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THIS PAPER MUST NOT BE REMOVED - TO BE RETURNED AT THE END OF THE EXAMINATION
UNIVERSITY OF
TECHNOLOGY,
SYDNEY
NAME: _________________________
COURSE: _______________________
_____________________________________________________________________________
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
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.
(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
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
(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
(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
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?
N,Ndiethylacetamide
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.
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.
(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.
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
(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
(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.
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.
(a) The amino acid L-threonine (P) has a melting point of 257 and []D of 28 (structure below).
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)?
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.
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).
END