THE UNIVERSITY OF NEW SOUTH WALES

SCHOOL OF CHEMISTRY

SEMESTER 2 2013

CHEM2021 ORGANIC CHEMISTRY: Mechanisms and Biomolecules

1. TIME ALLOWED 2 hours.

2. READING TIME 10 minutes.
3. THIS EXAMINATION PAPER HAS 8 PAGES.
4. TOTAL NUMBER OF QUESTIONS 6 (six)
5. ATTEMPT ALL QUESTIONS.
6. TOTAL MARKS AVAILABLE 120 (48.75 % OF THE COURSE MARK).
7. THIS PAPER MAY NOT BE RETAINED BY THE CANDIDATE.

SPECIAL INSTRUCTIONS
8. WRITE YOUR ANSWERS TO PARTS A, B AND C IN SEPARATE ANSWER BOOKLETS.
9. ENSURE YOUR NAME AND STUDENT ID ARE ENTERED CORRECTLY ON ANY ANSWER
BOOKLETS YOU USE.
10. CANDIDATES MAY BRING TO THE EXAMINATION: UNSW-APPROVED CALCULATOR.
11. CANDIDATES MAY BRING TO THE EXAMINATION: MOLECULAR MODELS.
 SECTION A

Allow 40 minutes for this section of the paper. Answer in a separate booklet. Total marks = 40

Question 1 (TOTAL MARKS = 20)

(a) One of the following compounds would be expected to react rapidly with potassium tert-butoxide in
tert-butyl alcohol and one would not.

(i) Identify the most stable conformation of each molecule (being sure to explain why it is most
stable).
(3 marks)

(ii) Determine the reaction that occurs and identify the product.
(2 marks)

(iii) Explain the conformational requirements for the reaction and hence, identify which of the
compounds above reacts rapidly and which does not.
(3 marks)

(b) Using a mechanism, explain the outcome of the reaction below, being sure to account for any selectivity
observed.

(8 marks)

(c) Using a mechanism, predict the outcome of the reaction below, being sure to account for any selectivity
observed.

(4 marks)

UNSW CHEM2021 FINAL EXAMINATION Nov 2013 Please see over 2

Question 2 (TOTAL MARKS = 20)

(a) Each of the following reactions might be explained using two mechanisms. Draw each of the possibilities
and explain which is likely to be the actual mechanism. In each case, give at least two pieces of
experimental evidence that might be used to confirm the mechanism that is operating. (One of these may
be stereochemistry, which is deliberately not specified in the cases below.)

(i)

(6 marks)

(ii)

t-BuO-K+
Br

(6 marks)

(b) Identify the major product of each of the following reactions. Explain briefly your choice and suggest the
mechanism through which it might be formed.
(Note: There is no need to draw out the mechanism in each case.)
(i)
CH3COOH

Br
(4 marks)

(ii)
Br KOH

0 oC.
(4 marks)

-- END OF PART A --

UNSW CHEM2021 FINAL EXAMINATION Nov 2013 Please see over 3

 SECTION B

Allow 40 minutes for this section of the paper. Answer in a separate booklet. Total marks = 40

Question 1 (TOTAL MARKS = 20)

(a) Using structural formul indicate the major organic product(s) formed in the following reactions. Show
stereochemistry clearly where it is important.
(2 marks each)

(i)

(ii)

(iii)

(iv)

(v)

UNSW CHEM2021 FINAL EXAMINATION Nov 2013 Please see over 4

(b) Complete the following equations by providing the missing reactants, reagents, and (where appropriate)
conditions.
(2 marks each; 10 marks total)

UNSW CHEM2021 FINAL EXAMINATION Nov 2013 Please see over 5

Question 2 (TOTAL MARKS = 20)
Answer all THREE of the following parts.

(a) Write a mechanism for the formation of the enamine of cyclohexanone and pyrrolidine, including the
structures of the key intermediates.
(5 marks)

(b) Outline all steps in the synthesis of 4-phenyl-2-butanone from ethyl acetoacetate. Include all relevant
reagents and structures of intermediates.
(10 marks)

(c) o-Phthalic acid does not give a di-acid chloride when treated with SOCl2 (thionyl chloride). Instead the
half-acid chloride undergoes an intramolecular reaction to yield another product. What is this product and
how is it formed?
(5 marks)

-- END OF PART B --

UNSW CHEM2021 FINAL EXAMINATION Nov 2013 Please see over 6

 SECTION C

Allow 40 minutes for this section of the paper. Answer in a separate booklet. Total marks = 40

Question 1 (TOTAL MARKS = 20)

(a) Using the four criteria for aromaticity, identify which of the following species are aromatic. Your answer
must include reasons for your decision in each case (this includes reasons for why something is not
aromatic).
(4 marks)

(b) Predict the major product from nitration (HNO3/H2SO4) of anisole. Draw the full mechanism for the
reaction, using appropriate arrows to indicate electron movement and the full structures of any
intermediate(s). Use the mechanism of the reaction to provide a rationale for why the major product
formed.
(8 marks)

(c) Predict the major product formed when sodium methoxide reacts with methyl 4-chloro-3-nitrobenzoate.
Draw the full mechanism for the reaction, using appropriate arrows to indicate electron movement and
the full structures of any intermediate(s). Use the mechanism of the reaction to provide a rationale for
why the major product formed.
(8 marks)

UNSW CHEM2021 FINAL EXAMINATION Nov 2013 Please see over 7

Question 2 (TOTAL MARKS = 20)

(a) For the following sequence, provide all of the missing structures (A-C) in the sequence. NO
MECHANISMS REQUIRED

(6 marks]

(b) Using no more than four steps, outline a synthesis of 1,3-dicyanobenzene from benzonitrile.
Clearly indicate all reagents needed. NO MECHANISMS REQUIRED

(8 marks)

(c) Friedel-Crafts acylation of the methoxytoluenes (D-F) with acetyl chloride and aluminium chloride yields a
single product, different for each isomer, in high yield in each case. Write the structures of each of
these compounds and provide a rationale for their formation. NO MECHANISMS REQUIRED

(6 marks)

- - - END of PART C - - -

- - - END OF PAPER - - -

UNSW CHEM2021 FINAL EXAMINATION Nov 2013 Please see over 8