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Cover Page - Type B:

THIS PAPER MUST NOT BE REMOVED - TO BE RETURNED AT THE END OF THE EXAMINATION

UNIVERSITY OF
TECHNOLOGY,
SYDNEY
NAME: _________________________

STUDENT NO.: __________________

COURSE: _______________________

____________________________________________________________________________________

subject number 65202


ORGANIC CHEMISTRY 1

SAMPLE PAPER

TIME ALLOWED: 2 hours 10 minutes

This examination is designed to be done in 3 hours.


It is recommmended that the extra 10 minutes be used
to read the paper carefully before commencing.

attempt ALL questions

WRITE EQUATIONS WHEREVER POSSIBLE


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question 1 (9 marks)

(c) Give reagents and reaction conditions needed to convert benzene to ethylbenzene.
Explain briefly why this reaction tends to give substantial quantities of diethyl- and
triethylbenzenes, and suggest a way to minimise this problem.

(d) Write a reaction sequence for preparing 4-trichloromethylbenzenesulfonic acid from toluene.

CCl3 SO3H

4-trichloromethylbenzenesulfonic acid

(e) Write a reaction sequence for preparing 4-methylbenzoic acid from toluene.

...../over
-2-

question 2 (10 marks)

(a) Write structural formulae for the major organic products of the following reactions.
NO2
i) ethanal with 2,4-dinitrophenylhydrazine
ii) propanal with HCN O2N NH NH2

2,4-dinitrophenylhydrazine

(b) Show how samples of benzaldehyde, 1-phenylethanone and 1-phenylpropanone can be


distinguished in the laboratory on the basis of two chemical tests.
Briefly describe what you would do and see, and write equations for any reactions which occur.

C H C CH3 C CH2CH3
O O O
benzaldehyde 1-phenylethanone 1-phenylpropanone

(c) Show reagents and reaction conditions you would use to make 1-phenylethanone (structure
above) from each of the following starting materials.
More than one step may be necessary.

(i) 1-phenylethanol
C CH2
(ii) 2-phenylpropene
CH3
(iii) benzene and ethanoic acid
2-phenylpropene

...../over
-3-

question 3 (15 marks)

(a) Ethanol, 2,2,2-trifluoroethanol (CF3CH2OH, TFE) and trifloroacetic acid (CF3COOH, TFA)
have pKa values of 0.23, 12.43 and 16.00 (not necessarily in that order).
Match the pKa values to the compounds, and briefly discuss why they differ.

(b) Write balanced equations for any reactions which occur when:

i) acetic anhydride is mixed with dimethylamine, (CH3)2NH CH3COCCH3 CH3CCl


ii) acetyl chloride is mixed with cyclohexanol O O O
acetic anhydride acetyl chloride

(c) Complete the balanced equation for the following ester hydrolysis reaction:

CH3 O
CH3CHCH2OCH + H2O
1 mole 1 mole
This reaction is accelerated when sulfuric acid or sodium hydroxide is added.
Describe any ways in which the reactions differ when promoted by acid or base.

(d) Write equations for a reaction sequence converting 3-bromopropanol to 4-hydroxybutanoic acid.

(e) Write structures for the reaction products when the following are treated with LiAlH4 in dry ether:
i) methyl benzoate
ii) benzamide .

...../over
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question 4 (13 marks)

(a) A bottle labelled “dimethylaniline” was known to contain either A, B or C. A group of organic 1
students tested the liquid inside. Interpret their observations (listed below) and work out which
compound it was; write a sentence to explain how each observation helped you decide.
CH3
CH3 H
N CH3 N NH2
CH3 CH3

CH3
A B C
liquid, bp 194° liquid, bp 210° liquid, bp 220°

1. the compound formed two layers with water, but one layer with 5M HCl;
2. reaction with benzenesulfonyl chloride, C6H5SO2Cl, and NaOH gave a crystalline product;
3. the product from (2) dissolved in excess 2M NaOH (2 and 3 make up the Hinsberg test).

(b) Write a sentence to explain the boiling point difference between A and C.

(c) The pH indicator methyl red can be made by the following steps.
Supply the reagents and reaction conditions for each step.

CH3 COOH COOH

NO2 NO2 NH2


step #1 step #2

step #3

COOH
COOH
N CH3
N N N N Cl
step #4
CH3
methyl red
D

(d) Write a balanced equation for the reaction which occurs when a solution containing D
(product of step #3, above), is warmed on a steam bath.

(e) Write a reaction sequence for converting nitrobenzene to 1,3,5-trichlorobenzene.


