I,F,S, EXAM-(M) 2018 FSI-D-CHM

CHEMISTRY

PAPER—II

Time Allowed : Three Hours Maximum Marks: 200

QUESTION PAPER SPECIFIC INSTRUCTIONS

Please read each of the following instructions carefully

before attempting questions

There are EIGHT questions in all, out of which FIVE are to be attempted.

Question Nos. 1 and 5 are compulsory. Out of the remaining SIX questions, THREE are
to be attempted selecting at least ONE question from each of the two Sections A and B.

Attempts of questions shall be counted in sequential order. Unless struck off, attempt of a
question shall be counted even if attempted partly. Any page or portion of the page left
blank in the Question-cum-Answer Booklet must be clearly struck off.

All questions carry equal marks. The number of marks carried by a question/part is
indicated against it.

Unless otherwise mentioned, symbols and notations have their usual standard meanings.

Assume suitable data, if necessary, and indicate the same clearly.

Neat sketches may be drawn, wherever required.

Answers must be written in ENGLISH only.

FSI-D-CHM/44 1 [ P.T.O.
 SECTION-A
•
1. Answer the following questions : 5x8=40

Explain why the dipole moment of naphthalene is 0.00 D and that of azulene is
1.02. D.

Which one of the following compounds is more acidic? Justify your answer:

and Ph3CH

Write the structure of the product(s) with proper stereochemical outcome of the
following reaction and also the corresponding mechanistic pathway :
Ph H Br2

CO2H

Predict the products of the following reaction showing distribution of the

labelled carbon a•) and the mechanism :
14 t..,
0
Cl
Na0Me

Account for the difference in reactivity of the following two reactions based on
diastereomeric chlorohydrins. Write the product in each case :

Cold -OH/ H20

Slow
KZL"'/C1

0:0H Cold OH/H20

Fast
Cl

The initial product formed from the reaction of 2-methylcyclohexadiene and

dimethylacetylene dicarboxylate on heating is transformed to another product
with elimination of a small molecule. Write the structure of each product
(initial and final). Also write how these are formed.

FSI—D—CHM/ 44 2
 (g) Acetylation of methanol using acetyl chloride and pyridine is proposed to
proceed through the following two pathways :

(i) Via formation of pyridinium acetate

(ii) Via formation of ketene

Can you devise an experiment to prove through which pathway the reaction
actually proceeds?

(h) When irradiated, tetrafluoroethene undergoes a cycloaddition reaction with

1-buten-3-yne to yield two products in almost equal amounts. What are the
structures of these products?

2. (a) Predict the product(s) of the following reactions with proper stereochemical
outcome and denote the corresponding pathways (abbreviated) : 5

Ph >4.;p 1l3
SOC12 SOC12
>?
OH

Explain why methyl alkyl ketones (RCH 2COCH3 ) undergo aldol condensation
via attack at the methyl group in the presence of base catalyst, but via attack
at the methylene group in the presence of acid catalyst. 5

Write the structures of [A] and [B) of the following sequence of reactions. Write
the mechanism of their formation. What type of rearrangement and electronic
shift are involved in the second step? 10

H3C OCH3 C2113CO2H

>< [A] --> [B]
OCH3

What type of mechanistic pathway is involved in each case of hydrolysis of S, S-

and S, R-2-acetoxycyclohexyl tosylate, separately? Which one reacts at a faster
rate and why? Write the structure of the product(s) with proper stereochemical
outcome and mention R/ S to the chiral carbons. Write the structure of the
intermediate also (where applicable). 10

Account for the formation of product(s) from a reaction of 3-bromoanisole with

2 /liq. NH3. 5

FSI-D-CHM/ 44 3 [ P.T.O.
 (I) Using the same coordinate system, draw two separate energy diagrams for the
following two reactions. How can you denote (abbreviated form) such
reactions?
5
Cl BnNH
NO2 NO2
+ BnNH2 --->

NO2 NO2

BnNH
NO2 NO2
+ BnNH2

NO2 NO2

3. (a) Discuss why p-dimethylaminobenzaldehyde does not undergo any reaction

with KCN, but a mixture of this and benzaldehyde does, giving a condensation
product. Name the reaction also. 5

Predict the product and draw the probable mechanistic pathway of the
following reaction : 5
i) Mg/Et20, A
& Cl ii) NH4C1 (aq)

(c) Write the structures (A to F) for the following sequence of reactions : 10

cr0 CH3 0H
K2CO3
A
CH3 CN Me0H

Dry HC1
A+ >B
Et20

Et20
B + MeMgBr > c

C + NH4 C1 (aq) > D

20% HCI
>E

FSI-D-CHM/44 4
 Write the appropriate reagent necessary for the following two conversions and
account for their formation : 10

Ph
0
>90%
Ph
HO
> Ph
>90%

Write the structure of the product of the following reaction and the
corresponding mechanistic pathway : 5
SnC14

CO2Me

Classify the following sigmatropic rearrangement and suggest if it would

proceed readily or slowly. Explain your answer : 5

—> CN
,-,<
113C H3C CO0C2H5
CO2C2H5

4. (a) When 4-bromonitrobenzene is reacted with cyanide ion, the product is devoid
of any nitrogen. Write the structure of the product, name the reaction and
write the corresponding mechanism. 5

