Department of Chemistry, Sikkim University

MPhil/PhD Entrance Examination, Admissions 2017

Max Marks: 100 Time: 1h
Answer any five (5 x 20 = 100)

1.

a. The major product formed in the following reaction is 4

b. The major product formed in the following reaction is 4

OH 1. NaH/THF

2. H3O+

O 3. O 4. O
1. 2.

c. The major product formed in the following reaction is 4

Conc. HNO3, H2SO4

N
NO2 NO2
O2N
1. 2. 3. 4.
N NO2 N N N

d. Which of the following compound will be major product of this photochemical reaction?
4
O
O h
Ph
Me
O O O
Me Ph O
O O O Me
1. 2. 3. 4. Ph
Ph Me O
 e. The product of the following reaction gave 6 line 13C NMR spectrums with peaks at 175, 52,
50, 46, 37, 33 ppm. The structure of the product is 4

O h
MeOH
N2

OMe
1. OMe 3. 4.
OMe 2.
OMe
OMe OMe OMe CO2Me

2.

a. Which of the following compound will be major product of this photochemical reaction?
4

2. 4. +
3.
1.

b. Reagents that can be used in the following conversion are 4

CO2H
CHO

1. i) Ph3P=CH2, ii) HCN, iii) H3O+ 2. i) HS(CH2)2SH, ii) n-BuLi, iii) BrCH2COOH

3. i) EtMgI, ii) KMnO4 4. i) Ph3P, CBr4, ii) n-BuLi, iii) CO2

c. Which of the following compound will be major product of this pericyclic reaction? 4
O
MeO RT
+ O

O O H
H
1. MeO O 2. O 3. MeO H 4. H

H H MeO O
MeO H O O
H O
 d. For the following reaction, the structure of the major product is 4

O N
H
CO2Et
O
O
CO2Et
1. 2. 3. 4.
CO2Et CO2Et CO2Et

e. Which of the following statements is correct about molecules A-D? 4

F H Cl
F
H
H C
F F
F
B F C D
A

1. All are optically active 2. A & B are optically active C & D are not

3. A & D are optically active, B & C are not 4. B & C are optically active A & D are not

3.

a. For the following reaction, the structure of the major product is 4

CO2H 1. I2, NaHCO3

2. Allyl-tri-n-butyl tin, AIBN
O
O O O
O O O
O
1. 2. 3. 4.

b. For the following reaction, the structure of the major product is 4

O
Me
Me S
O
Me
Me Me O
3. 4.
1. 2. Me Me
O O O
c. For the following reaction, the structure of the major product is 4
O
Me2CuLi
I Et2O

O
O O O
4.
1. 2. 3.

d. A compound with the molecular formula C10H13Cl gave the following H NMR spectrum:

4
i. singlet, 1.6
ii. singlet, 3.1
iii. multiplet, 7.2 (5H)
The most likely structure for the compound is:

e. Which option represents the correct order of Pople notation of following compounds 4
4.

a. Which of the following protons are chemically equivalent but magnetically non-equivalent?
4
OMe
F F H H 1. I, II and III
H Cl 2. I and III
3. II and III
H H Cl H NO2 4. I and II
I II III
b. The major product formed in the following reaction is 4

OMe
1. Na, in Liq. NH3, EtOH

2. O3, Me2S, MeOH

O
O OMe OMe MeO O
O O
MeO O
2. 3. 4.
1.
O
O O O O O O

c. Which of the following sequence of regents you will use for following transformation? 4

O H

H
1. Butadiene, 250 oC

2. a. (Allyl)2CuLi, Allyl bromide in THF, b. Grubb' s Catalyst, c. Tosylhydrazine, BuLi, THF

3. a. LDA, allyl bromide in THF, b. DABCO, allyl bromide, c. Grubb's catalyst d.Tosylhydrazine, BuLi, THF

4. a. (Allyl)2CuLi, Allyl bromide in THF, b. Grubb' s Catalyst, c. Tosylhydrazine, NaOMe in MeOH

d. For the following reaction, the structure of the major product is 4

O
Br
NaOMe

O
O O
CO2Me
1. 3. 4.
2.
 e. For the following reaction, the structure of the major product is 4
Me
NH2
NaNO2, HCl

OH
H

Me Me Me Me
1. 2. 3. O 4. CHO
O OH
H H H H

5. Write appropriate reagents for following transformations. 8 x 2.5 = 20

6.

a. Give mechanism for following transformations. 8

O O
O
ii) i) Na, Liq. NH3
O +
i) O N ii) H3O+
CO2CH3
CO2CH3

b. Comment about the chirality of following molwcules. 4

 c. Write products for following reactions with correct stereochemistry. Give brief reasoning.
4

d. Write products for following reactions with correct stereochemistry. Write intermediates and give
reason for your choice of stereochemistry. 4

7.

a. Compare the acidity of Ha and Hb. Give proper reasoning to support your answer. 4

b. For preparation of product which reaction you will choose and why? 4

Me H Me Me H
Ph LiAlH4 Ph PhMgBr H
Ph Ph Ph
O OH O

c. Explain the change in regioselectivity in following pairs of reactions. 4

d. How will you explain following difference in products? 4

F F Br
D D D D NH2
D D D KNH2
KNH2
NH3 (l) NH3 (l)
e. Write reagents and mechanism for following transformations. 4