YEAR 13

1.

A2

UNIT 4.8 ORGANIC EXAM QUESTIONS

Consider the following reaction scheme, then answer the questions which follow.

(a)

Give the reagents and conditions for steps 1.

Step 1 Reagent: ................................................................................................
Conditions: .......................................................................................................
(2)

(b)

(i)

Write an equation for the reaction of compound B with dilute aqueous

sodium hydroxide.

(ii)

What type of reaction is this?

..........................................................................................................................
(2)

(c)

Outline briefly how you would isolate a sample of the aromatic product of the reaction in
(b)(i).
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)

2.

Propane-1,2-diol, CH3CH(OH)CH2OH, can be used to manufacture a polymer.

(a)

Give the structure of a suitable compound which could react with propane-1-2-diol to
form a polymer.

(b)

Give the repeat unit of the polymer formed and name the type of linkage formed between
the molecules.

(c)

This polymer is not considered to be particularly hazardous to the environment. Comment

on possible reasons for this.
................................................................................................................
................................................................................................................
(Total 5 marks)

3.

(a)

Acyl halides such as ethanoyl chloride, CH3COCl, are useful synthetic intermediates
because they are quite reactive.
(i)

Suggest synthetic steps, giving reagents and conditions, by means of which ethanol
could be converted to ethanoyl chloride.
...........................................................
...........................................................
...........................................................
...........................................................
...........................................................
...........................................................
(5)

4.

Organic compounds which are used as drugs in medicine often have their structures modified in
order to make them more hydrophilic (soluble in water) or lipophilic (soluble in fatty tissue).
One such drug is chloramphenicol, A.
The CH2OH group in the molecule can be altered in the following ways:
(a)

(i)

Suggest which one of the compounds A, B, C or D would be most soluble in water

and hence suitable for intravenous injection.

(1)

N H C O C H C l2
C H (O H )C H C H 2 O H

N O

N H C O C H C l2
C H (O H )C H C H 2O O C C

N H C O C H C l2
15

C H (O H )C H C H 2 O O C (C H 2 ) 2 C O 2 H

31

N O

N O

N H C O C H C l2
C H ( O H ) C H C H 2 O O C ( C H 2 ) 2 C O 2 N a +

N O

(ii)

Explain your reasoning.

(2)

(b)

(i)

Which one of the compounds A, B, C or D would you expect to be least soluble in

water and hence suitable to be administered to patients as a suspension in water?

(1)

(ii)

Give a reason for your answer.

(1)

(c)

(i)

The conversion of A to B and that of A to C involves the same type of reaction.

What type of reaction is this?

(1)

(ii)

Under what conditions is this type of reaction often brought about in the laboratory?

(2)

(iii)

Give the formulae for the reagents required for the conversion of
A to B
C to D .
(2)

(d)

(i)

Outline a practical procedure by which a solid sample of D could be purified in the

laboratory.

(3)

(ii)

Suggest how the purity of this sample might be checked.

(1)

(e)

No matter which of the forms B, C or D is taken, the compound A is re-formed in the

acidic conditions in the stomach by the same type of reaction. What type of reaction
is this?
.
(1)
(Total 15 marks)

5.

This question concerns the three isomers A, B and C, each of which has a relative molecular
mass of 134.
O

C H

C H

C H

CH

C
H

C H

C H

C H 2O H

C
(a)

The mass spectrum of substance A is shown below. Identify the species responsible for
the peaks labelled 1, 2 and 3.
Peak 1 .........................................................................................................................
Peak 2 .........................................................................................................................
Peak 3 .........................................................................................................................
(3)

(b)

The infra-red spectra of two of these substances were also measured.

(i)

Use the table and the spectra below to identify which spectrum is that of
substance C.
Wavenumber
/ cm1

Bond

Wavenumber
/ cm1

CH (arenes)

3000-3100

OH (hydrogen bonded)

3200-3570

CH (alkanes)

2850-3000

OH (not hydrogen
bonded)

3580-3650

C==O

1680-1750

C==C (arenes)

1450-1600

Bond

The spectrum of substance C is spectrum number ..........................................

(1)

(ii)

Give one reason for your choice.

......................................................................................................................
5

(1)

Give one other reason why the other spectrum could not be that of substance C.
......................................................................................................................
......................................................................................................................
(1)

100

R e la t iv e in t e n s it y

80
60
1

40
20

0
25

50

m /e

75

100

125

T ra n s m itta n c e

100

50

4000

3000

2000
1500
W a v e n u m b e r /c m 1

1000

4000

3000

2000
1500
W a v e n u m b e r /c m 1

1000

100

T ra n s m itta n c e

(iii)

50

(c)

State which of the substances A, B and C will react with the following reagents and state
what would be observed.
(i)

Bromine dissolved in hexane.

