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org 20/08/2013
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Optical Isomerism
N Goalby
Chemrevise.org
Types of isomerism
Isomerism
Structural
isomerism
Stereoisomerism
Geometric
isomerism
Optical isomerism
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Optical Isomerism
Optical isomerism occurs in carbon compounds with 4 different
groups of atoms attached to a carbon (called an
asymmetric carbon).
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Mirror images
Non superimposable
Compounds that show optical isomerism are called chiral
compounds.
mirror
not isomers (same compound)
key
Optical Isomers
H
H
H
H
H
H
H
H
Can be rotated and
are superimposable
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C
H
C
H
C
H
H
H
C
H H
H
O
H
H
These four groups are arranged tetrahedrally around the carbon.
C
H
5
C
2
CH
3
H
OH
C
C
2
H
5
C H
3
H
OH
This causes two
different isomers
that are not
superimposable to
be formed. They are
mirror images
key
Chiral Carbons
The central asymmetric carbon is called the
chiral centre.
Optical isomers have similar physical and chemical
properties, but they rotate plane polarised light in different
directions.
One optical isomer will rotate light clockwise and the other
isomer will rotate light in an anti-clockwise direction.
key
Polarising
filter
Unpolarised
light
Light
source
Plane
polarised
light
Sample
solution of
chiral
substance
Plane
polarised light
after rotation
Angle of
rotation of plane
polarised light

Analysing
filter
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One optical isomer will rotate plane-polarised light clockwise
(+)(called dextrorotatory). The other will rotate it
anticlockwise(-)(called laevorotatory).
A mixture of equal amounts of the two optical isomers will
not rotate plane-polarised light. The mixture is called a
racemic mixture or a racemate
C
H
3
C
CN
H
OH
mirror
These stereoisomers are called enantiomers.
key
C
H
3
C
CN
H
OH
Brief method
first put water in sample tube and rotate analyser to block
out light
replace water with sample. If the sample is chiral light will
be seen
rotate analyser again to block out light. The amount the
analyser is rotated is the amount the light has been rotated.
Method for using polarimeter
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Chemical Reactions and Optical Isomers
Formation of a racemate:
A racemate will often be formed in a reaction when a
triagonal planar reactant or intermediate is approached
from both sides by an attacking species
:CN
NC:
C
CH
3
O
H
e.g. the reaction of ethanal and HCN
The carbonyl group is planar and can be attacked from both
sides
key
:CN
NC:
C
CH
3
O
H
C
C H
3
CN
OH
H
C
NC CH
3
OH
H
There is an equal chance of
either enantiomer forming so a
racemate forms. No optical
activity is seen
Chemical Reactions and Optical Isomers
key
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C H
2
CH CH
2
CH
3
H Br

-
C H
3
C
+
CH
2
CH
3
H
:Br
-
C
+
C CH
2
CH
3
H
H
H
H
:Br
-
C
CH
3
Br
H
CH
2
CH
3
C
CH
3
Br
H
CH
2
C H
3
CH
2
CH
2
CH
2
CH
3
Br
The bromide can attack
this planar carbocation
from both sides leading to
a racemate
If the alkene is
unsymmetrical, addition of
hydrogen bromide can
lead to isomeric products.
Addition of HBr to But-1-ene
Nucleophilic substitution mechanism
Bromoethane [Primary haloalkane] + aqueous hydroxide ions
+ -
CH
3
H
Br C
H
-
OH
CH
3
H
OH C
H
Br
-
This is the mechanism we learnt in module 2. There are, however, two
major types of nucleophilic substitution and the products formed by the
different mechanisms can show different optical activity.
The two mechanisms are called SN1 and SN2
EXT!
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C
CH
2
CH
3
H
C H
3
Br
Nucleophilic substitution mechanism, S
N
1
2-bromobutane [Secondary haloalkane] + aqueous hydroxide ions
+ -
-
OH
Br
-
CH
3
H
C
C
2
H
5
+
EXT!
The Br breaks off leaving a
planar carbocation
intermediate
The OH
-
ion can then attack from
either side resulting in different
enantiomers and a racemate
forms
C
C
2
H
5
C H
3
H
OH
C
CH
3
H
5
C
2
H
O H
or
C
CH
2
CH
3
H
C H
3
Br
Nucleophilic substitution mechanism, S
N
2
Bromoethane [Primary haloalkane] + aqueous hydroxide ions
+ -
-
OH
Br
-
CH
3
C
H
H
Br HO
EXT!
In the SN
2
mechanism no intermediates are formed and the
reaction occurs via a transition state.
If the reactant was chiral then during the reaction the
opposite enantiomer would form. The animation on the
next slide shows this happening.
C
CH
2
CH
3
H
O H CH
3
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C C H
3
H
H
3
CH
2
C
Br
C
C H
3
H
H
3
CH
2
C
HO Br
C
CH
3
H
H
3
CH
2
C
HO Br
C
CH
3
H
CH
2
CH
3
HO Br
-
HO:
Br
-
If the reactant was chiral then
during the reaction the opposite
enantiomer would form.
C
CH
3
H
CH
2
CH
3
HO
Ibuprofen
CH
C
CH
CH
C
CH
CH
2
C H
CH
3
C H
3
C H
CH
3
C
O H
O
Drug action and optical isomers
Drug action may be determined by the stereochemistry of
the molecule. Different optical isomers may have very
different effects
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Thalidomide
One enantiomer of thalidomide causes birth defects in
unborn children whilst the other had useful sedative
problems. Unfortunately is was given in a racemic
mixture when first used.
C
C
C
C
C
C
C
C
O
O
N
C
C
C
C
C
O
O
N
H
H
H
H
H
H
H
H
H
H
C
C
C
C
C
C
C
C
O
O
N C
C
C C
C
O
O
N
H
H
H
H
H
H
H H
H
H
Where is Chiral carbon?
R thalidomide (dangerous drug) S thalidomide (effective drug)