V Semester B.

Sc Examination, March/ April 2022

(CBCS)
CHEMISTRY
Organic Chemistry (Paper-V)
(Scheme of Valuation) (61503) Max. Marks : 70

PART-A
8 x 2: 16 M
1
What are enantiomers? Give an example.

Non- super imposable mirror images are called enantiomers.

Eg. Lactic acid
COOH COOH

H OH HO H
CH3 CH3
Def: 1 M
Structure: 1 M

2
How would ethylamine obtained from acetaldehyde?

When acetaldehyde is treated with ammonia in the presence of nickel,

reduction takes place to form ethyl amine.
Ni
H3C CHO + NH3
+ H2 H3C CH2 NH2

3 Write Haworth structure of Lactose.

Lactose is composed of β-D-Galactose and 1-D-glucose joined by β-D-
glycosidic linkage.

CH2OH CH2OH
HO O H OH
H H
OH H O OH H
H H OH
H OH H OH
Lactose

4 State isoprene rule.

The molecules of all terpenes are constructed of two (or) more isoprene units
(C5H8), usually joined in a head- to- tail fashion.
CH2
H3C tail
C CH
head
H 2C Isoprene (C5H8)

1
5
Write the Nitration of Quinoline.
O 2N
Fuming HNO3
Fuming H2SO4 +
N N N
O 2N 5-NitroQuinoline
Quinoline 8-NitroQuinoline

6 Write structure of menthol and its uses.

OH

Menthol
Uses: 1. used as antiseptic in ointments and nasal sprays.
2. It is used in face creams, shaving cream and tooth pastes.
3.it is used as flavoring agent.

7 What is Mordant?

Some dyes have no natural affinity with fabric. The mordant bind the fiber and
then combines with the dye to form insoluble coloured complex. This complex is
called lake.
Eg.Oxides of aluminum and chromium.

8 Write the structure of Dichlofenac and its uses.

COOH Cl
NH

Cl
Diclofenac
Uses: it is anti-inflammatory drug it possess anti-
pyretic and analgesic action. It is used for the treatment of rheumatoid
arthritis.

9 What is bathochromic effect? Give an example.

Absorption maxima are shifted to longer wave length is called bathochromic

shift (or) red shift. It is due to the presence of auxochromes (or) by change of
solvent. Increase in conjugation causes bathochromic shift.
Eg. Butadiene λmax = 217 nm β-carotene= λmax= 451 nm

2
10
What is principle of UV Spectroscopy?

Absorption of U.V and visible radiation causes electrons are promoted from one
energy level to a higher energy level within molecule

11
Write the D L configurations of Glyceraldehyde.

CHO CHO

H C OH HO C H

CH2OH CH2OH

D-Glyceraldehyde L-Glyceraldehyde

12
What are Epimers?

Pair of isomers which have identical configuration on all their asymmetric

carbon, except C2 (or α-carbon) carbon is called Epimers.

Eg. Glucose and Mannose.

3
 PART- B 9 X 6 : 54 M

13 A). Explain optical isomerism in lactic acid?

Lactic acid has chiral carbon and exists as non - super imposable mirror
images are called Enantiomers.
COOH COOH

H C OH HO C H

CH3 CH3

d (or)+ isomer l (or) - isomer

Enantiomers have identical physical and chemical properties but differ with
rotation of plane polarized light.
dextro (or) + isomer: it rotate plane polarized light towards right (or)
clockwise direction called as dextro isomer. It is optically active.
Laevo(or) - isomer: it rotate plane polarized light towards left (or) anti
clockwise direction called as laevo isomer. It is optically active.
Racemic mixture (or) dl-mixture: Equimolar molar mixture of dextro and
laevo isomers is called racemic mixture (or) dl-mixture. It is optically
inactive, due to external compensation. Because one molecule rotates
clockwise direction and another rotate anti clockwise direction. One
molecule is compensated by another.

b) Write E and Z configuration of 2- butene.

