Fundamental principles of ORD cotton effect curves, their characteristics and interpretation


Polarimeter ‡ An optical device used to measure the rotation of the plane of vibration of polarized light

Optical Rotatory Dispersion (ORD)
‡ Defined as "the rate of change of specific rotation or Rotatory power with the change in wavelength" Or ‡ "The variation of the molecular rotation of optically active substance with the variation in the wavelength of plane polarized light used is called as ORD" Or ‡ "It is the measurement of angle of rotation as a function of wavelength"

due to its circular birefringence (unequal refractive indices for RCPL and LCPL) results an unequal rate of propagation of (RCPL &LCPL) ‡ This unequal propagation of both RCPL and LCPL deviates the PPL from its original direction and called to be" optical rotation". 'When a PPL is passed through an optically active compound. Which are equal and opposite in nature. In the same way unequal absorption coefficient of the substance for the RCPL and LCPL is also observed (circular dichroism) which changes CPL to optically polarized light .Principle Of ORD ‡ According to Fresenel a PPL may be considered as the combination or two CPL (RCPL &LCPL).

Instrumentation of ORD ‡ Polarimeter ‡ Spectropolarimeter (combination of spectrophotometer and polarimeter) .

) ‡ Components of polarimeter:  Light source  Polarizer·  Sample tube  Analyzer  Detector .Instrumentation of ORD (Cont.

589-589 .1 nm.lnm.)  Light source ‡ common light source for polarimeter ‡ sodium vapor lamp and mercury vapor lamps  Other light sources are used SOURCE Xenon arc lamp Zirconium lamp Sodium Lamp Mercury lamp WAVELENGTH 260-340nm. 577. 546.0 nm and 579.Instrumentation of ORD (Cont. .8nm.6nm 435.6nm. 290-300nm. 491.

Prisms and gratings are mostly used as monochromator ‡ Litrrow monochromators are used for manually operated spectropolarimeter  Polariser ‡ production of plane-polarized radiation . Monochromators ‡ used in case of spectropolarimeter.

 Types of polariser Depending on the type of output ‡ Linear polariser ‡ Circular polariser ‡ Elliptical polarizer  Linear polariser ‡ In linear polarizer EMR filtered so that its electric field vectors oscillate in one plane. A linearly polarized light may be represented mathematically and graphically as a combination of right and left beams of CPL . in which the radiation is propagated.

During elliptical polarized light passes through ·a sample in a region where absorption takes place. the incident unpolarised light is converted into elliptically polarized light that is the resultant electric field vector takes an elliptical path. . along which axis the radiation is propagated: It can be described by examining the movement of electric field vectors only. The tip of the electric vectors E follows a helical path along surface of cylinder and helix as being pushed out of the light source in the direction of propagation but not rotated.  Elliptical polarizer ‡ It is the most general form and circular polarizer is special cases of elliptical polarizer. Circular polariser ‡ In circular polarizer EMR filtered so that the tip of the electric field vector describes a helix.

 Mechanism of action: ‡ Polarizer are based on four fundamental mechanisms ‡ ‡ ‡ ‡ Selective absorption (Dichroism) Reflection Scattering Birefringence (double refraction) .

 Selective absorption (Dichroism) ‡ Here the polarized light is produced by the used of Polaroid filters which are composed of strongly dichroitic crystal oriented in a plastic material. These components strongly absorb light vibrating in one direction and weakly absorb light vibrating in the perpendicular direction .

e. Tan i= Where i= angle of incidence = refractive index of mirror material The only component vibrating perpendicular to the plane of incidence (parallel to mirror surface) will be reflected . When the light strikes the mirror it gets polarized by reflection from a mirror it gets polarized by reflection from a mirror at Brewster's angle i. Reflection: ‡ Mirrors are used for production of PPL.

‡ Birefringence (double refraction): ‡ It is an optical phenomenon in which a crystal shows different refractive index for the light with the plane of polarization in two perpendicular orientations ‡ Uniaxial crystals have only one optical axis and two different principle indices of refractions about which atoms are arranged symmetrical .

‡ A birefrigent crystal divides an entering ray of monochromatic radiation into two rays.wavelet (extraordinary ray or Eray) .wavelet (Ordinary ray or O-ray) ‡ Ellipsoidal-E. ‡ Spherical-o. Two types of wavelength expand through a uniaxial crystal. which are perpendicular to each other in two different directions.

the ray traveling along the optical axis is O-ray and that along the principle plane is E-ray. E-ray has its vibration parallel to the principle section.‡ The O-ray has its vibrations perpendicular to the principle section of the crystal (opposite faces of the crystal). They vary in the angels of faces of the prism and of the cut diagonally through the prism . ‡ Several different varieties of polarizing and analyzing prism are known. Precisely.

 Different Types of Prisms: ‡ Nicol Prism. ‡ Nomarski Prism . ‡ Wollaston prism. ‡ Glan Thomson Prism.

and the term "crossed Nicols" (abbreviated as XN) is still used to refer to observation of a sample between orthogonally orientated polarizer . It was the first type of polarizing prism to be invented. an optical device used to generate a beam of polarized light. in 1828 by William Nicol (1770-1851) It consists of a rhombohedral crystal of calcite that has been cut at a 68° angle.‡ Nicol Prism ‡ It is a type of polarizer. split diagonally. and then joined again using Canada balsam ‡ Nicol prisms were once widely used in microscopy and polarimetry.