Substance(s) .....................................................................................................
Observation ......................................................................................................
(2)

(ii)

A warm ammoniacal solution of silver nitrate.

Substance(s) .....................................................................................................
Observation ......................................................................................................
(2)

(iii)

2,4-dinitrophenylhydrazine solution.
Substance(s) .....................................................................................................
Observation ......................................................................................................
(3)

(Total 13 marks)

6.

(a)

Three isomers A, B and B have the molecular formula C4H8O.

All three compounds give an orange precipitate with 2,4-dinitrophenylhydrazine reagent.
B and C also give a silver mirror when warmed with ammoniacal silver nitrate solution.
Write the structural formulae of A, B and C .
Substance A

Substance B

Substance C

7.

(a)

An alcohol with the molecular formula C4H9OH is chiral.

(i)

Explain what is meant by the term chiral.

............................................................................................................................
............................................................................................................................
(2)

(ii)

Draw two diagrams to clearly represent the optical isomers that result from the
chirality of this alcohol.

(2)

(iii)

Explain how you could distinguish between these two isomers experimentally.
...................................................................................................................
...................................................................................................................
...................................................................................................................
(2)

(b)

Alcohols react with carboxylic acids to form esters.

(i)

Write an equation for a typical esterification reaction.

...................................................................................................................
(1)

(ii)

Suggest how this type of reaction could be used to form polyesters.

Experimental details are not required.
...................................................................................................................
...................................................................................................................
..................................................................................................................
(3)

(iii)

Suggest, with reasoning, whether a laboratory coat made from a polyester might be
damaged by a spillage on it of hot concentrated aqueous sodium hydroxide solution.
............................................................................................................................
............................................................................................................................

............................................................................................................................
(2)

(iv)

Give another type of reagent that could be used to make an ester from an alcohol.
............................................................................................................................
(1)
(Total 13 marks)

8.

Consider the following reaction scheme starting from propanone.

(a)

Give the structural formula of:

H

(4)

(b)

Identify:
Reagent 1: ..................................................................................................................
Reagent 2: ..................................................................................................................
9

Reagent 3: ..................................................................................................................
(3)

9.

The pain-relieving drug ibuprofen has the formula

CH
H

C H

CH
(a)

C H

C O 2H

A molecule of this compound is chiral. Explain, with the aid of diagrams, how two
optical isomers result from chiral a centre. Identify the chiral centre in such a molecule
and explain how these isomers could be distinguished from each other.
(4)

(b)

Compounds A and B, shown below, are used as intermediates in the manufacture of

ibuprofen.
C H

CH

C H

C H

C H

C
C H

CH

C H

(i)

O H

Suggest how infra-red spectroscopy could be used to identify an impurity in a

sample of ibuprofen which is known to be one of these two compounds.
A table of infra-red absorbencies is given below.
Bond
C-H

Assignment

Wavenumbers/cm1

alkanes
alkenes, arenes

2850 - 2950
3000 - 3100

arenes

1450 - 1650

C=O

aldehydes, ketones, esters,

carboxylic acids

1680 - 1750

O-H

free
hydrogen bonded in alcohols or phenols
hydrogen bonded in carboxylic acids

3580 - 3670
3230 - 3550
2500 - 3300

benzene ring

(3)

(ii)

Suggest a simple chemical test which would distinguish between A and B.

(2)

(c)

Under the appropriate conditions ibuprofen reacts with ethanol to produce a substance
with a characteristic odour. Identify the functional group in ibuprofen that would react
with the ethanol. Suggest the conditions needed for the reaction to take place and identify
the product.
(3)

10

10.

(a)

Describe a chemical test, with results, to distinguish between the compounds propanone,
CH3COCH3, and propanal, CH3CH2CHO.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)

(b)

Propanal can be converted into sodium propanoate in two steps. State the reagents and
conditions required for each step.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)

(c)

The mass spectrum of propanone gave peaks at m/e values of 58, 43 and 15. Give the
structural formulae of the species responsible for these peaks.

(d)

State, with reasons, the number of peaks in the NMR spectra of propanone and propanal.

(3)

...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(4)

11

11(a) A compound, Z, C6H5(CH3)(CN)OCOCH3, has been proposed as a possible new insecticide.

