Lecture - IV

Optical Isomerism
• Conditions for Optical isomerism
• Diastereomers
• Resolution of Racemic mixture
• Racemization
• Questions on Geometrical Isomerism

Date : 2079- 02- 17

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 Conditions for Optical isomerism
In order to exhibit optical isomerism a compound should
fulfill following conditions.
No plane of symmetry - A compound should not have a plane
of symmetry (a plane through which a compound can be
divided into two identical halves) to show optical isomerism.
For example lactic acid & tartaric acid shows optical
isomerism since they do not have a plane of symmetry.
CH3
Both the compounds
cannot be divided
into two equal halves
COOH through any plane.
So no plane of
symmetry.
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 Conditions for Optical isomerism…
Presence of asymmetric carbon or chiral center or
chiral carbon -Presence of chiral carbon generally makes a
compound asymmetric. For example lactic acid and tartaric
acid are asymmetric molecules and show optical isomerism due
to the presence of chiral carbons. There are some compounds
which do not show optical isomerism even having chiral
carbon because of plane of symmetry. For example meso-
tartaric acid and meso -2, 3- dihydroxybutane.

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 Conditions for Optical isomerism…
Does not superimpose on its mirror image -An organic
compound which shows optical isomerism should not
superimpose on its mirror image. For example, d-lactic
acid is the mirror image of l-lactic acid and vice versa.
Both the isomers of lactic acid are not
superimposable to each other.

Non –superimposable mirror image form of one another. 4

 Diastereomers
The stereoisomers which are not mirror image to one
another are called diastereomers. For example 3 -bromo -2-
butanol exists in four forms as follows.
4
3
2
1

A & B – stereoisomers; A& C ; B & C – stereoisomers but not mirror image forms.

A&B; and C & D – Enantiomers –Why 5

A & C ; A&D; B & C;B & D; – stereoisomers but not mirror image forms( Diastereomers)
 Diastereomers…
A and B – Enantiomers Hence diastereomers are
C and D - Enantiomers stereoisomers that are not
B and C – Diastereomers mirror images of each other.
B and D - Diastereomers Two diastereomers have
A and C – Diastereomers different melting points, boiling
A and D - Diastereomers points, solubility etc.

Similarly, 2, 3-dichloropentane exists in four forms as shown

below.

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 Diastereomers…

1
2
3
4
5
2,3 - dichloropentane

A & B – stereoisomers; A& C ; B & C – stereoisomers but not mirror image forms.
C & D – stereoisomers; A& D ; B & D – stereoisomers but not mirror image forms 7
 Diastereomers…
Properties of Diastereomers
• They show identical chemical properties (as they
contain the same functional groups).

• They can be separated by techniques like fractional

crystallization, fractional distillation and
chromatography.

• They have different physical properties like melting

point, boiling point, densities , solubility in a given
solvent. 8
 Resolution of Racemic mixture
The process of separation of a racemic mixture into its
components i.e. d and l-isomers is called Resolution.

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 Resolution of Racemic mixture...

Micro-organism One of the components

Racemic
of Racemic mixture
mixture
consumed
For example Biochemical Separation of Racemic mixture of
Tartaric acid
Pencillium glaucum L- Tartaric acid
Racemic
Consuming
Mixture of
- a mold D- Tartaric acid
Tartaric acid
In Biochemical separation one of the components of
Racemic mixture is consumed by micro-organism leaving
one component. So called Sacrificial method
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 Resolution of Racemic mixture...
Chemical separation
Racemic Another Compounds with
+ optically active different physical
mixture
compound properties

For example chemical separation of Racemic mixture

of lactic acid.
(-) Strychnine (+) lactate
Racemic (- ) Strychnine (-) Strychnine (-) lactate
mixture of + An optically -Compounds having
Lactic acid active compound different physical
properties like solubility

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 Resolution of Racemic mixture...
Dissolve
in solvent Cool Less soluble
salt
Two salts separates out
By warming

Heat for
Filter

Time and
then cool
More soluble
salt
Fractional crystallization separates out

In this way two salts have been separated 12

 Resolution of Racemic mixture...

Treated separately with dil. HCl d and l – Lactic

Two salts acids in
to remove basic part the salts separated from

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Racemization

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 Questions on isomerism

• What do you mean by geometrical isomerism?

• Mention the conditions for geometrical isomerism.
• What isomerism is shown by maleic acid?
• What isomerism is shown by fumaric acid?
• Why does propene not show geometrical isomerism?
• What isomerism is shown by butenedioic acid?
• Why is cis –isomer less stable than trans- isomer?
• What isomerism is shown by the compound having general
formula ab C = Cyz?
• What isomerism is shown by the compound with formula
ClBr C = CFI?

