Department of Chemistry, IIT Bombay

CH 105: Organic Chemistry

End-Semester Examination
Marks: 25 Time: 2 hours August 20, 2016
All answers must be written using blue/black pen. Answers written with pencil will not be corrected.

1. Identify the following pairs as “Identical / Enantiomers / Diastereomers / Constitutional isomers”.

(2 marks)
a. b.
HO CO2Me CO2Me
HO H
H HO HO H
HO H
H CO2Me CO2Me
OH H

2. For the following two isomers, two sets of C−O bond distances [(a) 1.409 and 1.409 Å and (b) 1.395 and
1.415 Å] marked with the arrows were observed. Match these bond distances with the structures. Write
the bond distances on each arrow correctly. Explain your observation with the help of orbital
interactions. (3 marks)

3. Identify the structures of the products A and B in the following reaction sequence. (Mechanism not
necessary) (2 marks)
O
CO2Et 1. KOH (aq.)
A B
(C17H 28O4) (C14H 22O)
O NaOEt 2. H 3O+, heat
EtOH

4. Provide a suitable mechanism for the formation of the product in the following reaction. (3 marks)
O Ph 1. NaOMe O
CO2Me MeOH CO2Me
Ph
2. H 3O+

5. The stereoisomer Y of 1,2,3,4,5,6-hexachlorocyclohexane, undergoes E2 elimination of one equivalent

of HCl in aqueous ethanol 104 times faster than the stereoisomer X. Suggest a reason for the difference
in rates using conformational structures. (2 marks)

6. Assign the absolute configurations (R/S) for the following molecules. (2 marks)
a) b)
CH=NOH
N C SH
F 3C CH 3
Br Br
CH 3 N3 NO 2

1
7. Identify and pictorially show the symmetry elements present in the following compounds.
(2 marks)
a) b)
Ph Ph
O O Cl
Ti H
O O Cl
Ph Ph

8. The compound C on reaction with one equivalent of MeI gives a salt. What is its structure? Why only
this salt is formed? (2 marks)
N
N
H
C

9. Based on the analysis of the highest occupied molecular orbital (HOMO) (show picture) of the
intermediate, provide the relative stereochemistry (cis/trans) of the starred stereocentres of the final
product. Use wedge structures. (4 marks)

H OH OH O
O OH
H+ -H+
* * *
* * *
H Me H Me H Me H Me H Me

10. The energy diagram shows the relative energies of the conformations of 2,2,3-trimethylpentane produced
during the rotation about the C3-C4 bond. Match the structural representations provided to the
appropriate points on the energy profile. (3 marks)