Practice exam

ANSWERS
The answers provided are a rough guide only, in many cases more will be
expected from you in the exam to justify the marks associated with each
question.

Question 1
[11 marks]
(a) Amprenavir is a drug used to treat HIV. The structure given below is an
analogue of amprenavir; on the structure below please circle and name each
of the functional groups present.

(3 marks)

(b) Nandrolone is an anabolic steroid sometimes taken by athletes to build

muscle mass; on the structure below label the indicated atoms as 1o, 2o, 3o or
4o.

(2 marks)

(c) Draw the skeletal structures of the following molecules:

(i) 2-bromopropane

(ii) ethoxide ion

(iii) 3-amino-2-methylpropanoic acid

(iv) 2,4-diaminotoluene

(4 marks)
(d) Please name the following structures.

Answer:______

Answer
(2 marks)
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Question 2
[12 marks]
(a) Sighting along the C2-C3 bond of 2-chloropentane, there are four
possible Newman conformations. Please draw the most and the least stable
and explain your choice.

Steric hindrance

(3 marks)
(b) For each of the substituted cyclohexanes below, please draw its ring-flip
isomer, circle the most stable conformation and indicate if the structure is a
cis or trans isomer.

Isomer:_______________________________________

Isomer:_______________________________________

(4 marks)
(c) Rank the following alkenes in order of increasing reactivity; from least
reactive (1) to most reactive (4). Place the number corresponding to the
compounds rank below the compound.

(2 marks)
(d) On the structures provided below, please draw the arrows showing the
complete stepwise mechanism for this reaction.

(3 marks)

Question 3 [12 marks]

(a) Please draw the mechanism (including any relevant resonance
structures) to show the formation of the major product for the reaction of the
following diene with hydrobromic acid in ether.

(b) Label the following pairs of compounds as either; constitutional isomers,

enantiomers, diastereomers, meso or none of the above.

(3 marks)
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(c) Using any combination of the following reagents, to show how you would
synthesise the
following products from benzene by filling in the blank squares with both the
reagents and any intermediates as indicated. Assume that you can separate
ortho and para isomers as necessary.
(a) KMnO4, H3O+
(b)Br2, FeBr3
(c) Cl2, FeCl3
(d)CH3Cl, AlCl3
(e) HNO3, H2SO4
(f) H2, Pt Catalyst

(6 marks)
Question 4

[15 marks]
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(a)
Using the designations R, S, Z or E, specify the configuration of
each of the following molecules

(2 marks)
(b) 1-bromoheptane can be converted to 1-heptanol through an SN2 type
reaction. However, if the correct solvent and reaction conditions are not
used an E2 reaction will occur preferentially.
KOH
Br

OH

(i) How could you use IR spectroscopy to ensure that an E2 type reaction
had not occurred?
OH bond would appear at 3500 cm-1 while no C=C bond at 1600cm-1 would
appear

(ii) What type of solvent would you use to ensure that an E2 reaction did not
occur
Polar protic, solvate the nucleophile make it less reactive to elimination

(2 mark)
(c) Tertiary alkyl halides undergo SN1 and E1 type mechanisms in
competition. Please draw both mechanisms for the reaction of 3-bromo-3methylhexane with sodium hydroxide.

(3 marks)

(d) 3-bromo-3-methyl hexane has an optical rotation of -5.75, would you

expect the SN1 product of the above reaction to be optically active? Please
explain.
No, because SN1 proceeds via a planar carbocation, to give a racemic
mixture

(1 mark)

(e) Match the letters on the energy profile diagram with the structures on
the right

D
A

(2 marks)
(f) Draw the mechanism (using curly arrows) to show the halogenation of
(4R,5R)-4,5-dimethylcyclohex-1-ene with Br2

(3 marks)

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Question 5
[11 marks]
(a) Carvone is the major constituent of spearmint
oil
In the six spaces below complete the outline
structures thereby showing the structural formulae of substances which will
be formed when carvone reacts with each of the named reagents. (note that
just the bare skeleton of the product is shown. You must add in all the
necessary details, i.e. double bonds and functional groups.)

(4 marks)
(b) Lactose is a disaccharide and can be represented by the structure shown
below. On the structure please label both the hemiacetal and acetal groups
of lactose

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(1 mark)
(c) Write the stepwise mechanism for the Fischer esterification reaction of
benzoic acid and methanol. Show all electron movement using curved
arrows and include any intermediate structures.
H

O
H

OH

Cl

OH

OH
O
O
H

H2O
OCH3

CH3

Proton transfer

CH3

OH

OH
OCH3
O

OH2+

+ H3O

CH3

(4 marks)
(d) Calculate the theoretical yield of the following reaction:
250 mg of 1-bromopropane is reacted with 127 mg of methylamine.

