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Department of Chemistry
End-semester Examination (2012)

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. Due to the strained bonds between carbons in the cyclopropane ring, the bonding orbitals pucker
outword at an angle of 104° as shown below. It has been observed that cyclopropylmethyl
carbocations as shown below are as stable as allyl carbocation despite lacking π electrons or lone
pairs to participate in resonance stabilization. Using your knowledge of orbitals and bonding in
cyclopropyl rings, propose an explanation for its stability. Your answer should incorporate clearly
drawn orbitals. (2 marks)

2. Each of the following heterocycles has one or more nitrogen atoms. Mark each nitrogen atom as
strongly basic (SB) or weakly basic (WB), according to the availability of its lone pair of electrons.
(2.5 marks)

3. Draw pictorial representations for the three bonding πMOs and the two nonbonding πMOs of
cyclooctatetraene. Mark the nodal planes using dotted lines. Also arrange the obitals in the order of
increasing energy. You may show only the top view of the orbitals by drawing circles with
appropriate shadings (3 marks)

4. Trans-1,2-dimethylcyclobutane is more stable than cis-1,2-dimethylcyclobutane, but cis-1,3-

dimethylcyclobutane is more stable than trans-1,3-dimethylcyclobutane, Explain. Use proper
conformational drawings to justify the answer. (2 marks)
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5. One of the views of twist boat conformer of cyclohexane is shown below. Identify the number and
types of symmetry elements associated with this conformer. Also mark them in the structure using
dotted lines (2 marks)

6. The following intramolecular reaction (Schimdt reaction) proceeds via a bicyclic intermediate, which
undergoes a rearrangement (reaction in which bonds migrate) by eliminating N2. Propose a
reasonable mechanism for the formation of the product. Show all the arrow pushings. Draw the two
possible conformational structures that are possible for the intermediates with correct
configurations of atoms and groups (positions of hydrogen atoms in the ring except at the ring
junctions are not expected in the structures) and also identify the intermediate which is of lower
energy. (Hint: you may start with a conformational structure of the starting compound to reach the
intermediates). (4 marks)

7. A chemist finds that the addition of (+)-epinephrine to the catalytic reduction of 2-butanone gives a
product that is slightly optically active, with a specific rotation of +0.45°. Calculate the percentages
of ( + )-2-butanol and (_)-2-butanol formed in this reaction. The optical rotation of pure (+) butanol
is +15°. (2 marks)

8. Chair conformer of 1-methyl cyclohexane (A) is shown below. Draw a Newman projection by
viewing down the C1-C6 bond and C3-C4 bond and show that the equatorial methyl group is anti to
C5. Ring flipping of A gives structure B. Draw a Newman projection of B by viewing down C2-C1
and C4-C5 bond and show that methyl group is Gauche to C3. (3 marks)

9. Reaction of an aliphatic aldehyde Q with formaldehyde in the presence of aqueous K2CO3 gives
compound R, which upon treatment with HCN followed by acid hydrolysis and heating yielded the
product shown below. Write a synthetic scheme for the formation of the product, and identify the
correct structures of Q and R. (3 marks)
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10. Predict the major products expected for the following reactions (Mechanisms are not expected).
Partial credit will be awarded for showing correct intermediates. (2 marks)

11. A research student was studying enzymatic reductions of cyclohexanones when she encountered
some interesting chemistry. When she used an enzyme and NADPH (a cofactor) to reduce the
following ketone, she was surprised to find that the product was optically active even after the
removal of enzyme and the cofactor.

(A) Does the product have any asymmetric carbon atoms?

(B) Explain how and/or why the product is capable of showing optical activity? (1.5 marks)

12. How will you carry out the transformation shown below in 2 to 3 steps? Write reagents involved in
each step. Name the reactions involved (Mechanisms are not expected). Partial credit will be
awarded for showing correct intermediates (2 marks)

13. Assign configuration (R/S or E/Z) to the chiral centres or double bond of the following molecules.
(Consider only the central double bond in B) (3 marks)
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