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Department of Chemistry
End-semester Re-examination (2011)

Course No: CH 103, Chemistry

Total Time: 3hrs

Weightage: 50%

Total number of pages in the question paper: 4

Note: Write Part A & Part B in Separate Answer Books

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Section A: Organic Chemistry (Total Marks: 32)
Glance through the entire questions and solve the easiest problems first.

1. With the assistance of a Frost circle, write down a π MO diagram for cycloheptatrienyl cation.
Populate the orbitals and predict whether or not this compound is aromatic / non-aromatic / anti-
aromatic. (2 marks)

2. (a) Complete each of the Newman projections below to show the most stable and least stable
conformations of 2,2-dimethylbutane sighting along C2-C3 bond. (1 mark)

(b) Use the above Newman projections (from section 2a) to calculate the rotational barrier in
kcal/mol of 2,2-methylbutane sighting along C2-C3 bond. (2 marks)

3. A molecular rearrangement reaction (reaction in which bonds migrate) is shown below. Draw the
curved arrows to show the flow of electrons. Identify the frontier orbitals involved in the first step
of this rearrangement. Also identify the type of frontier orbital interactions (σ/π) involved in the
first step by showing the sketch of orbital interaction. (2 marks)

4. How will you carry out the transformation shown below? Write reagents involved in each steps
(Mechanisms are not expected) (3 marks)
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5. The reaction shown below is reported recently by Liang and co-workers in the Journal of American
Chemical Society (2011, 133, pp 1781–1783) for the synthesis of biologically active furopyridones.
Propose a reasonable mechanism for the formation of the product. Show all the arrow pushings.
(3 marks)

6. Lycopodine is an alkaloid compound used in Chinese herbal medicines and in homeopathic

preparations. It contains 4 fused 6 membered rings. A synthesis of (+) lycopodine can be achieved
from a key intermediate A shown below. Redraw the structure of A in the most stable chair
conformer. Identify the structures of the intermediates B and C and then identify the structure of
lycopodine. All structures should be shown in the chair forms and the there is no need to show the
position of hydrogen atoms. Also the reaction mechanisms are not expected. (Hint: B & C are
tricyclic compounds and all the intermediates and lycopodine contain a cyclic ketone fragment)
(3 marks)

7. It is difficult to form ketal X of compound A than ketal Y of compound B? Draw conformational

structures and justify your answer. (2 marks)
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8. Predict the major product expected for each reactions A - C shown below. (Mechanisms not
required; partial credits will be awarded for showing the correct intermediates) (4 marks)

9. In the Huckel MO treatment, orbitals on nonadjacent atoms are assumed to have no interaction. The
concept of homoconjugation suggests that such orbitals may interact especially in rigid structures in
which orbitals are directed toward one another. Consider e.g. norbornadiene, (bicyclo[2.2.1]hepta-
2,5-diene) shown below. Construct qualitative MO digram for norbornadiene based on the concept
of homoconjugtion and arrange the orbitals in the increasing order of energy. (3 marks)

10 Determine configuration of the chiral centres or the double bond. (3 marks)

..

11 Alkenes A and B (C6H12) are cis/trans isomers. Upon reaction with Br2, A gives a single meso
compound while B gives a racemic mixiture of two compounds, which are both distereomers of the
product from A. Remembering that Br2 adds trans across a double bond, deduce the stereo
structures of A and B as well as their respective products. Use Fischer structures to justify the
stereochemistry of products. ( 4 marks)