Consider the following scheme for the production of compound Z.

(i)

Identify the reagent used in step 2

(1)

(ii)

Give the reagents for Step 1, and draw and name the mechanism.

(5)

12

YEAR 13

A2

ORGANIC EXAM QUESTIONS - ANSWERS

1 (a) Step 1 ethanol (1)

concentrated sulphuric acid (1)heat / reflux (1)

(b)

(i)
C6H5CO2C2H5 + NaOH C6H5CO2Na + C2H5OH (1)
allow C6H5CO2C2H5 + OH C6H5CO2 + C2H5OH
not C6H5CO2H5 + H2O

(ii)

hydrolysis / saponification (1)

(c)
ethanol-distil off (1) must be clear this is ethanol
sodium benzoate-evaporate to small bulk (1)
crystallise (1)
OR
add acid (1)
filter (1)
react with NaOH (1)
2.
eg CIOCC6H4COCI
any di-acid / di-acid chlorides / di-esters / different diol (1)
if same diol used (0)
box representing backbone (0)
repeat structure (1) if diol used in (i) a polyether is formed
because the linkage is hydrolysable (1) and the products formed on breaking
down are not toxic (1)
can be treated with NaOH to decompose (1)
or will hydrolyse slowly etc. (2)
some indication that it will disappear over a period of time in the environment
is required
(Total 5 marks)
3

(a)

(i)

13

KM nO 4/ H 2SO 4 or
K 2 C r 2 O 7 /H 2 S O 4 (1 )

C H 3C H 2O H

h e a t (1 )

C H

C O O H (1 )
P C l 5 ( 1 ) r. t ( 1 )

C H

C O C l

Other possible reagents for step 2 include PCl3 and heat or SOCl2 at room
temperature; not P + Cl2
4(a) (i)

(b)

(c)

D (1) 1
(ii)

ionic (1) hydration energies of ions (OWTTE) / water is polar (1)

(i)

B (1)

(ii)

B has long alkyl etc chain i.e. focussing on the C15H31 group /
A and C have more sites for H bonding (1)

(i)

esterification (1)

(ii)

acid (catalyst) (1) H+ acceptable heat under reflux (1)

or
conc (1) sulphuric acid (1)

A to B:
C to D:

(iii)

(d)

(i)

(ii)

(e)

C15H31CO2H or the acid chloride (1) not C16H32O2

NaOH / NaHCO3 / Na2CO3 (1)

dissolve in min () quantity

hot () suitable solvent
filter when hot () cool () to crystallise
filter ()
wash () dry ()
(3 max 3)

determine melting point and compare to known values (1)

or sharp melting point (1)
if spectroscopy mentioned it must be explained fully

hydrolysis (1) not saponification

1
[15]

(a)

Peak 1
Peak 2
Peak 3

m/e 77: C6H5+ (1)

m/e 105: C6H5CO+ (1)
m/e 134: C6H5COCH2CH3+ (1)
14

(b)

if + left off penalize only once

(i)

IR spectrum number 2

(ii)

Because of the broad peak at 3320cm1 caused by OH / because peak at

3320 is OH / because it does not have a peak at 1750 and is only one

without

(c)

O 1

(iii)

The other has a peak at approx. 1700 cm1 caused by C=O

(i)

(brown) goes colourless

(ii)

silver mirror / black precipitate

(iii)

A (1) and B (1) red/orange/yellow ppt

2
1

6(a) Substance A is CH3CH2COCH3 (1)

Substance B and C are CH3CH2CH2CHO (1) and CH3CH(CH3)CHO (1)

7
(a)

(i)

Has two isomers that are nonsuperimposable (1)

mirror images (1) not stand alone
or
The molecule does not have a plane of symmetry
or
The molecule contains a single (1) asymmetric carbon
atom (1)
C 2H
(ii)

C
C H

(iii)

(b)

(i)

O H
H

C 2H

H O

C
H

C H

One correct 3 D diagram (1)

second molecule mirror image of first as drawn (1)
Stand alone provided two tetrahedral mirror image drawn of C4H9OH

Rotates the plane of plane polarised (monochromatic) light (1)

in opposite directions (1)
Consequential on mention of polarised light
or
Use polarimeter (1)
measure rotation (of plane of polarised light) in opposite
directions (1)

CH3COOH + C2H5OH
CH3COOC2H5 + H2O (1)
Any valid ester equation scores the mark but must be
actual molecules not ROH or RCOOH
Equilibrium sign not important

