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(b) Suggest suitable reagents and reaction conditions to accomplish each of the
transformations a.-i. below.
Br MgBr CO2H c. CO2Me
a. b.
d.
e.
h. CHO f. OH
i. g.
[9 marks]
(c) Determine the multiplicity (splitting pattern) of the protons at C1, C2 and C3
of molecule A. Comment on their relative chemical shifts and integration.
2 1
Ph 3
Cl H
A
[5 marks]
(d) Provide structures for compounds B and C, justifying your answers with
mechanistic reasoning.
O HCl, H 218 O
B
MeO OMe
HCl, H 218 O
H C
[6 marks]
CONTINUED
5 CHEM1032W1/1038W1/1022W1
SECTION B: Answer TWO questions
2. Answer ALL parts
(a) When optically active benzyl chloride D was treated with acetic acid it gave
racemic acetate E as a product. Suggest a mechanism for the reaction and
account for the loss of optical activity.
O
O
Cl O
OH
heat
D E
[4 marks]
(b) In the synthesis below, provide structures for unknown compounds F, G and
H and give mechanisms for all transformations shown.
O i) LDA iii) DiBAl-H O
F Li
O i) BnBr -78 oC, CH2Cl2 Ph LDA = N
NH 4Cl H 2O
NaOH, H 2O, H
Al
100 oC NH 2 KCN DiBAl-H =
H G
then acidic Ph H 2O
work up N
[15 marks]
(c) When the trichloride I was treated with potassium tert-butoxide J in tert-
butanol, an elimination product K was formed rather than the substitution
product L.
Cl O tBu
Cl + heat Cl
O– K+ K, C8H 6Cl2 NOT
tBuOH
Cl Cl
I, C8H 7Cl 3 J L
(ii) Explain why the substitution product L was not formed in this reaction.
[1 mark]
(iii) How would you expect the mechanism to change if the reaction were
conducted in a less polar solvent?
[2 marks]
TURN OVER
6 CHEM1032W1/1038W1/1022W1
3. Answer ALL parts
(a) (i) Suggest reagents and conditions to transform alkene M selectively into
EACH of the bromides and alcohols N, O, P and Q.
Br OR
Br
M N O
OH OR
OH
P Q
[4 marks]
(b) The reaction between R and MeLi gives alcohol S in high yield when 1
equivalent of MeLi is used. However, when an excess of MeLi was used, two
compounds were isolated from the reaction mixture, desired product S and
unknown compound T.
O OH
O O + T
O O
R S
(iv) NMR Spectrum III shows the unpurified reaction mixture. Use your
answers to the above to determine the ratio of S : T.
[2 marks]
(v) Use your answer to part (iv) to estimate how many equivalents of MeLi
were used in the reaction.
[2 marks]
CONTINUED
7 CHEM1032W1/1038W1/1022W1
4. Answer ALL parts
(a) In both of the reactions below a single major product was isolated in place of
the compounds W and Z.
OH OMe
i) 1 equiv. NaOMe
V NOT
ii) 1 equiv. MeI
CO2H CO2H
U W
i) 1 equiv. NaOMe
O O O O
Y NOT
ii) 1 equiv. MeI Me
OMe OMe
X Z
(i) Give structures for the major products V and Y and give the mechanism
of their formation. Justify why they are formed preferentially under these
conditions.
[6 marks]
(b) Outline a synthetic route to THREE of the compounds AA-DD shown below.
Your starting materials must be chosen from the list of substrates available.
You may use any common reagents. Each synthesis will involve more than
one step.
Cl O
O O
N
H MeO OEt
AA BB CC DD
Substrates Available
O O O
CH 3I Br Br Br H
H Cl
O CO2H
O
Br
HO OH
OH
[15 marks]
END OF PAPER