(1) H (2)
(1) H3C CH3 (1) H3C
C C C C
H H (2) (2) H CH3 (1)
(2)
Z-configuration E-configuration

14 A). Explain Resolution of Racemic mixture by Chemical method.

1. Chemical method: in this method racemic mixture is made to combine

with another optically active compound. For example racemic lactic acid is
allowed to combine with optically active base, (-) strychnine. Two different
salts are formed.
(+) lactic acid + (-) strychnine (-) strychnine (+) lactate.
(-) lactic acid + (-) strychnine (-) strychnine (-) lactate.
These two salts are not true enantiomers. They differ in soluble properties.
By fractional crystallization, they can be separated. Then treatment with
dilute acid removes the optically active base and leaves the two separate
samples of (+) lactic acid and (-) lactic acid.
b) Define Resolution.
The Separation of a racemic mixture into its optically active isomers of dextro
and laevo isomers is known as resolution

4
15 A). Describe Hinsberg test to distinguish primary, secondary and tertiary
amines.

This involves the treatment with benzene sulphonyl chloride (Hinsberg

reagent), then made alkaline with aqueous with NaOH.
2. The primary amines give N-alklylbenzene sulphonamide. This forms salt
with NaOH, which is soluble in water.
H H +
NaOH Na
-
SO 2Cl +H N R
- HCl
SO 2 N R SO 2 N R

N-alkylbenzene soluble
Primary amine salt
sulphonamide (insoluble)
3. The secondary amines gives N,N- dialklylbenzene sulphonamide. This do
not form salt with NaOH (no acidic hydrogen) and insoluble in alkali
solution.
R R
NaOH
SO 2Cl + H N R
- HCl
SO 2 N R No reaction

secondary N,N-dialkylbenzene
amine sulphonamide (insoluble)
4. The tertiary amines do not react with reagent because no acidic hydrogen
is available.

b) How benzene diazonium chloride is converted to Chloro benzene?

Benzene diazonium chloride is treated with cuprous chloride (CuCl) to form

Chlorobenzene. The reaction is known as Sandmeyer reaction.
+ -
N2Cl + CuCl Cl
Benzene
Chloro benzene
diazonium chloride

16 A). write classification of Carbohydrates , based on number of monomeric units

Present, with one example per each.

The carbohydrates are classified into three major groups based on number of
units are formed on hydrolysis.
1. Monosaccharides: These are poly Hydroxy carbonyl compounds, which
cannot be decompose on hydrolysis.
Eg . Glucose and Fructose.
2. Oligosaccharides: Oligosaccharides contain 2-9 monosaccharide units.
a) Disaccharides: it gives two Monosaccharides on hydrolysis.
Eg. Sucrose. Glucose and Fructose
Maltose : Two glucose units.
b) Trisaccharides: it gives three Monosaccharides on hydrolysis.
Eg. Raffinose : Glucose + Fructose + Galactose.
c): Tetrasaccharides: it give four monosaccharides . etc
3. Polysaccharides: it gives many Monosaccharides on hydrolysis.
Eg. Cellulose and starch.

5
 b) Write the structures erythro and threo isomers of tartaric acid.

In the isomer similar substituents present on the same side is known as

erythro isomer and if they present on the opposite side called as threose
isomer.
COOH COOH
H OH H OH
H OH HO H
COOH COOH
Erythrose Threose

17 A). Describe the Skraup’s synthesis of Quinoline.

OH OH OH Con. H2SO4
H2C CH CHO
H2C HC CH2 -2 H2O Acrolein
Glycerol
H H
OHC C
O C
HO
+ CH CH2 CH

NH2 CH2 NH CH2 CH2

NH
Aniline Acrolein β -Anilinopropionaldehyde Enol

H H H
HO C C C
H2 SO4
H CH C6H5NO2 CH
CH
- H2 O CH2 CH
CH2 N N
NH H
Dihydro quinoline Quinoline

b) Give an example for Chichibabin reaction.

Pyridine is heated with sodium amide in toluene solution to form 2-amino

pyridine. With excess of sodium amide to form 2,6-diamino pyridine, called as
Chichibabin reaction.
NaNH2
+ NaNH2
N N NH2 H2N N NH2
Pyridine 2-aminopyridine 2,6-aminopyridine

6
18 A). Write any four general characteristics of alkaloids.

1. Alkaloids are usually colourless, crystalline, non- volatile liquids.

2. They are readily soluble in ether and chloroform.
3. They are optically active, the majority being laevorotatory.
4. They are basic with bitter taste.

b) Structure of Nicotine and Chiral carbon.