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 Questions on Isomerism
• (a)What are geometrical isomers? Write the criteria for a
compound to exhibit geometrical isomerism. [2]
(b)Show your acquaintance to enantiomers and
diastereomers giving suitable example. 2076 [3]
• (a)What are geometrical isomers? Write the criteria for a
compound to show geometrical isomerism. [1+1.5]
(b)Write the points of differences between enantiomers &
diastereomers with suitable example of each.2075 [2.5]
• (a) Define enantiomers, racemic mixture and meso-
compound giving one example of each. Also comment
on their optical activity. 2067 [4]
(b)Draw the structure and specify Z and E configuration of
1- Bromo-1 chloropropene. [1]
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 Questions on Isomerism….

• (a) Distinguish between enantiomers and diastereomers giving

• suitable example. 2072[3]
(b)What are Cis and trans-isomers? Which of these two isomers is
more stable and why? [2]
• (a)How do enantiomers differ with diastereomers? Illustrate with
an example. 2070 [1+2]
(b)What isomerism is shown by 2-bromo 1-chloropropene? Mention
Z and E notation for the compound. [2]
• What are geometrical isomers? Geometrical isomer is not possible in
the compound CH3CH = CH2 explain. Why are trans isomers more
stable than Cis-isomers? 2073 [1+2+2]
• Write down the possible geometrical isomers of but-2-ene-1, 4-dioic
acid. Why does this compound exhibit geometrical isomerism?
Explain the difference between enantiomers and diastereoisomers
giving an example of 3-bromo-2-butanol. 2072 [1+1+3]
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 Questions on Isomerism….
• Distinguish between enantiomers and diastereomers. Show all
optical isomers of(a) 3-Bromo 2-butanol and (b) Tartaric acid. Also
show optically inactive meso form of tartaric acid. Explain why 3-
Bromo -2-butanol doesn't exist in meso form. 2072 [1+1.5+1+1+0.5]
• Distinguish between enantiomers and diasteromers. Write all
possible stereo isomers of a compound that contain two asymmetric
carbon atoms. 2067 [3+2]
• What isomerism is shown by hex-3-ene.Write the possible isomers
and mention E & Z notation.

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Z -1-Bromo-1-chloropropene E -1-Bromo-1-chloropropene

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 1 2 3 4 5 6
H3C – CH2 – CH = CH – CH2 – CH3
Hex – 3 – ene

H3CH2C H
H3CH2C CH2CH3

C=C C=C
H H CH2CH3
H

Cis-Hex – 3 – ene Trans - Hex – 3 – ene

H3C H
Same
C=C atoms
H H
Propene 20
21
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 But-2-
but -2 –ene
ene-1,4
-1,4- dioic
- dioicacid
acid

Cis - but -2 - ene -1,4 - dioic acid Trans -but -2 - ene -1,4 - dioic acid
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 Questions on Optical isomerism…
• What do you mean by optical isomerism?
• Mention the conditions for optical isomerism.
• What isomerism is shown by lactic acid ?
• What isomerism is shown by tartaric acid?
• Why does racemic mixture not show optical
isomerism?
• Why does meso - tartaric acid not show optical
isomerism?
• What isomerism is shown by but-2-ene?
• What isomerism is shown by 2,3-dihydroxybutenedioic
acid?
• What do you mean by enantiomers and
diastereomers?
• Give an account of Racemization and Resolution.
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 Questions on Geometrical isomerism
• Mention the conditions for geometrical isomerism.
• What isomerism is shown by maleic acid?
• What isomerism is shown by fumaric acid?
• Why does propene not show geometrical isomerism?
• What isomerism is shown by butenedioic acid?
• Why is cis –isomer less stable than trans- isomer?
• What isomerism is shown by the compound having
general formula abc C = C xyz?
• What isomerism is shown by the compound
• ClBr C = CFI

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 Questions on Optical isomerism…
• What do you mean by optical isomerism?
• Mention the conditions for optical isomerism.
• What isomerism is shown by lactic acid ?
• What isomerism is shown by tartaric acid?
• Why does racemic mixture not show optical
geometrical isomerism?
• Why does meso- tartaric acid not show optical
isomerism?
• What isomerism is shown by but-2-ene?
• What do you mean by enantiomers and
diastereomers?
• Give an account of Racemization and Resolution.
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