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Department of Chemistry
End-semester Examination

Course No: CH 103, Chemistry

Time: 9.30 - 12.30 PM, Date: April 20, 2010

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. A synthesis of tropone (cycloheptatrienone) involves treating 1-methoxy-1,3,5-cycloheptatriene

with bromine. During this process a salt is produced and that yields tropone on treatment with
aqueous NaHCO3 (base). What’s the likely structure of the salt? Write a mechanism for its
formation and for the formation of tropone on hydrolysis.
(3 marks)

2. Place the five compounds A–E in decreasing order of reactivity in the SN1 (substitution
nucleophilic unimolecular) reaction. Briefly explain your answer by drawing chemical structures of
appropriate intermediates.
(3 Marks)

3. Pentadienyl cation 1 undergoes ring closure reaction to form allylic cation 2.

(A) Based on molecular orbital symmetry considerations through the analysis of HOMO (show
picture) provide the relative stereochemistry of chiral centres (a & b) in 2. (wedge-and-dash
structure is expected)
(2 marks)

(B) The orbital coefficients of the two of the π MOs of pentadienyl cation are given below. Show
the orbital pictures and specify which is of lower energy. Classify each orbital as bonding and
nonbonding or antibonding; and specify whether each orbital is symmetric (S) or antisymmetric (A)
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with respect to the plane bisecting the molecule perpendicular to the plane of the structure.(3
marks)

ΨN = 0.5φ1 + 0.5 φ2 _ 0.5 φ4_ 0.5 φ5 ΨN' = 0.58φ1 _ 0.58 φ3 + 0.58 φ5

4. The synthetic cancer drug candidate E7389 processes so many chiral centres.

(A) Identify the number of chiral centres in this molecule (credit will be given only if you identify
all the chiral centres). (1 mark)

(B) Employing CIP rules, determine the absolute configuration of the chiral centre that is in the
upper most carbon n the formula (in ring A). (1 mark)

(C) Draw the conformation of the fused 6 membered rings labelled B & C and all the atoms
directly attached to it. (4 marks)

(D) Draw Newman projection to show the central pair of carbons connecting B & C. Use H for
hydrogen, O for oxygen and R for CH2. (1 mark)

5. E.J Corey (Nobel Prize 1990) and co-workers recently reported the synthesis of a C3 symmetric
amine (Organic Letters, 2010, 12, 1812). One of the key intermediate in the synthesis is shown
below. Starting from this intermediate using a multi-step strategy (maximum 5 to 6 steps), outline
the synthesis of C3 symmetric amine. Clearly depict the structure of the final product (with correct
stereochemistry) and all the intermediates and reagents involved. You may use both organic and
inorganic reagents. One of the steps involves the use of a phenyl Grignard reagent. Reaction
mechanisms are not expected. (4 marks)
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6. An equillibria are presented below.

(A) Identify the more stable equilibrium isomer (1 mark)

(B) Identify the origin of orbital stabilization of the favoured conformer.

Show graphical representation to justify your answer ( 1 mark)

7. Write a mechanism to explain the second step of the reaction sequence shown below (a two-step
method for isomerizing trans alkenes to cis alkenes). Pay attention to stereochemistry of all the
intermediates (wedge-and-dash structures are expected). (3 marks)

8. Predict the major product expected for each reaction shown below. (mechanism not required)
(3 marks)
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9. Paying close attention to the stereochemical representation , draw a “considerably strained”

candidate structure with formula C4H9N ( 2 marks)