*
N * Chiral carbon
CH3
N
Nicotine

19 A). How malachite green synthesized?

N(CH3)2
Con H2SO4 Oxidation
CH3 +2 N(CH3)2 HC
N(CH3)2

N(CH3) 2 +
N(CH3) 2 Cl-

C HCl
OH C
N(CH3)2 N(CH3) 2

Colourless Malachite green

b) Write the R and S configuration of 2- amino propanoic acid.

1 1
NH2 2 H2 N
3 2 3
H3C COOH HOOC CH3

H H
R-configuration S-configuration

7
20 A). Outline the synthesis of sulphanilamide.

HN CO CH3 HN CO CH3 HN CO CH3 H2N

ClSO2OH NH3 Hydrolysis

- H2O

ClO 2S H2NO2S H2NO 2S

p-acetamido benzene p-acetamido benzene sulphanilamide
Acetanilide
sulphonyl chloride sulphonyl amide

b) Write synthesis of pyridine from acetylene.

2 HC CH + HCN Pyridine
N

21 A). What is chemical shift? How it expressed?

The difference in the absorption position of a particular proton from the

absorption position of the reference of proton is called chemical shift. It is
denoted by symbol delta (δ). Chemical shift values proposed by Tau (3) values
also.
δ = 10 ppm 3 = 10 – δ.
Lower delta value and high tau value proton is highly shielded.

b) Why TMS used as the reference compound in NMR spectroscopy?

1) Chemically inert, highly volatile.

2) It gives only one peak for 12 protons and this peak is observed in the high
magnetic field, when compared to all other protons

22 A). Mention the number of signals and Multiplicity of the NMR spectra of 1,1, 2-
Trichloro ethane.

Cl Cl

CH CH2 1,1,2-Trichloro ethane

b a
Cl

a. Doublet, δ 4.2 for 2 H. b. Triplet, δ 5.7 for 1H.

8
 b) Write the Advantages of spectroscopic methods over conventional methods.

1) It requires a small amount for investigation.

2) These methods are quick and very sensitive.
3) These methods reliable and permanent record of observations.
4) The sample can be reused after analysis.

23 A). Explain Gabriel phthalimide reaction with an example.

CO CO
KOH
NH CH3CH2Br
NK
- H2O - KBr
CO CO
Phthalimide
CO
COOH
OH- /H2O
NCH2CH3 + H3C CH2 NH2

CO Ethyl amine
COOH

b) IUPAC name of tri methyl amine.

H3C N CH3
N,N-Dimethyl methanamine
CH3

24 A). How citral synthesized from methyl heptenone?

OH
O AC2O
zn + Br -CH2COOC2H5 CH2 COOH
H2o - H2 O

Methyl heptenone
β−Hydroxy acid

CH COOH (HCOO)2Ca CH
Distilation CHO

Citral
Geranic acid

b) Compare the basicity of pyrrole, pyridine.

The nitrogen lone pair electrons in pyrrole are in p-orbital are involved
delocalization with ╥ -molecular orbital and not available for protonation.
Whereas the nitrogen lone pair electrons in pyridine are not involved in the
formation of delocalized ╥ -molecular orbital. So these lone pair is readily
available for protonation. Hence Pyridine is more basic than pyrrole.

9
25 A).Draw the two conformations of 1, 2 dimethyl cyclohexane.

CH3
CH3
CH3
CH3
CH3 H3C
Cis 1,2 dimethyl cyclo hexane Trans 1,2 dimethyl cyclo hexane Trans1,2 dimethyl cyclo hexane
(a,e) (e,e) (a,a)
b) Significance of Finger print region in IR spectroscopy.

The region from 667 cm-1 to 1500 cm-1 is called finger print region. Some
molecules containing the same functional group, show similar absorptions
above 1500 cm-1, but their spectra differ in the finger print region. Such
compounds can be easily distinguished by comparing their finger print
region.

Name and Address of Chairman in BOE

Dr. Manzoor Hussain

Associate Professor of Chemistry
Govt, First Grade College
Doddaballapura. 561203

Mobile: 944801900.

Name and Address of chief examiner

Dr. K. Vasudeva Reddy

Associate Professor of Chemistry
Govt, College for Women,
Chintamani-563125.

Mobile: 9440359237.

10