Department of Chemistry, IIT Bombay

CH 105:Organic Chemistry
End-Semester Examination
Marks: 25 Time: 2 hours August 23, 2014
All answers must be written using blue/blackpen. Answers written with pencil will not be corrected.

1. Suggest a plausible step-wise mechanism for the following reaction. Clearly show all the arrow-pushing.
(2 marks)

2. How will you do the following conversion? You can use any other simple reagents/reactants. Your
reaction sequence should not contain more than five steps. Show the structures of the intermediate
compounds. Do not draw the mechanisms of the steps involved. (3 marks)

3. Consider the following transformations. (i) Draw the conformational structures of the starting materials
A and D. (ii) Based on the conformational structures, explain the formation of the products in both the
cases. Your answer should be explained with the help of arrows, clearly showing the mechanism. You
are expected to show configuration of hydrogen atoms ONLY at the ring junctions and at the reaction
centers. (3 marks)

4. Draw Newman projections of all conformers for meso-2,3-dibromobutane. Using the values of gauche
interactions given below, calculate the difference in the energy between the lowest energy and the next
higher energy conformer.
Gauche interactions: Me/Me = 0.9 kcal mol−1, Me/Br = 0.25 kcal mol−1, Br/Br = 0.75 kcal mol−1
(3 marks)

5. How many stereoisomers are possible for the compound (CH3CH=CH)2CH(OH)? Draw their structures
using wedge formula. (2 marks)
(Note: Marks will be awarded only if the first part is answered correctly)

1
6. Assign the absolute configurations (R and S) for the following molecules. (2 marks)
a) b)

7. Identify and pictorially show (use dotted lines) the symmetry elements present for all stereoisomers of
H(Cl)C=C=C=C(Cl)H (2 marks)

8. Identify the following compounds as aromatic/non-aromatic/antiaromatic. (2 marks)

a) b)

9. Based on the analysis of the highest occupied molecular orbital (HOMO) (show picture) provide the
relative stereochemistry (cis/trans) of ring-junctionhydrogens in the product. Your answer should clearly
explain the stereochemistry with the help of appropriate arrows. (3 marks)

10. The barrier for the following isomerization can be calculated as the energy difference between the
reactant and a diradical transition state, as shown:

 
 
Calculate the rotational barrier (in terms of α and β using the energies of the relevant molecular orbitals
given below:
1,3‐butadiene  ψ1= α+1.618β ψ2= α+0.618β
allyl  ψ1= α+1.414β ψ2= α
(3 marks)