CEMA-UG-S4-ES-C10-19

RAMAKRISHNA MissiON VIVEKANANDA CENTENARY CoLLEGE, RaHara, KoLKaTa

End Semester Examination 2019
Ivh Semester B.Sc. Chemistry Honours
Core Course X
Full Marks: 50
Time: 2 hours
(Symbols and notations have their usual meanings)
Answer three questions taking one from each Group

Group-A
a) Predict the product(s) of the following reactions and explain with mechanism.

Me 5x2 10
)
0-CH-CH=CH
CH3 CHCH=CH2

Me2C-CMe2 i) Conc. H2SO4

i)
OH OH ii) COH

CH3
iii) HCI
-NH-NH
EtOH

CH
NO2

iv) i)Zn,NH4CI, EtOH-H20

i) [Ag(NH3)]*
Me
v
Ph O OMe
i) PCls
18
OH ii) H0

b) Write down the steps for the synthesis of n-butylamine by Gabriel's Phthalimide
synthesis.Why is this method not viable for synthesizing tert-butylamine ? How will you
prepare tert-butyl amine from tertbutylchloride? 2+1+2=5

c) Convert (any three) 3 x2 =6

i) Aniline into o-bromoaniline
ii) Benzene into 2, 4 -dinitrophenylhydrazine
ii) Aniline into pure N-methylaniline
iv) Benzene into 4- bromo-3- chloroaniline

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mechanism (any two)

2x2 =4
d) Complete the following reactions with proper

(RCO),O
(i) RCN
heat
heat
(i) RNH2 + CHCl + KOH

(i) R2CHNO, 5/NaOH

and N N-dimetnyl
mixture of aniline, N-methylaniline
,

2 a
ow Can you separate a
3
aniline by Hinsberg's method?
as uic

b) Explain all the steps of Von Richter reaction taking

p-bromonitrobenzene
starting material.

c) Carry out the following transformation through Curtius rearrangement.

CHCH(OH)CO2H >CHCHO

and anisole is dissolved in hydrochloric

d) When a mixture of N,2,4-trichloroacetanilide 2
acid, among the products isolated are o-and p-chloroanisole. Explain.
3
e) Find the product and give explanation.
CH3CONH2 + Br2(0.5eq) + NaOH(0.5eq)

contaminated with alkyl isocyanide and alkyl

)How purify alkyl cyanide when
can you
isocyanide when contaminated with alkyl cyanide.
giving mechanism.
g) Complete the following reactions
Me Me CH3
1) H
+

OH OH
*stands for c
cOH
OH
A
+ KOH >A >B
ii) CH CH,SO,N(CH)NO

O H0 /heat
C
RCH2-C-CH-R 2
iii)
CN
between the following two compounds? 2
h) How can you distinguish
CH,CHCH,NO2 and (CH)2CHNO

Group-B
ot the following compounds and carry out synthesis
3. Show the retrosythetic analysis
3x5 15
(Any five): Ph. Ph
oH ph
ii) ii)
1) Ph
Ph Ph
coH O
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 CEMA-UG-S4-ES-C10-19

HO,C
iv) CO,H v)
O Vi)
CO,H
HO,C HC

4. a) CO,Et
Complete the following reactions
stereochemical approach : showing the major product with proper
i) R-CH-co.cocH(Mc Ph) PhMgBr 2x2=4

CH
) PhCHO +
H OLi

b) How does high dilution

technique help the formation of ring compounds- discuss the
principle.
2
c)Write true or false with proper
explanation 1x 3 3
i) All diastereoselective syntheses pass through diastereomeric transition states.
ii) All enantioselective syntheses pass through enantiomeric transition states.
ii) The term 'Asymmetric synthesis' is more acceptable than 'Stereoselective
synthesis'.
d) Using suitable protecting group how will you bring about the
following
transformation? 2
O OH

COEt
Br

e) Draw the Felkin-Anh model for (S) - benzoin and show the reaction with CHaMgl and

give the preferred stereochemistry of the major product formed. 2

f) Write synthetic equivalents of the following synthons. 2

i) HOCH,CH2 i) H;CO;Et. ii) Ph-O and iv) OOH

Group-C

a) Write the product(s) the following reaction and explain its/their formation based on
5.
FMO approach.
Me

i)

CHO

2
i) Buti, -78"c
ii) Warm to 0"c
ii) H

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 CEMA-UG-S4-ES-C10-19

b) Write down the product considering the correct regio and stereo selcctivites.

2x3=6
CH
i) HC Heat
CN+ N

CH

ii) light

a) The tollowing compound racemizes when heated. How can you explain this '
.

CH

HC

its formation based on FMO

b) Write the product in the following reaction and explain
2
approach.

HC H

H CH

c) Write the product with explanation. 3

Et CH3 Heat
o CH
d) Write down the major product with FMO explanation.

Ph
Heat

Ph
 CEMA-UG.S4-MS-CC 19-19

RAMAKRISHNA MIssION ViVEKANANIDA CENTENARY CoLLEGE, RAHARA, KOLKATA

MID SEMESTER EXAMINATION 2019
FOURTH SEMESTER
B.Sc. CHEMISTRY HONOURS
CORE COURSE X
Full Marks: 25 Time: 1 hour

Group-A
1. a) Carry out the following conversions: 2x 3=6

i) PhCO,H PhCH C0;Et

i)PhCH,CO,H-PhCH;NH
b) Convert 3

i)p- Toluidine intom - bromotoluene

ii)p - Nitroaniline intop - dinitrobenzene

c)How do alkyl cyanide and alky isocyanide differ towards hydrolysis by alkali? 2
d) What happens when primary nitro-compound is treated with NaNO,/HCI and then
made alkaline?

OR

a) Predict the products of the following reactions with mechanism. 2x3 6

2 O
i) OH
Ph-C OMe-
O
OH OH
H
i) PhC-Ç -OMe-

CH CH3
b) Complete the following reaction and write mechanism.
Aq. NaOH
CsHNCI+ CgHNO
c)Complete the following reaction giving mechanism 2+2 4
NO2 KCN/aq. EtOH
)
CH3

(i) PhCH,CN
NaOEt
A
H B
B
A
Group-B
a) What is the difference between stereospecific and stereoselective synthesis- Explain
with suitable examples.
b) Convert (any two): 22

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 CEMA-UG-S4-MS-CC 10-19

i) Benzene into m - dibromobenzene

ii) Aniline into 1, 3, 5 - tribromobenzene

iin)p Nitrotoluene into 3- bromo 4- nitrotoluene
-
-

OR

A. with Al-
d) rredict the product with proper stereochemistry when 2-octanone is treated
R-2-butoxide in R-2-butanol. 3
b) p Toluidine reacts with CoHsN,CI in faintly acidic solution to form a compound
which, on boiling with dilute H,SO4, gives four products along with nitrogen. Explan.
4

Group-C
5. Write down the major product and explain stereochemistry using FMO theory.
2% x 2 =F5
HaD heat
(a)
heat
(b)

OR

6. a) Compound A is light sensitive but not heat. Explain 3

A
2
b) Indentify X and Y.
hv heat
X Y