UNIVERSITY OF SOUTHAMPTON CHEM1032W1/1038W1/1022W1

SEMESTER 2 EXAMINATION 2015/6

FUNDAMENTALS OF ORGANIC CHEMISTRY II

DURATION 120 MINS (2 HOURS)

This paper contains a total of FOUR questions and SEVEN pages

Answer ALL questions in Section A and TWO questions from Section B

Answer EACH question in a separate answer booklet

You are advised to spend no more than 40 mins on Section A

Section A Question 1(a) is on a separate sheet which must be attached to your

answer book with a treasury tag.

EACH question carries 25 marks. The mark allocations shown in square

brackets provide a guide to the relative distribution of marks within a question

A Periodic Table is provided on Page 2 of this paper and a table of Physical

Constants is provided on Page 3

Candidates may only use University approved calculators

Candidates may use molecular model kits

A foreign language word to word® translation dictionary (paper version) is

allowed provided that it contains no notes, additions or annotations

PLEASE NOTE: whilst this examination paper is focused on assessing your

knowledge and understanding of the module it also assumes retention of
learning from all previous, relevant core chemistry modules

Copyright 2016 © University of Southampton

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 4 CHEM1032W1/1038W1/1022W1
SECTION A: Answer THIS question
1. Answer ALL parts
(a) On the sheet provided complete the reaction mechanisms depicted in
Scheme 1 by adding the missing curly arrows.
[5 marks]

(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

(i) Identify K and outline a reasonable mechanism for its formation.

[3 marks]

(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]

(ii) Outline reasonable mechanisms for EACH of the reactions leading to

bromides N and O from alkene M.
[6 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

(i) Using your knowledge of carbonyl chemistry, suggest a structure for T

and provide a mechanism for its formation.
[3 marks]

(ii) Predict the appearance (number of environments, relative integration

and multiplicity) of the 1H NMR spectra of each of S and T.
[6 marks]

(iii) Determine which of attached Spectrum I and Spectrum II belong to S

and T, respectively, justifying your answer based on your predictions in
part (ii).
[2 marks]

(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
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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]

(ii) Propose a synthesis of compound W starting from compound U. More

than one synthetic step may be required.
[4 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