Tyield = 146 mg

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(2 marks)
Question 6
[8 marks]
(a) Dimestrol can be prepared from only p-methoxypropiophenone, please
fill in the blanks below to complete the synthesis.

(2 marks)
13

(b) In the UV spectra of the two compounds below, the important

absorptions for the C=C double bonds will occur at a longer wavelength in
one of the compounds. Circle this compound and please give a brief
explanation as to why this is so.

(a) Due to conjugation

(1 mark)
(c) A mass spectrum of chlorobenzene shows a number of molecular ions.
112 m/z
114 m/z
77 m/z

(i) The exact mass for chlorobenzene is 112 m/z why is it then that a second
peak at 114 m/z is visible? Please explain
Isotope effect
(ii) Based on your knowledge of fragmentation patterns, what does the
molecular ion at 77 m/z represent? Please draw a structure.
Phenyl cation

(2 marks)
14

(d) Deduce the structural formula for compound A from the 1H NMR
spectrum shown below. The compound has a formula of C5H9BrO and an IR
stretch at 1725 cm-1. Please indicate on the structure, which hydrogens give
rise to each signal and account for the IR stretch.
3H,singlet

2H, triplet

2H, triplet
2H,quintet

(3 marks)
Question 7

[10 marks]
15

(a) Fill in the missing intermediates in the following reaction schemes?

(i)

(ii)

(iii)

(iv)

(4 marks)
16

(b) At what position(s) and on which ring, is bromination of phenyl benzoate

expected to occur? Please explain your answer and draw the product

Left hand ring is deactivated due to carbonyl, ring hand ring is activated due to O group.
Bromination can occur at either of the indicated positions.

(4 marks)
(c) Fill in the blanks to complete the reaction scheme

(2 marks)

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Question 8
[11 marks]
(a) Please explain the observed pKa difference between p-nitrophenol, pbromophenol and p-methylphenol.

O2N

OH

p-nitrophenol pKa = 7.15

Br

OH

p-bromophenol pKa = 9.35

H3C

OH

p-methylphenol pKa = 10.17

Methyl is activator, gives electrons towards OH, increases electron density,

less likely to lose proton, hence high pKa
Bromo is a deactivator, reduces electron density at OH, stablises conjugate
base, hence more likely to lose proton compared with methylphenol
Nitro is the strongest deactivator, electron withdrawing by resonance and
induction, lose of proton yields most stable conjugate base.

(3 marks)
(b) Rank the following compounds in order of increasing basicity, from least
basic (1) to most basic (4). Place the number corresponding to the
compounds rank below the compound.

(2 marks)

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(c) Devise a synthesis of compound A from compound B, indicating all

reagents and intermediates required. No mechanism is needed.

Use CN, then LiAlH4

(2 marks)
(d) The amino acid histidine has three pKas; Please assign each of these
pKas to the correction functionality on the structure of histidine given below
and explain your choice
pKa1 = 1.82
pKa2 = 6.00
pKa3 = 9.17

(3 marks)
(e) Calculate the pI (isoelectric point) of Histidine based on the pKa values
given above
pI = 7.59
(1 mark)
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Question 9

[16 marks]

(a) What is the purpose of an acid-base buffer

Maintain constant pH
(b) Find the pH of a buffer that consists of a 1.0 M sodium acetate and 1.2 M
acetic acid pKa (acetic acid) = 4.75 using the Henderson-Hasslebach
equation as given

pH = 4.67

(3 marks)
(b) Chlorambucil is a synthetic drug mainly used in the treatment of chronic
lymphocytic leukemia. It has only one pKa under physiological conditions.
What is the degree of ionization of Chlorambucil at pH 6.5, if its pKa is 5.8

= 83.36%

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(2 marks)
(c) Label the diagram of the peptide shown below to identify:-

(i) each amide bond

(ii) each primary hydroxyl group
(iii) each ester
(iv) each chiral carbon
(4 marks)
(d) There are three isomeric forms of tartaric acid (molecular formula HO 2CCHOH-CHOH-CO2H). Write Fischer projections for each of these three forms in
the space below. Also indicate on your diagram which two of these are
enantiomers, and which is a meso compound.
[3]

(4 marks)
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(e) Phosphoric acid (see the structural formula below) is an example of a

triprotic acid, with
pKa1 = 2.12, pKa2 = 7.21 and pKa3 = 12.67.

(i) Explain what is meant by a triprotic acid.

Three protons can be lost
(ii) Sketch below the form of the titration curve (i.e. pH against volume of
base added) you might expect to obtain in a titration of phosphoric acid with
NaOH. Indicate clearly on your diagram where the pH coincides with the
three pKa values of phosphoric acid.

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(3 marks)

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Supplementary Data
Buffers
Acetic Acid pKa = 4.76
Pyridine
pKa = 5.23
HEPES
pKa = 7.66
Phenol
pKa = 9.89
1

H NMR chemical shift data

IR spectral data

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