................................................

observation with C
[2]
..........................................................................................................................................
..........................................................................................................................................
observation
with F
observation with F
9701/04/M/J/03
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[2]
..........................................................................................................................................
[2]

9701/04/M/J/03
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9
(e) The efficiency of a tear gas is expressed by its intolerable concentration, I.C. The I.C.
of the tear gas CN has been measured as 0.030 g m3 of air.
How many moles of chloroacetophenone need to be sprayed into a room of volume
60 m3 in order to achieve this concentration?

For
Examiners
Use

..........................................................................................................................................
..........................................................................................................................................
......................................................................................................................................[2]
(f)

Residues of CN can be destroyed by hydrolysis with an aqueous alkali.

COCH2Cl + OH

COCH2OH + Cl

D
Compounds G and H are isomers of compound D.
CH2COCl

Cl

G
(i)

COCH3
H

Arrange the three isomers D, G and H in order of increasing ease of hydrolysis.

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

(ii)

Explain the reasoning behind your choice.

...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
[3]
[Total : 10]

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