CHIROPTICAL PROPERTIES

OPTICAL ROTATION

Optical rotation: the rotation of linearly polarized light by the sample. Chiral
structure can be distinguished and characterized by polarized light

• Usually reported as a specific rotation [], measured at a particular T,

concentration and  (normally 589; the Na D line)
• Molar rotation [] = []MW10-2

10 2 α
α 
lc
l  pathlength in decimeters
g
c
100 mL
 OPTICAL ROTATION


rotation rad cm -1
 
   nL  nR 


n = refractive index
l = wavelength of light
f = angle of rotation
 What is optical rotary dispersion(ORD)?
Optical rotary dispersion is the variation of optical rotation as a function of
wavelength. The spectrum of optical rotation.
Optical rotatory dispersion is the variation in the optical rotation of a substance
with a change in the wavelength of light. It can be used to find the absolute
configuration of metal complexes. For example, when plane-polarized white light
from an overhead projector is passed through a cylinder of sucrose solution, a
spiral rainbow is observed perpendicular to the cylinder

• If the refractive indices of the sample for the left and right handed polarized
light are different, when the components are recombined, the plane-polarized
radiation will be rotated through an angle 
• nl, nr are the indices of the refraction for left-handed and right-handed
polarized light
•  is in radians per unit length (from )
nl  nr
α
λ
 What is optical rotary dispersion(ORD)?
When white light passes through a polarizer, the extent of rotation of light depends
on its wavelength. Short wavelengths are rotated more than longer wavelengths, per
unit of distance. Because the wavelength of light determines its color, the variation of
color with distance through the tube is observed. This dependence of specific rotation
on wavelength is called optical rotatory dispersion. In all materials the rotation varies
with wavelength. The variation is caused by two quite different phenomena. The first
accounts in most cases for the majority of the variation in rotation and should not strictly
be termed rotatory dispersion. It depends on the fact that optical activity is actually
circular birefringence. In other words, a substance which is optically active transmits right
circularly polarized light with a different velocity from left circularly polarized light.
In addition to this pseudo-dispersion which depends on the material thickness, there is a
true rotatory dispersion which depends on the variation with wavelength of the indices of
refraction for right and left circularly polarized light.
For wavelengths that are absorbed by the optically active sample, the two circularly
polarized components will be absorbed to differing extents. This unequal absorption is
known as circular dichroism. Circular dichroism causes incident linearly polarized light to
become elliptically polarized. The two phenomena are closely related, just as are ordinary
absorption and dispersion. If the entire optical rotatory dispersion spectrum is known, the
circular dichroism spectrum can be calculated, and vice versa.
What is optical rotary dispersion(ORD)?
 What is optical rotary dispersion(ORD)?

α
α 
c' d'

• Concentration of an optically active substance, c’, expressed in g cm-1

(as density of a pure substance)
• d’ = thickness of the sample in decimeters

Mα 10 2
M   M α10 2

c' d '

• M = molecular weight of the optically active component

• the 10-2 factor is subject to convention and is not always included in [M]
 What is optical rotary dispersion(ORD)?

Mα 10 2
M   M α10 2

c' d '

• M = molecular weight of the optically active component

• n. b. the 10-2 factor is subject to convention and is not always included
in [M]

• ORD curve is a plot of molar rotation [] or [M] vs 

• Clockwise rotation is plotted positively; counterclockwise rotation is plotted
negatively
• ORD is based solely on the index of refraction
• So-called plain curve is the ORD for a chiral compound that lacks a
chromophore
• Chiral compounds containing a chromophore can give anomalous, or Cotton
effect, curves
What is optical rotary dispersion(ORD)?
ORD is valuable only for chiral compounds-justify it
 WHAT IS CIRCULAR DICHROISM(CD)?

Circular Dichroism: the difference in absorption of left and right circularly

light. Circular dichroism (CD) spectroscopy measures differences in the
absorption of left-handed polarized light versus right-handed polarized light
which arise due to structural asymmetry. The absence of regular structure
results in zero CD intensity, while an ordered structure results in a spectrum
which can contain both positive and negative signals.

