Optical Isomerism

Optical isomers are compounds of identical structure but differencing from

each other in their absolute value of specific rotation and the phenomenon of
their existence is called optical isomerism.
Plain polarized light : The wave theory of light tells us that ordinary light rays
consists of electromagnetic radiations of different wavelengths vibrating in
many planes. the plane of vibration of each light wave is perpendicular to the
direction of its propagation. Such types of light is ordinary light or many sided
light which can be made to vibrate in a single plane by passing them through a
specially constructed prism, called Nicol prism. the light wave which vibrates
in a single plane is said to be plane polarized light; and the plane, through the
ray, perpendicular to the direction of the vibration is called the plane of
polarization of the plane polarized light.
Plane polarized light
Optical activity
When plane polarized light is passed through a solution of urea in
water, the plane of polarization of the emergent light remains the same
as that of the incident light; but when such a light beam is passed
through an aqueous solution of glucose, the plane of polarization of
incident light gets rotated through a certain angle therefore the plane
of polarization of the emergent light becomes different from that of the
incident light. Thus glucose molecules are capable of rotating the plane
of plane polarized light, while urea molecule fail to do so. substance
capable of rotating the plane of polarization of plane polarized light are
said to be optically active and those which fail to rotate the same are
said to be optically inactive; Thus urea is an optically inactive substance
but glucose is an optically active substance.
Dextro and Levorotatory substance
An optically active substance may rotate the plane of polarization of a
plane polarized light either to the left or to the right the substance
which rotates the plain of polarization of a plane polarized light to the
left or anti clockwise is said to be levorotatory ( Latin word 'leavus'
meaning left ) and that which rotates to the same to the right or
clockwise is called dextrorotary ( Latin word 'dexter' meaning right ).
Dextro and Levorotatory and dl
Symmetric and Asymmetric molecules
Symmetric molecule
The molecule which can be divided into two equal parts is called
symmetric molecule.
Asymmetric molecule
the molecule which cannot be divided into two equal parts is called
asymmetric molecule.
Asymmetric carbon ( chiral center )
The carbon which is bonded with four different atoms or groups is
called asymmetric carbon or chiral center or chiral carbon. itis
represented by asterisk (*).
Symmetric molecule
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Asymmetric molecule and Asymmetric carbon ( chiral center )
Enantiomers
The chiral molecules which are non-superimposible mirror-images of each
other are enantiomers. They have the opposite crystal structures and
configurations. they rotate plane of the plane polarized light in the opposite
directions but to the same extent. the physical properties of enantiomers are
identical ;e.g., b.p, m.p,. and solubility in optical inactive solvents are the same
- (+)-and ( - )- tartaric acids melt at 170 C and their solubility in water at 20 C
is 1390 g/litre. the chemical properties of the enantiomers are identical in a
symmetrical environment; this means that two optical antipodes behave
similarly towards achiral reagent, achiral solvent and achiral catalyst. if any one
of the reagent, the solvent and the catalyst is chiral the enantiomers react at
different rates. In other words in an Asymmetric environment the enantiomers
react at different rates and form products in different amounts. For, this
reason, enantiomers have different solubilities in the same chiral solvent.
Enantiomers
Diastereomers
Diastereomers are stereoisomers that are not mirror-images of each
other.
diastereomers have different physical and chemical properties even
towards achiral reagents, solvents and catalysts; this is because they
have different amount of free energy. Hence, it is possible to prepare
optically active substance from an optically active molecule creating a
new asymmetric center because in the process two diastereomers
result and one of which will be in excess over the other.
We know that(+)-tartaric acid is diastereomers with meso-tartaric acid,
these two have different melting points. e.g170C and 206C respectively.
Diastereomers
Meso Compounds
The compound which contains more than one chiral center but has a
plane of symmetry is known as meso compound. such compound are
optically inactive because the rotation caused by one half of the
molecule is cancelled by equal and opposite rotation caused half of
the molecule, which is the mirror image of the first half.
Racemic Mixture
A mixture having equal amount of d or l- isomers is called racemic
Mixture or dl mixture. It is also optically inactive because the rotation
caused by one molecule of atom is cancelled by equal and opposite
rotation caused by another molecule which is the enantiomer of the
first. It is denoted by (+,-).
Resolution of Racemic mixture
The process of separation of racemic mixture into its components is
called resolution of racemic mixture.
