Stereochemistry

Optical Isomerism
(Week-4)
CHEM-309
Dr. Ehsan Ullah Mughal
Assistant Professor
Department of Chemistry
University of Gujrat

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 Table of Content
Sr. No. Contents Slide No.
1. General Terms related to Optical Isomerism 3
2. Plane-Polarized Light 4
3. Rotation of Plane-Polarized Light 5
4. Optical Isomers 7
5. Polarimetry & Working of Polarimeter 8
6. Optical Rotation & Enantiomeric Excess 12
7. Specific Rotation 13
8. Optically active compounds 15
9. Symmetry & Chirality 18
10. How optical isomers can be formed? 24
11. Synthesis of 2-hydroxypropanoic acid (lactic acid) 25
12. Applications 26
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 General Terms Related to Optical Activity
 Optical activity – the ability to rotate the plane of plane–polarized light.
 Plane polarized light – light that has been passed through a nicol prism or
other polarizing medium so that all of the vibrations are in the same plane.
 Polarimeter – an instrument used to measure optical activity.
 Plane-polarized light that passes through solutions of achiral compounds
remains in that plane ([α] = 0, optically inactive)
 Solutions of chiral compounds rotate plane-polarized light and the
molecules are said to be optically active.

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 Optical Isomerism
 Ordinary light consists of waves that vibrate in all planes perpendicular to
its direction of travel.
 Plane polarized light is composed of waves that vibrate in only one plane.

Plane-Polarized Light

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 Rotation of Plane-Polarized Light

 When polarized light passes through a solution containing a chiral

compound, the chiral compound causes the plane of vibration to

rotate.

 Rotation of the plane of polarized light is called optical activity, and

substances that rotate the plane of polarized light are said to be

optically active.

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Plane-Polarized Light through chiral compound

Plane-Polarized Light through an achiral compound

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 Optical isomers
Some organic molecules has the ability to rotate the plane polarized light (PPL). These
compounds were termed optically active compounds.
When the compound rotate the PPL to right “clockwise”, it is termed (+) or
Dextrorotatory (d) but when the compound rotate the PPL to left “anti-clockwise”, it is
termed (-) or levorotatory (l)
 The organic molecules that not able to rotate the plane polarized light (PPL) called
optically Inactive compounds.

Polarimeter
 Polarimeter is an instrument used to determine the optical activity of optically active
compounds.
 The simplest polaramiter is composed of:
1)light source (usually sodium lamp).
2)polarizer: it can convert a beam of light of mixed polarization into a beam with
well-defined polarization e.g.(Nickel prism).
3)tube for holding the sample.
4)Analyzer
5) Measuring scale to determine the number of degrees of rotation. 7
 Polarimeter and its Working
 A polarimeter measures the rotation of polarized light.
 It has a tubular cell filled with a solution of the optically active material and a
system for passing polarized light through the solution and measuring the
rotation as the light emerges.
 The light from a sodium lamp is filtered so that it consists of just one wavelength
(one color), because most compounds rotate different wavelengths of light by
different amounts.
 The wavelength of light most commonly used for polarimetry is a yellow emission
line in the spectrum of sodium, called the sodium D line.

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Pictorial Representation of Polarimeter

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 Working of Polarimeter
 Monochromatic (one-color) light from the source passes through a polarizing filter,
then through the sample cell containing a solution of the optically active
compound.
 On leaving the sample cell, the polarized light encounters another polarizing
filter. This filter is movable, with a scale allowing the operator to read the angle
between the axis of the second (analyzing) filter and the axis of the first
(polarizing) filter.
 The operator rotates the analyzing filter until the maximum amount of light is
transmitted, then reads the observed rotation from the protractor. The observed
rotation is symbolized by the Greek letter alpha.

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 Dextrorotatory – Compounds that rotate the plane of polarized light
toward the right (clockwise) are called dextrorotatory, from the Greek
word dexios, meaning “toward the right.”
(+) or (d) do not confuse with D
 Levorotatory– Compounds that rotate the plane toward the left
(counterclockwise) are called levorotatory, from the Latin word laevus,
meaning “toward the left.
(-) or (l) do not confuse with L

 The angle of rotation of plane polarized light by an optically active

substance is proportional to the number of atoms in the path of the light.

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 Optical Rotation and Polarimetry
randomly oriented
light
detecto
chiral r
material
maximum
signal

monochromatic light
source optical
polarizer

optical polarizer - only allows "vertical" light to pass

through

 The amount (in degrees) that a chiral material will rotate light is called the
optical rotation. Different chiral molecules will have optical rotations that
vary in direction and size of the optical rotation. Enantiomers will always have
equal optical rotations but in opposite directions.
 The optical purity of a substance can be measured by comparing the optical
rotation of the sample to the known optical rotation of a single entantiomer of
that compound. Optical purity is usually reported in percent entantiomeric
excess (%ee).

sample rotation
%ee = X 100
single enantiomer rotation

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Enantiomeric excess is the % of the sample that is non-racemic. For example, 80%
ee means that there is 90% of one enantiomer and 10% of the other.
 Specific rotation
 The number of degrees that the plane of polarized light is rotated as the light passes
through a solution of enantiomers depends on the number of chiral molecules in sample.
This of course, depends also on the length of the tube and the concentration of the
enantiomers.
 Enantiomers are stereoisomers that are non super-imposable on its mirror image.
 Enantiomers rotate the plane of polarized light by exactly the same number of degrees
but in opposite directions
 Specific rotation *α+can be calculated by the following equation: [α] = α/cl
α = observed rotation
c = concentration in g/mL
l = length of tube in dm
 Specific rotation is defined as the rotation produced by a solution of unit concentration
(1g/ml) and unit length (10 cm).

