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

UNIVERSITY OF
TECHNOLOGY,
SYDNEY
NAME: _________________________

STUDENT NO.: __________________

COURSE: _______________________

_____________________________________________________________________________

SAMPLE EXAMINATION PAPER

AUTUMN SEMESTER

subject number 65202

ORGANIC CHEMISTRY 1

start: _____. - finish: _____.

TIME ALLOWED: 3 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.

please attempt ALL questions

WRITE EQUATIONS WHEREVER POSSIBLE

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question 1 (14 marks)

H H
(a) Muscalure (M), a sex attractant pheromone, has been used for C C
CH3(CH2)7 (CH2)12CH3
biological control of the common housefly. Male flies are drawn to M
muscalure
traps baited with muscalure and an insecticide.

(i) Show how muscalure can be synthesised from acetylene (ethyne), CH3(CH2)12Br
N
1-bromooctane, and 1-bromotridecane N. 1-bromotridecane

(ii) Palmitic acid, CH3(CH2)10COOH, (represented as RCOOH below) is a readily

available precursor for the synthesis of N:

RCOOH RCH2CH2Br
palmitic acid N, 1-bromotridecane

(p) (q again)
(q) (r) (s)
RCH2OH  RCH2Br  RCH2MgBr  RCH2CH2OH

Suggest reagents and reaction conditions which can be used for steps p, q, r and s.

(b) You are provided with acetylene (ethyne), iodomethane, and bromoethane, plus any
inorganic reagent. Show how you would prepare the following:
(i) cis-2-butene (ii) 3-hexanone

Question 2 (5 marks)
Show how the Williamson ether synthesis can be used to prepare the following compounds.
Using structural formula, write a balanced equation , show all possible reactants and any other
reagents you would require for each compound.

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question 3 (10 marks)

(a) Compound A, known to have molecular formula C8H8O, was tested in the organic 1 lab.
 When A is boiled with hydrazine (N2H4) and NaOH solution
(Wolff-Kishner reaction), ethylbenzene is formed.
 Reaction of A with 2,4-dinitrophenylhydrazine produces orange crystals of B
 Reaction of A with hydroxylamine (H2NOH) gave a white crystalline solid C.
 Boiling A with Fehling's solution (CuSO4 + tartrate + NaOH) gave a red-brown
precipitate; addition of 2M sulfuric acid to the solution gave an organic product
D which was insoluble in water but soluble in 2M sodium hydroxide.
H
H2N N NO2

O2N N2H4 / OH

B A CH2CH3
2,4-dinitrophenylhydrazine C8H8O
ethylbenzene
NH2OH Fehling's

C D

(i) Explain how you can work out the structure of A from the results above.
(ii) Write structures for B, C and D.

(b) Which of the IR spectra (X, Y or Z) shown is consistent with the structure of A in part (a)
above? Assign the labelled peaks in the spectrum you have chosen.

1604 2895

3064 1595
X 3340 Y 1724 Z

wavenumbers (cm-1) wavenumbers (cm-1) wavenumbers (cm-1)

(c) Give structures for the product(s) (including any stereoisomers) of these reactions:
H / CN
+
i) propanal  A
O
+
H2C CH2 H / H2O
ii) CH3CH2CH2CH2MgBr   B Q(c) ii, is not covered in the
lecture materials
xs NaBH
iii) C C 
4
C
O O

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question 4 (14 marks)

(a) Show how 1-bromo-3-methylbutane can be converted to 4-methylpentanoic acid by

i) the Grignard synthesis
ii) via the nitrile.

(b) Which (if either) method in (a) could be used to prepare benzoic acid from
bromobenzene? Very briefly justify your answer.

O
(c) Write balanced equations for the following reactions:
H 2C C
O
i) reaction of succinic anhydride with water H 2C C

ii) conversion of butanoic acid to its acid chloride O

iii) conversion of the acid chloride from (ii) to the methyl ester succinic anhydride

(d) Following from (c) (ii) and (iii), what if any advantage is there in preparing the ester in
two steps rather than directly from the acid and alcohol?

(e) Write equations for the following two-step conversions

CH3CH2CH2CH2NH2
(i) 1-bromopropane to 1-butanamine
1-butanamine
(ii) 1-bromobutane to 1-butanamine

(f) Write a balanced equation for a one step preparation of CH3CH2 O

N C
N,N-diethylacetamide from diethylamine and any other CH3CH2 CH3
appropriate carbon compound.