Jasco J-810 Circular Dichroism System

 WHAT IS CIRCULAR DICHROISM(CD)?

• Measurement of how an optically active compound absorbs right- and

left-handed circularly polarized light
• All optically active compounds exhibit CD in the region of the
appropriate absorption band
• CD is plotted as l-r vs 
• For CD, the resulting transmitted radiation is not plane-polarized but
elliptically polarized

kl  k r
molar circular dichroism   l   r 
c
k from I  I o10 kd
CIRCULAR DICHROISM

2.303 AL  A R 
 
 rad cm-1 
4l

 ellipticity
l path length through the sample
A absorption
 CIRCULAR DICHROISM

•  is therefore the angle between the initial plane of polarization and the
major axis of the ellipse of the resultant transmitted light
• A quantity  is defined such that tan  is the ratio of the major and minor
axis of the ellipse of the transmitted light
• ’ approximates the ellipticity
• When expressed in degrees, ’ can be converted to a specific ellipticity []
or a molar ellipticity []
• CD is usually plotted as []


specific ellipticit y    
c' d
molar ellipticit y  θ  M  10 2
ε l  ε r  0.3032 10 3 θ
 CIRCULAR DICHROISM

The difference between the absorption of left and right handed circularly-polarised
light and is measured as a function of wavelength. CD is measured as a quantity
called mean residue ellipticity, whose units are degrees-cm2/dmol.
 Comparison between ORD and CD

• CD plots are Gaussian rather than S-shaped.

• Positive or negative deflections depend on the sign of  or [] and
corresponds to the sign of the Cotton effect
• ORD spectra are dispersive (called a Cotton effect for a single band) whereas
circular dichroism spectra are absorptive. The two phenomena are related by
the so-called König-Kramers transforms.
• Maximum of the CD occurs at the absorption max
• Where more than one overlapping Cotton effect, the CD may be easier to
interpret than the ORD with overlapping S-shaped bands
 Comparison between ORD and CD

ORD spectra are dispersive (called a Cotton effect for a single band) whereas
circular dichroism spectra are absorptive. The two phenomena are related by
the so-called König-Kramers transforms.
 Uses of ORD and CD

(a) For identification of functional groups

(b) To determine the position of functional groups
(c) To determine the configuration of molecules
(d) In the study of conformational changes
(e) To determine the structure of polypeptide, protein, nucleotide
Comparison between optical rotation and circular dichroism
Scheme of circular dichroism
 What is Circular Birefringence?

Circular Birefringence is the difference in refraction (and the associated speed of

light) of left and right circularly polarized light.

• The polarization plane of linearly polarized light traversing a Circularly

Birefringent medium is rotated.
 What is Circular Birefringence?

Birefringence is the optical property of a material having

a refractive index that depends on the polarization and
propagation direction of light These
optically anisotropicmaterials are said to
be birefringent (or birefractive). The birefringence is often
quantified as the maximum difference between refractive
indices exhibited by the material. Crystalswith non-
cubic crystal structuresare often birefringent, as
are plastics under mechanical stress.
Birefringence is responsible for the phenomenon of double
refraction whereby a ray of light, when incident upon a
birefringent material, is split by polarization into two rays
taking slightly different paths.
 Types of polarized light

• Plane polarized light consists two circularly polarized components of

equal intensity
• Two circularly polarized components are like left- and right-handed
springs
• As observed by looking at the source, right-handed circularly polarized
light rotates clockwise
• Frequency of rotation is related to the frequency of the light
• Can be resolved into its two circularly polarized components
• When added together after passing through an optically isotropic
medium, plane polarized light results
Types of polarized light
 What is Linear Polarized Light?

z  2
E x ( z, t )  E0 sin 2   t   E0 sin z  ct 
c  
E y z, t   0
 What is Circular Polarized Light?