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 Specific rotation – the angle of rotation of plane polarized light by a 1.00 gram
per cm-3 sample in a 1 dm tube. [α ]D (D = sodium lamp, λ = 589 mμ).
 The more molecules of a chiral sample are present the greater the rotation of
the light = concentration dependent.
(observed rotation in degrees) 
[ ] D  
(pathlength in dm)(concentration in g/ml) l C
where α = observed rotation
l = length (dm)
d = concentration (g/cc)

(+)-alanine [ α ]D = +8.5
(-)-lactic acid [α ]D = -3.8
Specific Rotation depends on the nature of substance, wavelength of light used,
concentration of the solution, thickness of the layer, nature of the solvent and
temperature at which experiment is conducted. 14
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CHIRAL MOLECULE

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CHIRAL MOLECULE

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 Symmetry and Chirality
 Plane of symmetry- imaginary plane that bisects a molecule
into halves that are mirror images of each other

 Centre of symmetry- imaginary point in the molecules such

that if a line is drawn from any group of the molecule to this Optically active
molecules will not
point and then extended to an equal distance beyond the point, have a plane of
meets an identical group. symmetry and
centre of symmetry
 Axis of symmetry- imaginary axis around which by rotating
through a minimum angle of rotation, the original compound is
obtained

 Alternating axis of symmetry- line passing through the

molecular structure around which if rotated through an angle X
followed by reflection on a mirror placed at right angle to the 18

axis produces the same face of the molecule

Plane of symmetry

Centre of symmetry

Axis of symmetry

Alternating axis of
symmetry 19
 Assymmetric molecule: does not have any element of symmetry.
 Dissymmetric molecule: does not have plane of symmetry, centre
of symmetry and alternating axis of symmetry.

Dissymmetry is
Assymmetric the condition
molecules for optical
activity

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 OPTICAL ISOMERISM
another form of stereoisomerism
Occurrence
occurs when compounds have non-superimposable mirror images

Isomers  the two different forms are known as optical isomers or

enantiomers they occur when molecules have a chiral centre
 a chiral centre contains an asymmetric carbon atom
 an asymmetric carbon has four different atoms (or
groups) arranged tetrahedrally around it.

CHIRAL CENTRES

There are four different 2-chlorobutane exhibits optical isomerism

colours arranged tetrahedrally because the second carbon atom has four
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about the carbon atom different atoms/groups attached
 OPTICAL ISOMERISM
Spatial differences between isomers
 two forms exist which are NON-SUPERIMPOSABLE MIRROR IMAGES of each
other
 non-superimposable means you you can’t stack one form exactly on top of the
other

Some common objects are mirror images and superimposable spoons

superimposable but not mirror images books
non-superimposable mirror images hands

NB For optical isomerism in molecules, both conditions must apply...

they must be mirror images AND be non-superimposable
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 OPTICAL ISOMERS - DIFFERENCE
 isomers differ in their reaction to plane-polarised light
 plane polarised light vibrates in one direction only
 one isomer rotates light to the right, the other to the left
 rotation of light is measured using a polarimeter
 rotation is measured by observing the polarised light coming out
towards the observer

• If the light appears to have turned to the right turned to the left
DEXTROROTATORY LAEVOROTATORY
d or + form l or - form
Racemate a 50-50 mixture of the two enantiomers (dl) or (±) is a racemic
mixture. The opposite optical effects of each isomer cancel each
other out
Examples Optical activity is common in biochemistry and pharmaceuticals
• Most amino acids exhibit optical activity
• many drugs must be made of one optical isomer to be effective
- need smaller doses (safer and cost effective)
- get reduced side effects 23

- improved pharmacological activity

 OPTICAL ISOMERISM
How optical isomers can be formed
Carbonyl compounds undergo nucleophilic addition. If there are two different groups
attached to the C=O bond, the possibility of forming optical isomers arises.

THE NUCLEOPHILIC ADDITION OF HCN TO ETHANAL

 If the nucleophilic cyanide ion

attacks from above one optical
isomer is formed

 However, attack from below, gives

the non-superimposable mirror
image of the first

 The reaction produces a mixture of the two optical isomers because both modes of
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attack are possible
 OPTICAL ISOMERISM
Synthesis of 2-hydroxypropanoic acid (lactic acid)
LACTIC ACID can be formed from ethanal in a two stage process.
1. Nucleophilic addition of hydrogen cyanide to ethanal
2 Hydrolysis of the nitrile group

HCN H+ / H2O

 During the first stage, the nucleophilic CN- ion

can attack from below, or above, the aldehyde.
 A mixture of the two enantiomers is formed.
 Acid hydrolysis of the mixture provides a mixture
of the two lactic acid forms.
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Working of Polarimeter - Video

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 APPLICATIONS
Quantitative application
 If the specific rotation of sample is known its concentration in the
solution can be estimated.
Qualitative application
 Optical activity is the only parameter available for distinguishing
between D and L isomeric forms.

Saccharimetry
 Important practical application of polarimetry
 Determination of high conc. of sugars
 Visual saccharimeters called Polaroscopes

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