UNIVERSITY OF COLOMBO, SRI LANKA

FACULTY OF SCIENCE

M. SC. IN APPLIED ORGANIC CHEMISTRY EXAMINATION 2016

MOC 5001 – Advanced Organic Chemistry (Three hours only)

Answer FOUR questions only

Number of questions: 06
Number of pages: 09

Important Instructions to Candidates

 If a page or a part of this question paper is not printed, please inform the supervisor immediately.
 Enter Your Index Number on all pages of the answer script.
 Start answering a new question on a new page.
 Electronic devices capable of storing and retrieving text, including electronic dictionaries and
mobile phones are not allowed.

1
Q1.
a) Give the product/intermediate of each of the following reactions.

(50 marks)

2
 b) How would you synthesize disparlure starting from an alkyne with 9 carbons? You may
use any other reagents or conditions that you require in the synthesis. Briefly outline the
retrosynthetic analysis before you propose the synthesis.

(Note: disparlure is a cis epoxde)

disparlure

(30 marks)

c) Retrosynthetically analyze the following target molecule and propose a synthesis from
cyclohexanone.

(20 marks)

Q2.

a) Retrosynthetically analyze the following target molecule to obtain the starting materials given
below. Propose structures for the halide and the amine

(20 marks)

i. Propose a mechanism for the reaction between cyclohexanone, formaldehyde and the
amine.
(10 marks)

ii. Propose a synthetic scheme starting from the identified starting materials. You may use
any additional reagents required for the synthesis.

(20 marks)

3
 b) Give the structures of the intermediates E –G

(20 marks)

c) Explain as to how the information given below within the two reactions provide evidence for
a particular mechanism for nucleophilic substitution. Write mechanisms to show the formation
of the products .

CF3

Br
NaNH2 / Liquid NH3
No substitution product

CH3

NH2
NaNH2 / Liquid NH3 NH2
Br
+ +

NH2

CF3 CF3 CF3

CF3
Major Product
(30 marks)

4
 Q3.

a) Give synthetic pathways for the following conversions. Each conversion may require more
than one step. In such cases give reagents and intermediates for each step. The mechanism
should also be given.

i)

(15 marks)

ii)
O CHCH2CH3
C-C(CH3)3 C-C(CH3)3

HO2C
HO2C
(15 marks)

iii)
CH2CH3
Br Br

(25 marks)

b) What is meant as the kinetically controlled product and the thermodynamically controlled
product of a reaction . Explain these terms by taking the sulphonation of naphthalene as the
example .
(25 marks)

5
c) Write the structures of the compounds A- D

A(C9H16O)

1. Li Al H4
2. H3O+

conc. H2SO4
B C(C9H16) O3/Zn
D

CrO3/H+

CH3COCH2CH2CH2CH-COOH
C2H5
(20 marks)
Q4.

a) i) Explain as to why pyrrole is considered as an aromatic compound. (The bonding of the

atoms should be discussed)

ii) At which carbon atom is electrophilic substitution preferred in pyrrole? Give reasons for
your answer
(35 marks)

b) How would you synthesize the Pyrrole A and Quinoline B from readily available starting
materials? Give reagents, intermediates.
H3C

H3CH2C CH3
N
H

A (45 marks)

6
 CH3

MeO N (20 marks)

Q5.

a) Catalysts play an important role in many industries. Selection of a suitable catalyst is

based on various parameters. A typical heterogeneous catalyst is comprised of three
components: an active phase, a promoter, and a supporter.

i. Briefly explain why the use of homogeneous catalysts for industrial process is not
common.

ii. List two main advantageous of using a supporter in heterogeneous catalyst.

iii. Briefly explain two methods that can be used to combine a catalyst with a suitable
supporter.
(30 marks)

b) Diatomic reactant X2 shows both physisorption and chemisorption on to a solid absorbent

W under two different conditions. These adsorbed reactants can react with a second
reactant Y to produce a product XY. The equation for this process in the presence of solid
W is given below. The powder of solid W acts as a catalyst for this reaction.

X2 + 2Y 2XY + Y2 + X

2 moles of X2 and 4 moles of Y reacted in the presence of 0.1 g of catalyst W, and the
amounts of XY, Y2, X and unreacted reactants after 10 minute are given below.

7
 Initial Final
X2 2 moles 0.4 moles
Y 4 moles 0.4 moles
XY 3.0 moles
Y2 0.3 moles
X 0.2 moles

Based on these data, answer the following questions.

i. Calculate the activity of the catalyst in mol g-1 h-1

ii. Calculate the selectivity of W on this reaction.
iii. Calculate the turn over frequency of the catalyst
(The molecular weight of W is 800 g mol-1 and each molecule of W has one active
center).
iv. If the catalyst was active for a period of seven days, calculate the turn over number of
W.
(50 marks)

c) Using the Lennard-Jones potential energy diagram, explain why physisorption of reactants
on to the catalyst surface can reduce the activation energy of certain chemical reactions.
(20 marks)
Q6.

a) Write down the Woodward-Hofmann Selection rule for pericyclic reactions.

(8 marks)

b) Use the above theory to predict whether the following pericyclic reaction takes place under
thermal conditions or photochemical conditions.

COOCH 3
Ph COOCH 3
Ph
CH3 CH3
CH3 COOCH 3
Ph
Ph COOCH 3
CH3

(14 marks)

8
 c) Using Frontier Orbital Theory (FOT) predict whether the following pericyclic reactions are
allowed or not.

CH3
CH3 h
i)
CH3
CH3

CH3
ii)
CH3
+
H3C

CH3

(28 marks)

d) The ideas and concepts behind nanoscience and nanotechnology started with a talk entitled
“There’s Plenty of Room at the Bottom” by physicist Richard Feynman at an American Physical
Society meeting at the California Institute of Technology (CalTech) on December 29, 1959

i. What is Nanotechnology?

ii. Give any two salient points addressed by Feynman.

iii. Discuss briefly the important landmarks in the history of nanotechnology.

iv. Define nano structured material and classify nanostructured materials.

v. Give 3 examples of nanomaterials that differ in properties when at the nanoscale vs. bulk

(50 marks)

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