ORD and CD

Linearly and Circularly Polarized light

• Natural light is having two components electric component and magnetic component, and
both are perpendicular to each other in different planes.
• Both these electric components and magnetic components are also perpendicular to the
direction of propagation of light.
• In ordinary light, electric waves oscillates in all directions perpendicular to the direction of
propagation. This is Unpolarized light.
• If such unpolarized light is filtered through a polarizer (Nicol prism), it will allow only
those electric waves which is parallel to it. (i.e.) light is travelling in a specified direction.
This is called linearly polarized light.
• When one of the polarized states is out of phase with the other by a quarter-wave, the
resultant will be a helix and is known as circularly polarized light (CPL).
• The optical element that converts between linearly polarized light and circularly polarized
light is termed a quarter-wave plate.
• Circularly polarized light can be produced by passing linearly polarized light through a
specially cut glass prism (Photoelastic modulator or Pockel cell)
• It is the EMR filtered in such a way so that the tip of its electric field vector describes a
helix along the axis of propagation of radiation.

Plane polarized waves in a medium showing circular birefringence

• There are materials having a special property: their refractive index is different for left and
right circularly polarized light. This phenomenon is called Circular birefringence.

Causes for Optical Activity

• Due to opposite chiralities, these rays (RCP ray and LCP ray) establish diastereomeric
relationship with a particular enantiomer.

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
 • They interact differently rotating the plane of the polarized light either in a clockwise
direction (dextrorotatory enantiomer) or in an anticlockwise direction (Levorotatory
enantiomer).
• This phenomenon is called Optical rotation, α , the angle by which the polarization plane
is rotated as the linearly polarized light passes through the sample.

Plane polarized waves in a medium with circular dichrorism

• Some materials possess a special property: they absorb left circularly polarized light to a
different extent than right circularly polarized light. This phenomenon is called circular
dichroism.

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
 • When a linearly polarized beam passes through a dissymmetric medium, its two circularly
polarized components show different refractive indices (n L ≠ nR) and different absorption
coeffecients (kL ≠ kR) giving rise to two chiroptical properties of a chiral medium known
as Circular birefringence and circular dichrorism.
• The refractive index n for any medium equals C o/C, where C is the velocity of light in the
medium and Co is the velocity of light in a vacuum
• When Left and Right circularly polarized beams pass through an achiral sample or a
racemic mixture, they travel with the same velocity and therefore enter and exit, the
medium in phase.
• Optical Rotatory Dispersion (ORD) and Circular Dichrorism (CD) are absorption
spectroscopy methods similar to ordinary UV-Vis except that they employ polarized light.
• ORD and CD are also known as chiroptical techniques.
• In ORD, the rotation (specific rotation) of a beam of linearly polarized light is measured as
a function of the wavelength.
• In one sense, ORD is very similar to the classical determination of the specific rotation, in
a Polarimeter; the difference being that determination of specific rotation is performed at a
single wavelength.
• In CD, the absorbance of a circularly polarized beam light is measured as a function of the
wavelength.
• CD measures the differential absorption of chiral light by enantiomers
• Both ORD and CD require that the compound being measured is chiral and “Optically
active”.

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
 • The rate of change of specific rotation with wavelength is ORD.
• ORD is a technique in which optical activity is due to rate of change of specific rotation
with wavelength of light

Cotton Effect:
The combination of circular dichrorism and circular birefringence
There are two types of cotton effects.
1. Positive cotton effect
2. Negative cotton effect
• Positive cotton effect:
It is where the peak is of higher wavelength than the trough.
• Negative cotton effect
Negative cotton effect is opposite
• Optically pure enantiomers always display opposite cotton effect/ORD curves of identical
magnitude.

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
 Axial haloketone rule
• This rule is applied for ketosteroid that are axially substituted with a halogen atom at the
α-carbon.
• Axial substitution is preferred because of dipole-dipole repulsion in equatorial isomer.
• Assignment of configuration based on this rule is carried out by viewing the carbonyl
carbon at the head of the chair.
• If the axial α-halogen is found on the right side in the compound it shows positive cotton
effect.
• If the axial α-halogen is found on the left side in the compound it exhibits negative cotton
effect.
• Project the molecule into four quadrants defined by a horizontal plane B passing through
C-6, C-1 and C-2, and a vertical plane dividing the cyclohexanone across C=O and C-4.
• Label the four quadrants with (+) and (-) as shown.
• Substituents in a (+) sector contributes to the positive Cotton effect and the reverse applies
to a substituent in a (-) sector.
• The halogen (X) in the projected structure is in the lower right quadrant, a (+) sector and
hence Cotton effect is positive.

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
Applications:
Determination of Absolute Configuration
12-ketosteroid undergoes bromination to form 11-bromo-12-ketosteroid product. The
configuration of the product will be decided by the sign of cotton effect.
The product formed shows negative cotton effect. Hence deduced to be (R) configuration.

Octant rule
• This rule is applied for substituted cyclohexanones.
• For assigning configuration based on this rule is to divide the space around the carbonyl
group into eight sectors (octant).
• C=O group lies along z axis
• XY plane bisects C=O bond
• YZ plane bisects C-1 and C-4.

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
 • Substituents lying in the co-ordinate planes make no contribution.
• Substituents lying on the back upper left and back lower right, then octant make positive
contribution. (Positive rotation).
• Substituents lying on the back upper right and back lower left, then the octants make
negative contribution. (Negative rotation).
• Substituents at C2 axial and C6 axial contribute more than C2 equatorial and C6 equatorial.
• Axial and equatorial substituents at 5th position and 3rd position contribute equally.
• Substituent at 5th position and 2nd make +ve contribution whereas substituent at 3rd and 6th
position make –ve contribution to CE.

Applications:
1. Determination of conformation of known configuration
The compound (R)-(+)-methylcyclohexanone exhibit a positive cotton effect. From the application
of the octant rule indicated that preferred conformation is equatorial. According to octant rule,
XVa give positive cotton effect and XVb gives negative cotton effect.

2. Configuration
Trans-10-methyl-2-decalone
The absolute configuration of (+)-enantiomer shows positive cotton effect

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials
The mirror image would show negative cotton effect.

Dr. A. S. Stella Shalini St. Joseph’s College, Trichy-2 ORD and CD materials