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UNIVERSITY OF BOTSWANA

END OF SEMESTER ONE EXAMINATIONS 2007-2008


FRONT PAGE

COURSE NO: CHE 331


TITLE OF PAPER:

DURATION: 3 HOURS

DATE: 20 November 2007

Organic Chemistry II

SUBJECT: CHEMISTRY

TITLE OF EXAMINATION:

CHE 331

INSTRUCTIONS
ALL CANDIDATES MUST ANSWER ALL QUESTIONS IN SECTION A AND ANY THREE
QUESTIONS FROM SECTION B.

_____________________________________________________________________
DO NOT OPEN THIS PAPER UNTIL YOU ARE TOLD TO DO SO BY THE SUPERVISOR
No. of Pages including this cover page

SECTION A
QUESTION ONE - Compulsory question
I.

[20 marks]

Answer questions a-f below: [2 marks each, total 12 marks]

a) Draw meso 2,3-dichlorobutane in its most stable conformation using the wedge and dash lines.
b) Draw the two flip chair conformations of trans-1-tert-butyl-3-methylcyclohexane and
indicate the more stable conformer.
c) Describe the characteristic infrared absorption frequencies that would allow you to distinguish
between paracetamol and benzocaine.
O

H
N

CH3

O
and

HO

H2N
Benzocaine

Paracetamol

d) Arrange the following in increasing order of expected max in UV absorption (lowest wave
length first).

i)

iii)

ii)

iv)

e) What are the masses of the ions produced in the mass spectrum of 2pentanol (shown on the right), by (a) -cleavage and (b) the McLafferty
rearrangement?

OH

f) How many signals do you expect in the proton decoupled 13C NMR and DEPT spectra of ethyl
acetate?
O
O

CH3

Ethyl acetate

II.

Complete the following equations by supplying the missing starting materials, reagents and reaction
conditions or products.
[2 marks each, total 8 marks]

a)

NaOEt

OEt

KMNO4
b)
H2O
O

c)

Br
O
d)

OH

O
OH

QUESTION TWO -Compulsory question


Identify the full structure of compound A (molecular formula C4H8O2) whose 1H NMR, 13C NMR, Mass
and IR spectra are given below. Assign the 1H and 13C NMR chemical shifts to the protons and carbons
respectively, in your structure. Rationalize the formation of fragment ions at m/z. 29, 43, 73 and 88. What
conclusions do you deduce from the IR spectrum?
[20 marks]

H NMR spectrum of
Compound A

13

C NMR spectrum of
Compound A

(ppm)integration4.12
2.03
1.262
3
3

(ppm)
171.1
60.4
21.0
14.3

Mass spectrum of
Compound A

IR spectrum of
Compound A

SECTION B:

ANSWER ANY THREE QUESTIONS FROM QUESTIONS THREE,


FOUR, FIVE AND SIX

QUESTION THREE
I. Consider the following reaction and answer the questions that follow.
Br2
CH3

II.

i)

Draw the reaction products showing stereochemistry at each chirality center.

[2 marks]

ii)
iii)
iv)
v)

What is the stereoisomeric relationship of the reaction products?


What will be the relative amount of each product?
Comment on the optical activity of each reaction product.
Comment on the optical activity of the reaction mixture.

[2 marks]
[2 marks]
[1 mark]
[2 marks]

The Scheme below shows the application of the malonic ester synthesis to the preparation of a
carbcyclic acid cyclobutane carboxylic acid (E) and its methyl ester (F). Notice that in this
case dimethyl malonate is used instead of the more common diethyl malonate. Answer the
following questions about the Scheme below:
O
O

H3CO

1. BASE
OCH3

H3CO

2. B

H3CO

O
H
C

O
O

OCH3 BASE

OCH3

Br

1.H3O+
2. Heat

O
OCH3

O
OH

F
E

i)
ii)
iii)
iv)

What is the most appropriate base to deprotonate the dimethyl malonate? How about for
the deprotonation of C?
[3 marks]
Write the structure of the alkylating agent B.
[2 marks]
Write the mechanism for the conversion of D to E.
[4 marks]
D can also be converted in one step to F by what is known as the Krapcho reaction.
What reagent can be used for this purpose?
[2 marks]

QUESTION FOUR
I.

i)
ii)
iii)

II.

Sketch a diagram of potential energy versus angle of rotation about the C1 - C2 bond of
propane [CH3CH2CH3].
[4 marks]
Label each minimum and maximum with the appropriate conformation of propane.
[4 marks]
Which conformation of this compound is present in greatest amount?
[1 mark]

Look at the following Scheme carefully, taking note of the arrows and answer the questions
below the Scheme.

O
OH
L
K

O
M

HOAc

Br2

J
P

O100%
Q

i)

What reagents(s), (K), can be used for the J

L interconversion? [2 marks]

ii)

What is product O? And what other product is formed with it?

iii)

Write the mechanism for the conversion of J to O, taking into consideration the roles of
Br2 and HOAc.
[4 marks]

iv)

What reagents (P and M) can be used to convert J to Q and J to N?

[3 marks]

[2 marks]

6

QUESTION FIVE
I.

The signal for the CH2 protons in the NMR spectrum of two compounds, B and C appear at
2.5 and 4.5. Which chemical shift belongs to which compound? Explain the difference in
chemical shifts.
[2 marks]
O
O

O
O

O
O

II.

i)
ii)
iii)

Draw all the stereoisomers of 2,4-dibromo-3-chloropentane.


Show the meso form, pairs of enatiomers and diastereomers, if any.
Indicate which are optically active.

[3 marks]
[2 marks]
[2 marks]

III.

Determine whether the following are aromatic or antiaromatic.

IV.

Show how you would synthesize the following aromatic compound (X) from benzene. Assume
that ortho and para isomers can be separated.
[4 marks]

[3 marks]

Br
O2N

V.

Show how you can obtain the following compound (Y) using a Michael reaction. [4 marks]
O

CO2Et
CO2Et
Y

QUESTION SIX
I.

Which of the following pairs of molecules (indicated by double-headed arrows) are


diastereomers, enantiomers, or identical?
[5 marks]
3

1
HO

CO2H

HO

CO2H

HO
NH

NH

NH

CO2H

HO

CO2H
NH

4
II.

Draw the two "flip" chair conformations for the following compound (Z) and indicate which
one is more stable.
[4 marks]
CH3
CH3
H3C

CH3
CH3

III.

Z
Show how the diester below can be converted to cyclohexenone.

[5 marks]
O

O
EtO

IV.

O
OEt

Show how you could employ an intramolecular aldol reaction to synthesize the
dimethylcyclohexene W shown below. Pay particular attention to show the most suitable bases
and reaction conditions that are required.
[6 marks]
O

W
END OF EXAMINATION
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