Passing plane polarized light through a

birefringent plate (in the z-direction)
which splits the light into two plane-
polarized beams oscillating along
different axes (e.g., fast along x and slow
along y). When one of the beams is
retarded by 90º (using a quarter-wave
retarder) then the two beams which are
now 90º out of phase are added together,
the result is circularly polarized light of
one direction. By inverting the two axes
such that the alternate beam is retarded
than circularly polarized light of the other
direction is generated.
The result of adding the right and left
circularly polarized that passes through
the optically active sample is elliptically
polarized light, thus circular dichroism is
equivalent to ellipticity.
 Circularly Polarized Light

Left-handed right-handed
 z ct 
E x z, t   E0 sin 2     z ct 
E x z, t   E0 sin 2   
     
 z ct 1 
E y z, t   E0 sin 2      z ct 1 
E y z, t    E0 sin 2    
  4   4
Circularly Polarized Light
Circularly Polarized Light
Difference between Linearly & Circularly Polarized Light
 Linearly & Circularly Polarized Light

Linear polarized light can be viewed different absorption of the left- and
as a superposition of opposite circular right hand polarized component leads
polarized light of equal amplitude and to ellipticity (CD) and optical rotation
phase (OR).
 Linearly & Circularly Polarized Light

Electromagnetic radiation consists of an electric (E) and magnetic (B) field

that oscillate perpendicular to one another and to the propagating
direction,[7] a transverse wave. While linearly polarized light occurs when the
electric field vector oscillates only in one plane, circularly polarized light
occurs when the direction of the electric field vector rotates about its
propagation direction while the vector retains constant magnitude. At a single
point in space, the circularly polarized-vector will trace out a circle over one
period of the wave frequency, hence the name. The two diagrams below show
the electric vectors of linearly and circularly polarized light, at one moment of
time, for a range of positions; the plot of the circularly polarized electric
vector forms a helix along the direction of propagation (k). For left circularly
polarized light (LCP) with propagation towards the observer, the electric
vector rotates counterclockwise. For right circularly polarized light (RCP), the
electric vector rotates clockwise.
What is Cotton Effect?
 What is Cotton Effect?

•Positive Cotton effect is where the peak is at a higher wavelength than

the trough
•Negative Cotton effect is the opposite
•Optically pure enantiomers always display opposite Cotton effect ORD
curves of identical magnitude
•Zero crossover point between the peak and the trough closely
corresponds to the normal UV max
•The Cotton effect is called positive if the optical rotation first increases as
the wavelength decreases (as first observed by Cotton), and negative if the
rotation first decreases. A protein structure such as a beta sheet shows a
negative Cotton effect.
What is Cotton Effect?
 What is haloketone rule?
A haloketone in organic chemistry is a functional group consisting of
a ketone group or more generally a carbonyl group with an α-
halogen substituent. The general structure is RR'C(X)C(=O)R where R is an
alkyl or aryl residue and X any one of the halogens. The
preferred conformation of a haloketone is that of a cisoid with the halogen
and carbonyl sharing the same plane as the steric hindrance with the carbonyl
alkyl group is generally larger.

Haloketones and halo carbonyl compounds in general are synthesized by

reaction of carbonyl compounds with halogenation agents:
Halogens, bromine and chlorine give monosubstitution, fluorine gives
polysubstitution
Tetrabutylammonium tribromide
N-Bromosuccinimide
In the Hell-Volhard-Zelinsky halogenation a carboxylic acid reacts with
bromine in presence of phosphorus tribromide.
In the Nierenstein reaction an acyl chloride reacts with diazomethane
 Reactions of haloketone
Haloketones take part in several reaction types. In reaction with a nucleophile, two
electrophilic sites are available and in reactions with a base several acidic protons exist
due to the presence of two electron withdrawing groups. The carbon halogen bond
experiences increases polarity from the inductive effect of the carbonyl group making
the carbon atom more electropositive.
In nucleophilic aliphatic substitution reactions with potassium iodide in acetone, 1-
chloro-2-propanone reacts faster than n-propylchloride by a factor of 36000.
In the Favorskii rearrangement a base abstacts first an acidic α-proton and the
resulting carbanion then displaces the halogen.
The same sequence is observed in the Bingel reaction with fullerenes
In crossed Aldol reactions between haloketones and aldehydes the initial reaction
product is an halohydrin which can subsequently form an oxirane in the presence of
base.
Haloketones are important in heterocyclic chemistry. An example is the use of
haloketones in the Hantzsch pyrrole synthesis and the Hantzsch thiazole synthesis.
Haloketones react with phosphites in the Perkow reaction.
The halogroup can be removed in reductive dehalogenation of halo ketones
Historically, treatment of haloketones with zinc dust in the Reformatsky reaction was
one of the first reliable methods for generating unstabilized enolates. This has largely
been superseded by bases such as lithium diisopropylamide.
 Application of haloketone rule?