15

(ii)

(iii)

(iv)

double alcohol / alcohol at each end (1)

double acid / acid at each end (1)
or
Alcohol group at one end and acid group at the other (2)
Could be shown on an equation or as diagrams
React at each end / illustrate with equation or diagram to
show production of a long chain polyester (1)

Esters react with alkalis/ ester linkages are hydrolysed (1)

conc / hot will attack polyesters / coat will be damaged (1)
too slowly to be a problem (1)
Second mark consequential on first

Acyl chlorides / acid chlorides / acid halides / RCOCl / acid

anhydride (1)
Not specific reagent

1
[13]

8(a) H is CHl3 (1)

J is CH3 COONa/CH3COO (1)
Not CH3COOH
Note H and J can be reversed
CH
K is C H

O H (1)

CN
If cyanide group shown displayed show C N must be correct
Allow CH3 C(OH)(CN)CH3 only if brackets present
C H
M is C H

C H

N H

or

C H

C l
(b)

C
N H

O H

(1 )

Reagent 1 Named dilute acid /correct formula

e.g. HCl(aq) or NaOH (aq) then add HCl (1)
Allow conc HCl
Reagent 2 PCl5 / SOCl2 / PCl3 / or name (1)
Reagent 3 (Conc) ammonia (solution) / NH3 (1)

CH
(a)

C
CH

C H

C H
3

C O 2H
Identification of chiral centre (1)
16

2 diagrams to show two isomers of non-superimposable molecules

3D diagram (1)
mirror image (1)
Distinguish by rotation of the plane of (plane)-polarised light (1)

NB could identify their own real molecule.- correctly shown.

Not necessarily Ibuprofen
(b)

(i)

(ii)

(c)

COOH is present anyway absorbs at app 280and 1700

If A is present nothing else
If B peak at 3600
or
A spectrum will include 1700 but not 3600
B will include 3600
Marking points
identification of groups to note (1)
link to peaks in spectrum (1)
how to distinguish (1)

Correct test (1)

PCl5
or
2,4 dinitrophenylhydrazine
or dilute sulphuric acid plus potassium dichromate(VI)
or sodium hydroxide and iodine
2 correct observations (1)

COOH (1)
warm with a little conc sulphuric acid (1)
ester (1)

10(a) Heat with Fehlings solution or heat with ammoniacal silver nitrate
(1)
Ketone: no change (1)
Aldehyde: red ppt. or silver mirror (1)
3
Alternatives
Allow: heat with dilute sulphuric acid and potassium
dichromate (VI) OR heat with dilute sulphuric acid and potassium
Ketone: no change (1)
Aldehyde: solution turns orange to green OR purple to colourless
(1)
Allow: iodine + sodium hydroxide solution/potassium iodide +
sodium chlorate (l) (1)
17

Ketone: yellow ppt. (1)

Aldehyde: no change (1)
(b)

(c)

K2Cr2O7 / H2SO4 OR KMnO4 / H2SO4 (1)

Heat (under reflux) Consequential on correct reagents/OR
identify propanoic acid as the intermediate (1)
NaOH/Na2CO3 + aqueous/dilute/room temp. (not heat) (1)

CH3COCH3+ (1)
CH3CO+ (1)
CH3+ (1)

Penalise omission of + charge once only

if m/e not stated, assume ions are listed in m/e order 58, 43 and
15
(d)

Propanone has 1 peak (1)

Only one type/environment of hydrogen/proton (in a CH3 group) (1)
Propanal has three peaks (1)
One in a CH3, one in a CH2 and one as part of a CHO group OR
other suitable justification (1)

NB Answers in terms of e.g. I. R./M. S. scores zero

Reagent: ethanoyl chloride / CH3COCL (1)

Conditions Room temp
(ii)

Reagents: potassium cyanide + named acid / potassium cyanide buffered

between pH 6 to 8 / hydrogen cyanide + named base / hydrogen
cyanide buffered
between pH 6 to 8 / HCN + KCN (1)
1
Names or full formulae acceptable
Mechanism:

CH
C
:C N
(1 )

C H

(1 )

C
C N

11(a) (i)

or H

CN

(1 )

Marks awarded for:

Curly arrow from C (not the minus) of -CN ion towards C of C=O (1)
Curly arrow from C=O bond to O atom (1)
Intermediate with its charge and a curly arrow from O (not the minus)
to H+ or to H of HCN (1)
18

3
Type: nucleophilic addition (1)

19