The special methods for the resolutions of racemic mixture are as
follows;
1. Mechanical separation
2. Chromatographic separation
3. Biochemical separation
4. Chemical separation
 Mechanical separation
Since(+)- and (-)- forms have opposite crystalline shapes, this property can be used in
separating two forms from a racemic mixture; because this type of racemic modification
contains two distinct crystals of opposite shapes . In fact, Pasteur used this process to
separate (+)- tartaric acid and (-)- tartaric acid from (+,-)- conglomerate of tartaric acid
obtained by crystallization of the same from water at a temperature of below 27C.
To resolve the enantiomers by process, crystals of opposite facets are to be seen
distinctly under the microscope; then with the help of a tweezer the two types of
crystals are to be picked up one by one and to be collated in in separate containers.
However this process has some demerits:
a) the method of mechanical separation has no value in practice. this is because it is
not applicable to racemic compounds and solid solutions.
b) distinctive crystal facets are seldom found in racemic; mixtures this makes the
separation troublesome and incomplete.
c) the process is tedious. Therefore the process of mechanical separation has historic
interest only.
 Chromatographic separation
Enantiomers react with an optically active reagent at different rates and produce
diastereomers of different stabilities. This property is utilized in chromatographic
separation of enantiomers.
The process consists in allowing a solution of the racemic form of a chosen solvent to
pass slowly down optically active absorbent like starch. Then the enantiomers are
absorbed by the active absorbent at different rates to form diastereomers of different
stabilities. now the column is cluted with the solvent. the enantiomer forming less
diastereomer comes down the column than the other elution is collected in a separate
vessel. In this way a partial separation of enantiomers may be possible. (+,-)- Mandelic
acid is resolved almost completely using starch as an absorbent. paper chromatography
can also be used for the purpose. Here cellulose acts as an optically active substance.
This process is very useful in deciding whether a given substance is a dl pair or a
compound containing symmetric molecules. If the elution is found to be optically
active, the substance under investigation is definitely a dl pair; if not, it consist of
symmetric molecules.
 Biochemical separation
When living organisms are added to or developed in a racemic modification, they eat up one of the
enantiomers preferentially leaving the other behind. Thus resolutions of racemic forms can be done
using this specific property of living organisms. Living organisms contain optically active bio-catalyst
called enzymes; these being optically active, react at different rates with a pair of enantiomer. Thus a
particular enzyme of an organism helps it to digest one of the enantiomers. As chemical reaction occurs
in this process with the help of bio-catalyst, the process is known as bio-chemical separation.
penicillium, glaucum and mould, cats up preferentially (+)- ammonium tartrate when it is added to (+,-)-
ammonium tartrate.
This method has limited use because:
a) it is difficult to find proper organism,
b) one gets one of the enantiomers at the expense of the other.
c) dilute solutions must be used; if otherwise, organisms may die and hence small amount of resolved
product will be obtained.
However, since biological processes are highly specific, this method leads to a high extent of resolution
provided proper organism is applied for the same. Bio-chemical separation was discovered by pastuer.
Chemical separation or separation by conversion into Diastereomers
Enantiomers have identical physical properties while diastereomers have different
physical properties. this fact is utilized in resolving racemic modifications by this
process the racemic form to be resolved is allowed to react with an optically active
substance, two diastereomeric derivatives are then formed. These have different
solubilities, boiling point etc. So, by fractional crystallization, the solid diastereomers
can be separated. Each of the enantiomers may then be regenerated and isolated from
the diastereomers. Nowadays gas-chromatography is also used to separate the
diastereomers. Fractional distillation has minimum scope. The overall procedure is
shown below.
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R and S system of Nomenclature Cahn-Ingold-Prelog System
To design the configurations, Cahn-Ingold-Prelog developed R and S system of Nomenclature,
whose salient features are given below:
1. On the basis of sequence rule, the four atoms/groups attached to the asymmetric carbon
atom or assigned precedence order 1,2,3 and 4.
2. After giving priority to four atoms /groups attached to the asymmetric carbon atom, rotate
the group of the lowest priority so that the atom or group of lowest priority is directed away
from the observer. Then view the arrangement of the remaining three atoms/groups in the
decreasing order of their priority.
3. While viewing the above sequence if eye moves in:
i. a clockwise direction then the configuration is assigned as R Notation.
ii. an anticlockwise direction then the configuration is assigned as S Notation.
NOTES: i ) A racemic mixture is assigned as (R,S).
ii ) An R or S compound may be either dextrorotatory or laevorotatory, since the direction of
rotation of plane polarized light has nothing to do with R and S Notation.