(b) Write the structure of the major product in the following two reactions and
justify their formation : 5

EtOe >

(c) Carry out the following transformations : 5x2=10

N Glycerol —>

(ii) HCHO —> C(CH2011)4

FSI-D-CHM/44 5 [ P.T.O.
 (d) Write the structure of the products (A to E) in each step of the following
sequence of reactions : 10
0

CH3
H3
AlC13 Py/Ac20 mCPBA
A >B >C
A
Hydrolysis FeC13
>D E

What happens when salicylic acid is reacted with bromine in acetic acid?
Justify your answer. 5

Would you require the following conversion to require heat or light? Explain. 5

SECTION-B

5. Answer the following questions : 5x8=40

Calculate Mn of a polymer consisting of three fractions with molecular weights

1 x105, 2 x105 and 3 x10 5 . The mole fractions are found to be 0-1, 0.5 and 04
respectively.

Zimmer plot constructed from light scattering results on polymer solutions,

provides useful information. Justify your answer.

Determine the molecular weight of a polystyrene sample. Given a = 0-60,

K =1.6x10-4 dL/g and limiting viscosity number n = 04 dL/g.

Compound A consisting of carbon, hydrogen and oxygen shows in 1H-NMR

(100 MHz) a singlet (9H) in the upfield region, another singlet (214) in downfield
compared to the previous protons and a third broad singlet (1H) that appears in
the most downfield region. A on heating with H2SO4 produces B, which again
on catalytic hydrogenation produces 2-methylbutane. Write the structures of A
and B, and account for the 1H-NMR.

4-Methyl-3-penten-2-one has two absorption bands in its UV spectrum—one

at 236 nm and one at 314 nm.
0 CH3
CH3CCH=C—CH3
Why are there two absorption bands?
Which band shows the greater absorbance?

FSI-D-CHM/44 6
 (fl The mass spectra of two different cycloalkanes both show a molecular ion peak
at m/z = 98. One spectrum shows a base peak at m/z = 69 and the other
shows a base peak at m/z = 83. Identify the cycloaLlcanes.

(g) Give the product of the following reaction :

0
II i) NaBH4
CH3CH=CHCH2—C—CI 3
ii) H2O

Predict the stereochemistry of the product in the following reaction :

„CH3
CH3

ci
NCH C H3

6. (a) Give reasons for the following : 5x4=20

Teflon is an inert polymer, while LDPE is a branched polymer.

Natural rubber on masticating with about 30% sulphur becomes a hard
plastic.
Proteins are considered as monodispersed polymers.
Threshold molecular weight of polyethylene is higher than that for nylons.

Ethylbenzene shows a characteristic peak at m/z = 91, while n-propylbenzene

shows strong peak at m/z = 92. Explain with the help of fragmentation
pattern. 10

Identify the compounds X and Y in the following transformation : 5

cyH3 mCPBA LiA1H4

X Y
CHC13 Et20

Which will show an oxygen-hydrogen stretch at a greater wave number—

ethanol dissolved in carbon disulfide or an undiluted sample of ethanol?
Justify your answer briefly. 5

7. (a) Write the structure of the major and minor products formed in the following
reaction and give a suitable explanation : 10

Na, NH3(1) >

FSI-D-CHM/ 44 7 [ P.T.O.
 (b) Justify your answers for the following statements : 5x4=-20
Light scattering is a highly useful technique for the determination of
molecular weight of a polymer.
The determination of molecular weight by end-group analysis of a polymer
is carried out only if the number of determinable groups of molecules is
known.
Osmometric method is preferred over viscosity method for the
determination of molecular weight of a polymer.
Softening temperature of nylon 6,6 is higher than that of nylon 6,10.

(c) Of the following two compounds A and B, one cannot be oxidized by periodic
acid. Identify it and justify your answer : 10
OH

A
8. (a) 2,2-Dimethylcyclopropanone undergoes ring-opening when attacked by
methoxide ion. The product (b.p. 101 °C) has the following spectral properties:
IR : 1740 cm ' (s), 1160 cm-1 (no absorption near 1600 cm -1 or 3100 cm -1)
1 H-NMR : S 3.6 (3H, singlet), 81.2 (9H, singlet)

UV : Transparent above 200 nm

Mass : m/z 116, 85, 59, 31
Deduce the structure of the product and assign the spectral data. From the
mechanism, an alternative product might have arisen. What is it? 15

(b) (i) Write the structure of the product in the following reaction :

Ph
HO BH3-THF
14-
THF, Room temp.
Me Ph

How many moles of BH3 are needed to react with 2 moles of the starting
material? 5
What stereoisomer would be formed from the reaction of cyclopentene with
0s04 followed by hydrolysis? Explain. 5
Draw the ESR spectrum of CH3CHOCH2CH3. 5

(c) Sketch the chemical reactions in the preparation of polystyrene starting from
benzene and list a few important properties. 10

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FSI-D-CHM/44 8 BS9-90