OPTICAL ROTATORY
DISPERSION (ORD)
BY
MANJULA.K.C
1st M PHARM
DEPARTMENT OF PHARMACHEMISTRY
KLEUʼS COP
HUBBALLI.
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CONTENTS
o COTTON EFFECT(CE)
o ORD AND CE CURVES
o OCTANT RULE
o APPLICATIONS OF ORD AND CE CURVES
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COTTON EFFECT
Any medium that exhibit circular birefringence may
also
exhibit circular dichroism.
The combined phenomenon of Circular birefringence
and Circular dichroism are called Cotton Effect.
Cotton Effect is studied by observing the change of
optical rotation with wave length (ORD).
It was discovered by a French physicist A. Cotton in
1896
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ORD Curves- Types
They are of two types:
1. Plain curve
2. Anomalous curve
(a) Single cotton effect curve
(b) Multiple cotton effect curve
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Plain curve
They are called smooth curves – do not show
any Maxima or Minima.
Divided into Positive and Negative curves,
according to the rotation of compounds.
Rotation becomes more Positive or Negative as
the wavelength changes from longer to shorter.
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Rotation
Wave length
They do not contain any peaks, troughs and do not
cross zero rotation line-also called Normal Curves.
Eg : Alcohols ,acids
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Anomalous curves
They are produced when compd has an
absorption maximum in or near the region of
measurement (presence of chromophore).
Anomalous curves has a high point called
“peak” and a low point called “Trough”.
Peak
Trough
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Single cotton effect curve
It is called single because it has only one peak
and one trough.
It may be Positive or Negative.
While approaching the region of cotton effect
from longer wave lengths, if peak is passed
first - Positive Single Cotton Effect.
If trough is passed first – Negative Single
Cotton Effect
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+ ve & - ve Single cotton effect curve
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Multiple cotton effect curve
These curves exhibits 2 or more peaks and troughs.
Eg : Keto steroids
(φ)
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0CTANT RULE
• It is the rule used in predicting the sign and
magnitude of the cotton effects.
• This rule applies to the only cyclohexanones.
• If an organic molecule is placed at the origin of three
dimensional orthogonal axes the three orthogonal
planes will cut the molecule into eight parts.
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OCTANT RULE
Three mutually perpendicular
planes – octants.
In cyclohexanone,
Y-plane passes through the –C=O bond and the 4th C atom
(vertical plane).
X-plane passes through , and (horizontal plane).
Z-plane passes mid way through the –C=O bond and at right
angles to it.
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Octant rule(cont..)
• Thus the mid point of –C=O bond is the origin of the
co-ordinate system.
• Three planes Y , X and Z divide the region into
octants, four back and four front .
• The rotatory dispersion of the molecule, depends
on, which of the octants, the substituents (or
majority of the substituents ) fall into.
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The octant rule states that substituents in the lower left and far upper
right octants makes a –ve contribution to the cotton effect.
Substituents in the far lower right and far upper left makes
+ve contribution.
Substituents in the any three planes do not make contribution.
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Equatorial substituents on -C atoms (2 and 6) make no contribution
to the rotatory dispersion because they lie on the XY plane.
Substituents at make no contribution as they lie on the XZ plane.
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APPLICATIONS
• Useful for quantitative analysis-ORD curves do
not exhibit detailed structure as in IR or NMR
Spectra, so not commonly used in compound
identification.
Cotton effect is used at either maxima/ minima
to compare the unknown with standard.
• Identification of carbonyl group
• Location of carbonyl groups
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• Determination of conformation of optically
active compound- chair / boat form.
• Determination of relative configuration.
• Determination of absolute configuration.
Specific application of CD Spectroscopy
• protein conformational studies
• conformation of nucleic acid is studied
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REFERENCE
• Organic Spectroscopy,3rd Edition.
-William Kemp
• Spectroscopy Of Organic Compounds.
-P.S.Kalsi
• Organic Chemistry, Volume 2: Stereochemistry and
Chemistry of Natural Products. -
-I.L.Finar
• Instrumental methods of chemical analysis by
-Gurudeep R. Chatwal
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