SIKKIM UNIVERSITY

Department of Chemical Sciences

Organic Chemistry: CHE-PG-C202
June, 2019

Full Marks: 50 Time: 2 hour

Answer Question No. 1 and any Four questions from the rest. (5 x 10 = 50)
1. a. Draw the orbital state correlation diagram for the ethylene-ethylene dimerization reaction. 3

b. Predict the product of the following reaction. 1

tBu
OMe

c. Which product do you expect from following reaction? Give mechanism. 2

B. C. D.
A.

d. Which product do you expect from following reaction? Give mechanism. 2

H H
A. C. D.
B.
H H

e. Which product do you expect from following reaction? Give mechanism. 2

O
Ph
+ O
Ph
O
Ph O Ph O
Ph Ph H
H O H O H

C. O D. O
A. O B. O
H H O
H O H O Ph O Ph
Ph Ph

2. a. Suggest a mechanism to account for each of the following solvolysis reaction. Which solvolysis
reaction would be expected to occur more rapidly? Explain. 3
Br H
H Br
H AgClO4
H AgClO4 ii)
OH H Acetone-water
i) H Acetone-water
OH
b. What product A do you expect from following reaction? Give mechanism for each of the following
steps. O O 3
Grubb's catalyst, 1st gen Dimerization
O A O O
CH2CL2
O
(±)-Differolide
c. The following thermal reaction takes place via two pericyclic steps. In which the intermediate
could not be detected. Identify A, and identify the class of pericyclic reaction. 2

D
A
D
D D

d. Write structures of products with correct stereochemistry. Give mechanism. 2

HO
H2, Pd(CO3), PbSO4
A B C
OH

3. a. How will you carry out following transformations? Give mechanism for each steps. 3
MeO
OMe
OMe
O
O O OMe

b. How will you carryout following transformations? Give mechanism in each case. Give reason for
region-selectivity of the reagents. 3
D O OO O
O O E
OMe Ph OMe
Ph

c. What products do you expect from the following reactions? Give mechanism for each steps. 2
O mCPBA
LDA, THF, -78oC, 1h A B

H2C=NMe2 I

d. How will you carryout following transformation?

O Give mechanism for each step. 2
NH

MOMO MOMO
H H
O O
H H
OMOM OMOM

4. a. What are the reagents are will you use for following organic transformations. Give mechanism
for the formation of the product and reason for particular region-selectivity in each case. 7.5
CHO O O
B C
A

SeO2 SeO2

D E

b. How will you carry out following transformations? Provide suitable reagents and mechanism for
each steps. 2.5
OH OH
CO2Me
CO2Me CO2Me

RO I RO

5. a. Fill the following scheme with suitable reagents and products with proper stereochemistry. Give
suitable mechanism for the formations of the products. 3
H H
O O
O A O 4% aq. H2SO4 Ph N
OH C
B
O O O H O
b. Write the expected product with proper stereochemistry. Give mechanism. 2
SMe2I

NaH

O
Me

c. Choose appropriate reagents for each of the following transformations. 2

SiMe3
O
O

O O RO
O RO
i) ii)

c. Fill the following reaction scheme with suitable products. Give mechanism for each O
steps. 3
O H2SO4 or NaOH
vinylMgBr (excess)
A B
O THF

6. a. Fill the following scheme with suitable reagents and products. Give proper mechanism for the
formation of the product. O 3
A H2O2, NaOH i) TsNHNH 2
B C
ii) AcOH, Heat

b. Write suitable reagents

H
for following transformations. Give mechanism inH each case. 3
H
O O O
O O

H H H

c. What product do you expect from following reactions? Give suitable mechanism for the formation
of product(s). O 4
Br NaOMe O
Et2O B
Na, Liq NH3
A
i) ii) N

7. How will you carryout following transformations? Give mechanism in each case. 10
O

O
B

A Et H
C D Pr H
CHO
O OH
E OH
G
F
O
O

Thank You