...../over
-1-

question 5 (14 marks)

(a) What compound would you react with benzene and aluminium chloride
to prepare a sample of 1,2-diphenylethane?

(b) Arrange the following compounds in order of increasing rates of bromination


(write the slowest one first):

C(CH3)3 C(CH3)3 OCH3 C(CH3)3

OCH3 NO2
J K L M

(c) Write a balanced equation for the reaction of K (above) with one mole of bromine.

(d) A shows a gas-liquid chromatogram (GC) of the product mixture from the nitration of
chlorobenzene. On this exam paper, sketch the missing part of chromatogram B, the
product mixture for the chlorination of nitrobenzene (Cl2/AlCl3). (Assume the GC is run
under the same conditions as in A).

A: experiment B: your prediction


nitration of chlorobenzene chlorination of nitrobenzene

para
solvent Cl solvent

NO2

ortho
meta

min 0 1 2 3 4 5 6 7 8 9 10 min 0 1 2 3 4 5 6 7 8 9 10

gas-liquid chromatogram gas-liquid chromatogram


(crude reaction mixture) (crude reaction mixture)

...../over
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question 5 (cont’d)

(e) Each of the diagrams C - H below shows three energy profiles 1-3. Which diagram best
represents the nitration of chlorobenzene to form ortho, meta and para
chloronitrobenzenes? Explain in one or two sentences how the features of your chosen
diagram fit what is known about this reaction.

C D E

F G H

(f) Are the reactions in part (d) thermodynamically or kinetically controlled?


Briefly, what evidence do you have to support your answer.

(g) Write equations for the preparation of 4-nitrobenzoic acid from toluene.

...../over
question 6 (13 marks)

The non-steroidal anti-inflammatory drug ibuprofen (A) is the active


ingredient in a number of over-the-counter medicines in
Australia, including ‘ACT-3’, ‘Brufen’ and ‘Nurofen’. It is
COOH
manufactured in very large quantities in North America, where it
ibuprofen
makes up 25% of a market which includes aspirin and
paracetamol.

The industrial precursor for ibuprofen manufacture is (2-methylpropyl)benzene, which is made from
benzene. However, the reaction below cannot be used, as it leads to the wrong product:

CH3 AlCl3 CH3 CH3


CH CH2 C CH3 CH2 CH
CH3 excess C 6H6
Cl CH3 CH3
(1,1-dimethylethyl)benzene (2-methylpropyl)benzene
[t-butylbenzene] [isobutylbenzene]
NOT FORMED

(a) With the help of mechanisms for each step (using arrows to show electron movements),
explain how and why t-butylbenzene (and not isobutylbenzene) is formed in this reaction.

(b) Why is excess benzene routinely used?

(c) Write steps for a practical synthesis of isobutylbenzene from benzene (no mechanism necessary),
and a sentence pointing out two advantages of your method.

(d) The following steps can be used to convert isobutylbenzene to ibuprofen.


Give reagents and reaction conditions for steps a, b and c, and for converting D to E.
O
a b
C CHCH3
CH3 OH
A B C
c

CHCH3
COOH Br
E D
ib uprofen

end
question 8 (7 marks)

Chilo auricilius is one species of borer whose larvae infest sugarcane crops in south Asia.
A strategy for controlling this moth is to disrupt the reproductive cycle by distributing small baits
containing the female sex pheromone, thus confusing the males. A major component of the pheromone
was determined in 1985 to be 7-Z-dodecenyl acetate (A). Parts (a) and (b) of this question describe a
published synthesis of A which uses reactions studied in organic chemistry 1.

(a) 1-Hexyne was prepared from 1-bromobutane , acetylene Please note Q8a and
1-bromobutane and acetylene (ethyne). Write 8c
(a)
are not covered in
balanced equations for each reaction step. the lecture
H
C
C 1-hexyne materials
same
method as in
(b) The 1-hexyne was converted to (a)

7-dodecynoic acid (B), and then by a series of OH


C C
steps to A as shown. C
B O
7-dodecynoic acid

(i) Which reagent, H2SO4, NaOH, LiAlH4,


(i)
KMnO4 or AlCl3,
OH
C
is most suited for step (i)? C

(ii)
(ii) Suggest a reagent for step (ii). Are any
special precautions required to ensure that no OH
C C
E-isomer is obtained? H H

(iii)
(iii) Suggest a reagent and reaction conditions
O CH3
for step (iii). C C C
H H O
A
7-Z-dodecenyl acetate

(c) In the reaction below, the initial product C spontaneously changes into the stable product D. Give
the structures of C and D.
H
C H2SO4 fast
C + H2O [C] D
HgSO4
unstable form of stable
product D

end

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