N,Ndiethylacetamide

(g) Which is a stronger base, N,N-diethylacetamide or diethylamine?

Briefly show how their molecular structures account for the difference in base strength.

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question 5 (14 marks)

(a) The diagram represents energy diagrams for two reactions,

namely the bromination of benzene and the bromination of
phenol in the para position.
B

energy
(i) Briefly explain how you can tell which curve is which.
b A
a
(ii) Draw resonance structures for the two species A and B,
and show how they help account for the relative rates
of the two reactions.

(b) Which of the following substituents deactivate an aromatic ring towards electrophilic
substitution? -COOH -CH2CH3 -Br -CCl3 -N(CH3)2 -+N(CH3)3
What do all deactivating groups have in common?

(c) Arrange the compounds G - L in increasing order of reaction rate with Br2/AlCl3.

COOH CH2CH3 COOH COOH COOH

Br

CH2CH3 Br Br
G H J K L

(d) Following from (c), write a balanced equation for the reaction of compound J
with one mole of Br2/AlCl3.

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question 6 (10 marks)

(a) 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 reaction of nitrobenzene with Cl2 and AlCl3. Label the peaks you
have drawn; 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)

(b) Are the reactions in part (f) (above) under thermodynamic or kinetic control?
Briefly, what evidence do you have to support your answer?

O CH2CH3
C
(c) Write equations for converting benzene to the compound shown.
In which of these reactions is it advisable to use excess aromatic reactant?
Very briefly explain why this is so.
CH2CH3

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question 7 (22 marks)

(a) You are given samples of p-cresol and p-toluidine CH3 CH3
(both are solids, insoluble in water). Explain how
you can distinguish between them:
i) using 2M HCl solution OH NH2
ii) using 2M NaOH solution p-cresol p-toluidine
Write equations for all the chemical reactions involved.

(b) Three groups of organic 1 students were asked to prepare some brominated benzenes.
i) Group A reacted benzene with bromine until a tribromobenzene was formed.
Write the structures of the isomer they obtained.

ii) Group B reacted aniline with excess bromine, then removed the NH2 group.
Write a reaction sequence they may have used.

iii) Group C did a series of steps, converting benzene to 3-bromobenzenediazonium

ion, which was then further reacted to give 1,3-dibromobenzene. Write a
possible reaction sequence, providing details for all the steps.
several
benzene N N 1,3-dibromobenzene
steps

Br
3-bromobenzenediazonium ion is not in the scope of our lecture
material
iv) Following from (iii), when group C tested their diazonium solution by
N(CH3)2
adding N,N-dimethylaniline, a bright red precipitate was formed.
Write the structure of this bright red product. N,N-dimethylaniline

(c) The structures of p-toluidine and N,N-dimethylaniline are shown above. Briefly show
how these compounds can be distinguished using benzenesulfonyl chloride, C6H5SO2Cl.
Write equations for any chemical reactions.

oc1 sample final exam .../over

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question 8 (11 marks)

(a) The amino acid L-threonine (P) has a melting point of 257 and []D of 28 (structure below).

i) Give the systematic name of P and OH H

CH3 C C COOH
the systematic names and structures of its
H NH2
enantiomer (Q) and a diastereoisomer (R).
P
L-threonine
ii) Are any of the compounds P, Q or R examples of a []D = 28°; mp 257

meso isomer? Explain very briefly.

iii) What (if anything) can you predict for the melting point
and specific rotation, D, of Q or R, given the values for P (above)?

(b) i) Under what circumstances is a sample of 2-butanol optically inactive?

ii) For each of the reactions below, state whether the 2-butanol formed is optically active
or optically inactive. Write one or two sentences to justify each answer.

 S-2-bromobutane + H2O / Ag+ (SN1 mechanism)

 S-2-bromobutane + 5 M NaOH (SN2 mechanism)

(c) Optically inactive amphetamine can be resolved using (R)-lactic acid.

Explain what “resolve” means in this context. Briefly describe the procedure involved,
writing equations for any reactions.

OH
CH2CHCH3 CH3 C COOH
NH2 H
amphetamine (R)-lactic acid

(d) Comment briefly on whether any of the compounds below could be resolved
using R-lactic acid and following the same procedure as in (c).

CH2CHCH3 CH2CH2 CH2CHCH3

NHCH3 NH2 OCH3

END