Poc Unit-1
Poc Unit-1
Poc Unit-1
B. PHARM
UNIT-1: STEREOISOMERISM
1. Introduction
Page No.
1.1 Structural Isomerism 2
1.2 Stereoisomerism 2
2. Optical Isomerism 2
2.1 Plane polarized Light 2-3
3. Optical Activity 4
3.1 Angle of Rotation 4
3.2 Specific Rotation 4
4. Chiral and Achiral Molecule 4-6
5. Element of symmetry 6-7
6. Enantiomers and Diastereomers 7
7. Meso Compound 7-8
8. Racemic mixture 8
8.1 Resolution of racemic mixtures 8-9
9. Configuration 9
STEREOISOMERISM
1. INTRODUCTION: Many organic compounds have same molecular formula but are different
in their physical and chemical properties. These compounds are known as isomers and this
property is known as isomerism.
1.2 STEREOISOMERISM: The isomers have the same structural formula but differ in relative
arrangement of atoms or groups in space within the molecule are known as stereoisomers and the
phenomenon as stereoisomerism. It can be further classified into three types:-
1. Geometrical isomerism
2. Optical isomerism
3. Conformational isomerism
2. OPTICAL ISOMERISM:- Any substance that rotates the plane polarized light is optically
active and the phenomenon related to it is called optical isomerism.
2.1 Plane polarised light:- Ordinary light consists of electromagnetic waves that oscillate in all
planes perpendicular to the direction in which the light travels. Passing light through a polarizer
allows light in only one plane to come through. This is plane-polarized light (or simply polarized
light), and it has an electric vector that oscillates in a single plane.
With chiral compounds, the plane of the polarized light is rotated through an angle α. The angle
α, measured in degrees (°), is called the observed rotation. A compound that rotates the plane of
polarized light is said to be optically active.
3.1 Angle of rotation:- The angle through which the plane polarized light is rotated by an
optically active substance is called as angle of rotation. It is denoted by α.
3.2 SPECIFIC ROTATION:- The observed rotation depends on the number of chiral molecules
that interact with polarized light. This in turn depends on the concentration of the sample and the
length of the sample tube. To standardize optical rotation data, the quantity specific rotation (*α+)
is defined using a specific sample tube length (usually 1 dm), concentration, temperature (25 °C),
and wavelength (589 nm, the D line emitted by a sodium lamp).
- Specific rotations are physical constants just like melting points or boiling points, and are
reported in chemical reference books for a wide variety of compounds.
or groups is called an asymmetric carbon atom or a chiral atom. A chiral atom is indicated by an
asterisk (*).
If a molecule contains only one chiral centre/atom, then the molecule has to be optically active
(i.e. non superimposable on its mirror image) as it will not contain any element of symmetry.
Molecules containing two or more chiral centers may or may not be chiral (optically active).
whole which is optically active, whereas chiral centre is for an atom which is attached to form
different atoms/groups.
5. ELEMENT OF SYMMETRY:-
To exhibit optical activity molecule must not have the symmetry elements, (a) plane of symmetry
(b) centre of symmetry (c) n-fold alternating access of symmetry. If these three are absent then
only the compounds exhibits optical activity.
Plane of symmetry: A molecule is said to possess a plane of symmetry if the atoms or groups on
one side of the plane forms the mirror image of those on the other side. In other words, a plane
which bisects a molecule/object in two equal halves.
Centre of symmetry:
- A centre of symmetry in a molecule is said to exist if a line is drawn from any atom or group to
this point and then extended to an equal distance beyond this point meets the identical atom or
group. A centre of symmetry is usually present only in an even membered ring.
Enantiomers Diastereomers
An enantiomer is one of two stereoisomers that are Diastereomers (or diastereoisomers) are
non-superimposable complete mirror images of each stereoisomers that are not enantiomers (non-
other. superimposable mirror images of each other).
Molecules must contain atleast one chiral centers. Molecules must contain more than one chiral
center.
Enantiomers have, when present in a symmetric Diastereomers can have different physical properties
environment, identical chemical and physical and different reactivity. In another definition
properties except for their ability to rotate plane diastereomers are pairs of isomers that have opposite
polarized light by equal amounts but in opposite configurations at one or more of the chiral centers
directions. but are not mirror images of each other.
Racemic mixture is not possible.
A mixture of equal parts of an optically active isomer
and its enantiomer is termed Racemic and has a net
rotation of plane polarized light of zero.
2-bromo-3-chlorobutane
7. MESO COMPOUND
- An optically inactive compound whose molecule is superimposable on its mirror image inspite
of the presence of chiral carbon atoms is called a meso compound.
- If a molecule has two or more chiral centers, it is usually chiral. The exceptions are meso‐
molecules, which are not chiral. These are molecules that due to symmetry have chiral centers that
‘cancel’ each other out.
- Has two or more chiral centers
- Has a plane of symmetry.
I and II are enantiomers (non-superimposable); III and IV are meso form (superimposable).
8. RACEMIC MIXTURE
- A racemic mixture is a 1:1 mix of two enantiomers (Each of a pair of molecules that are mirror
images of each other).
JGIPT (AHERA) Page 7
COURSE: B. PHARMACY, 4 Sem, MODULE-1: STEREOISOMERISM
- No matter how many molecules are in a mixture, it is racemic if there are equal numbers of the
two enantiomers.
- The racemic mixture produces a net optical rotation - of plane polarized light - of zero degrees.
This is because the mixture contains equal amounts - equimolar mixture - of both enantiomers
that have opposite rotations.
- A racemic mixture is a solution containing equal amounts of a pair of enantiomers.
method.
For example, when the mould, racemic ammonium tartarate, the mould completely
decomposes the d form white l form is left practically unaffected. The main drawback of the
method is that half of the material is destroyed during resolution. The process is very slow and
only small amounts of the materials can be separated.
(iii) Chemical separation:
of resolution. The racemic mixture is made to combine with
another optically active compound and the resulting solubility in various solvents.
Relative to the position of the methyl group, the chlorine atom is on the same face of
the cyclohexane ring. The stereocenter bearing the chlorine atom has an R absolute configuration
(this configuration does not involve or depend on positions elsewhere in the molecule). Hence this
molecule is cis-1-chloro-2-methylcyclohexane or (1R, 2S)-1-chloro-2- methylcyclohexane.
Cis-2-pentene Trans-2-pentene
(Z)-2-pentene (E)-2-pentene
In cis-2-pentene, the methyl and ethyl groups are on the same side of the alkene. The groups with
highest Cahn-Ingold-Prelog priority are on the same face of the alkene, so this is also (Z)-2-
pentene. In trans-2-pentene, also named (E)-2-pentene, the methyl and ethyl groups are on opposite
faces of the alkene. Cis, trans, E, and Z are all designations of relative configuration.
D-glyceraldehyde D-glucose
At the stereocenter next to the CH2OH carbon, both of these monosaccharides have the OH group
pointing to the right, so they have the same relative configuration. This relative
configuration is indicated with the prefix D. D and L are designations of relative
configuration.
Rule 2: If two or more of the atoms that are bonded directly to the chiral center are the same, then
prioritize these groups based on the next set of atoms (i.e., atoms adjacent to the directly bonded
atoms). Continue until priorities can be assigned. Priority is assigned at the first point of difference.