SIKKIM UNIVERSITY

Department of Chemical Sciences

M. Phil. Entrance Test Examination 2014
Organic Specialization
Full Marks: 60

Time: 2 hour

Answer any Four questions. (15 x 4 = 60)

1. a) Radical monochlorination of a compound having molecular formula C4H8 gave a
mixture of monochlorinated products, A, B, C, and D, that were then separated and
characterised. It was found that both A and B existed as a pairs of enantiomers (ie. A/A',
B/B') and that A and B were diastereomers. The relative yields of the products was A = B
> C > D (you could check this by calculating the % yields expected). In a series of
reactivity studies with AgNO3 / H2O / EtOH, the relative rates of reaction were C > A =
B > D. With NaI / acetone, the relative rates of reaction were D > A > B > C
a. Identify the monochlorinated isomers A, B, C and D and the original hydrocarbon
H.
5
b. How many types of hydrogen are there in the original hydrocarbon H ?
1
c. What would the major isomer have been if the company had used a radical
bromination instead of chlorination?
1
b) Compare the acidity of Ha and Hb. Give proper reasoning to support your answer. 3
Hb

Ha

c) Write products with mechanism giving consideration to stereochemistry.

KCN
Acetone

H
Et
Me

Cl

AgCN
H2O

d) Write down the mechanism of following reaction. Account for the fact that the
compound in which R = H reacts 35 times as fast as the one in which R = CH3.
3
H
N

NO2
R

R
N

O2N
R

Br

2. a) Explain differing outcome in both the following pairs of reactions with mechanis. (3+3 = 6)
O
HNO2
H2SO4

i)
t-Bu

CHO
OH

OH
NH2

HNO2
H2SO4

but
t-Bu

NH2

t-Bu

t-Bu

O
O

Ph

OH

Me
Me

but

Me
Me

ii)

OH

Ph

Ph

O
Ph

b) For preparation of product which reaction you will choose and why?
Me H

Me

Ph

LiAlH4

Ph

Me H

PhMgBr

Ph

H
Ph

Ph

OH

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

O

O
CN

CN

KNH2 (2equiv)

i)

KNH2 (1equiv)

CN

MeI

MeI
O

NH2NHSO2Ar

NH2NHSO2Ar
ii)

2 equiv LDA

NaOEt

3. Write appropriate reagents for following transformations.

(10 x 1.5 = 15)

O

O
O
O

G
B

H
O

O
D

C
I

O
HN

4. a) Give mechanism for following transformations.

O

O
i) Na, Liq. NH3

ii)

O +
i) O

(2.5 x 2 = 5)

ii) H3O+

CO2CH3

CO2CH3

b) How following transformation can be achieved?

(1.5 x 4 = 6)
O

Me

i)

Me

CHO

O
O

O
O
I

ii)

c) What products do you expect from following reactions? In which case the reaction will be
faster and why?
2
AgClO4

AgClO4

H2O

H2O

d) Write as many diene compounds possible from which following compound can be prepared
by ozonolysis.
2
O
O

5. a) Write the structure of A and B with due consideration to the stereochemistry. Give reason
for your choice of stereochemistry.
5
Me

Me
I2/K2CO3

Me

CO2H

I2/K2CO3

Me

HO2C

b) Write the structure of A and B. Give reason for your answer.

Me

Me
MCPBA

Major

B
Minor

c) How will you explain following difference in products?

F
D

Br

F
D

KNH2
NH3 (l)

KNH2
NH3 (l)

NH2

d) Write the products of following reaction. Give reasons for your answer.

Me
MeO

OMe

CO2Me

CO2Me

CO2Me

OMe

6. a) Write reagents and conditions for following multistep synthesis.

b) Give appropriate reagents for following transformations.

(1 x 5 =5)

i.

H3C

HO
OH

10

CH3
H

H
dl-Pair

ii.
OH

OH

7. a) An organic compound has the molecular formula C12H17NO. Identify the compound using the
spectroscopic data given below. Give step by step explanation for you logical structural
elucidation.
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max (KBr disc): 3296, l642 cm-1
1
H NMR (CDCl3 solution): 07.23-7.42 (m, 5H); 5.74 (brs, exch. D2O , lH); 5.14 (q, J = 6.7 Hz, lH);
2.15 (t, J = 7.1 Hz, 2H); 1.66 (m, 2H); 1.48(d,J = 6.7 Hz, 3H); 0.93 (t, J = 7.3 Hz, 3H) ppm.
13
C{IH} NMR (CDC13solution): 172.0 (C), 143.3 (C), 128.6, 127.3, 126.1,48.5 (CH),
38.8 (CH2), 21.7 (CH3), 19.1 (CH2), 13.7 (CH3) ppm.
Mass spectrum: m/e 191(M+, 40), 120(33), 105(58), 104(100), 77(18), 43(46).

b) A compound having molecular formula C7H8O, gives following 1H and 13C NMR spectra.
Deduce the structure of the compound from these NMR value. Give explanation for you logical
structural elucidation and assignments.
4

c) Deduce the structure of following compound (C11H14O2) fro following 13C NMR spectrum?

Thank you