(a) To determine the absolute configuration

(b) To locate the halogen atom in a molecule
(c) To determine boat conformation of a compound
(d) In the study of changeable conformations
What is octant rule?
What is octant rule?
 Application of octant rule?

(a) To determine conformation of a molecule

(b) To determine configuration of a molecule
(c) To detect steroidal compounds
 What are Molecular asymmetry and dissymmetry?
Asymmetry and dissymmetry have two different meanings in chemistry

In chemistry, the term 'chiral' (stemming from the greek word for hand)
describes the property of not overlapping with one's mirror image. Left and
right hands are chiral because they are mirror images of each other, but
however you reorient them, you will not be able to make them overlap.
Conversely an object such as a chair can be reoriented such that it is
indistinguishable from its mirror image, and therefore is achiral.
Every asymmetrical object, or an object which lacks any elements of
symmetry, is chiral, but not vice-versa. Dissymmetrical objects lack a
particular element of symmetry called an 'axis of improper rotation', but they
may or may not have other elements of symmetry. Every chiral object is
dissymmetrical (asymmetrical objects are dissymetrical by definition), but not
vice-versa. A chair happens to be dissymmetrical, but is achiral. A screw is an
example of a dissymetrical object which is not asymmetrical (screws have
rotational symmetry) and is chiral (right and left handed screws are non-
overlapable mirror images). In a qualitative nutshell, dissymmetric is not
equivalent to asymmetric, since dissymmetric objects may possess some
symmetry elements, while asymmetric objects lack all elements.
 What are Molecular asymmetry and dissymmetry?
Asymmetry is absence of all elements of symmetry. An asymmetric molecule
will be optically active. It will have one more molecule which is it's non
superimposable mirror image, they are termed a pair of enantiomers.

Dissymmetry is the property of non superimposability on its mirror image, a

dissymmetric molecule may have a simple axis of symmetry yet it will be
optically active and exist as a pair of enantiomers.

asymmetry and disymmetry are two different things. Asymmetry means

having no symmetry whereas disymmertry means lacking some symmetry
elements like symmetry plane and rotation axis etc...so disymmetry is imp for
rotation.

Note: Both asymmetric and dissymmetric molecules are optically active.

Define the Molecular asymmetry and dissymmetry
 Define the Molecular asymmetry and dissymmetry

Symmetric molecules: If any symmetry is present in the molecule then molecule

will be symmetric molecule.

Dissymmetric molecules: Molecule will be a dissymmetric molecule if it has no

plane of symmetry, no centre of symmetry and no alternating axis of symmetry.

Asymmetric molecules: Dissymmetric molecule having at least one asymmetric

carbon is known as asymmetric molecule. All asymmetric molecules are also
dissymmetric molecules but the reverse is not necessarily true.
atomic dissymmetry
conformational asymmetry
Plane of symmetry: an imaginary plane which passes through atoms and bonds
in a molecule so that it divides it into two halves each one a mirror image of the
other.

Simple axis of symmetry: A "n" fold simple axis of symmetry is an axis passing
through a molecule in such a way that rotation about this axis by an angle of
360/n degrees brings the molecule into a position indistinguishable from the
original position.
Centre of symmetry: A point within the molecule such that if a straight line is
drawn from any part of the molecule through it and extended on either side to an
equal distance meets with similar environment. For a sphere the geometrical
centre represents the centre of symmetry.
Alternating "n" fold axis of symmetry(Rotation-reflection symmetry):
It is an axis such that the molecule containing such an axis is rotated by 360/n
degrees about the axis and then reflection is effected across a plane at right
angles to the axis a new molecule is obtained which is indistinguish able from
the original one.