‡ Wollaston prism: ‡ It is an optical device. linearly polarized outgoing beams ‡ It consists of two orthogonal calcite prisms. with the angle of divergence determined by the prisms' wedge angle and the wavelength of the light . It separates randomly polarized or Unpolarized light into two orthogonal. cemented together on their base (typically with Canada balsam) to form two right triangle prisms with perpendicular optic axes. Outgoing light beams diverge from the prism. invented by William Hyde Wollaston. giving two polarized rays. that manipulates polarized light.

Eg: Nicotine in ethanol . The length' of the tube may be determined by measuring the rotation and known strongly rotating liquid usually 5-25 cms in length. The glass 'must be free from stains. Sample tubes: ‡ These are cylindrical tubes having plan parallel glass discs at tile ends.

They have same construction as that of polarizer but are rotatable and have vernier scale fixed to it to measure the angle of rotation. Analyzer: ‡ They are used to determine the direction of rotation of plane polarized light. A polarizer is fixed to the instrument .

 Detectors: ‡ Eye serves as a detector for most of the polarimeter ‡ For UV and Visible -Photo multiplier is usually chosen ‡ For IR thermocouple. bolometer is used .

when an optically active compound in the sample tube rotates the PPL. The polarizer produces a PPL when the analyzer is in the same position as that of the polarizer. This angle of rotation can be measured by vernier scale fixed to the analyzer. then no waves passes through it and the field view will be dark. ‡ The same phenomenon occurs. . Hence the analyzer has to be rotated to that particular angle (a) to view for the PPL. which gives the measure of the optical rotation.‡ Operating procedure: ‡ Initially no sample is placed in the sample tube. the light waves from the polarizer passes through the analyzer is rotated at right angles.

 spectropolarimeter is based upon null balance instrument in which null balance reading is achieved in one of the two ways  Some instruments used mechanical null balance device in which the analyzer and polarizer is turned by servomotor  Other instrument uses an electrical Faraday effect in which polarizer and analyzer are at fixed position while the rotation of sample is carried out electrically using Faraday effect .

‡ Rudolf photoelectric spectropolarimeter: .

2. rotation changes 0'. full scale sensitivity is 0.5 mille degree with favorable conditions and sample densities of 2 to 18nm can.600 nm. A motor energized by the amplified current form the photo multiplier moves the polarizer by means of mechanical linkage. ‡ The polarizer and analyzer of this instrument is double image prism.‡ Cary's Spectropolarimeter: ‡ This is similar to Rudolf instrument. except that in this instrument the mechanical oscillation of the analyzer is replaced by magnetic optical effect. a Faraday cell is placed a head of the analyzer. To achieve this. The wavelength range is 185 .02 . be used .

As one approches certain optical activity absorption band in a compound from long wavelength side the rotatory at first increases strongly .the combination of circular dichroism and cicrular birefringence known as cotton effect .then fall off and changes sign. This is known as cotton effect and the curves describing such effect is called cotton curves .which may be studied by observing the change of optical with the wavelength so called ORD Š The curve obtained by plotting optical rotation v/s wavelength down to above 220 nm using photoelectric spectropolrimeter is known as ORD-curves or cotton curves Š Cotton discovered a relation between RP and light absorption in optically active compound.COTTON EFFECT Š A french physicist A.cotton discovered this effect .

plain curves Š 2.anmalous curves a)Single cotton effect curve b)Multiple cotton effect curve  Plane curves Š Cotton effects is not seen for compounds . The increase optical activity is directly proportional to the decrease in the wavelength .which is far UV well bellow 220nm because it occurs only near absorption maximum Š The curve obtained do not contain any peak or inflections and the curve do not have absorption in the wavelength region where optical activity is being examined.e.COTTON EFFECT  They are of two types: Š 1. the plot of against is a plane curve this curve show no minimum i. of the compound s exhibiting such plane curve are alcohol and hydrocarbons. they are smooth Š e.


2. . Anamolous curves ‡ These curves shows a number of extreme peaks and troughs depending on the number of absorbing groups and there fore known as anamolous dispersion of optical rotation ‡ This type of curves is obtained for the compounds which contain an asymmetric carbon atom and also contains chromophore which absorbs near UV region.

Š Single cotton effect curves Š These are anomalous dispersion curves which shows minimum and maximum both of them occurring in the region of maximum absorption .the cotton effect is said to be positive. the vertical distance between the peak and trough is called the amplitude ³a´ and it is conventionally expressed in hundreds of degrees Š Molecular amplitude. If the trough is reached first and then the peak it is called a negative cotton effect curve.if in approaching the region of cotton effect from the longer wavelength. a= 2. one passes first through maximum (peak)and then a minimum (trough).1/100 .

g. . exhibit such curves.champhor etc.e. ketosteroides . ‡ 2=molar rotation of extreme peak or trough from larger wavelength & 1= molar rotation of peak or trough from shorter wavelength ‡ b)multiple cotton effect curves: ‡ in this type of ORD curve two or more peak or trough are obtained .Where. functional groups i. ‡ e.

carbohydrates. nucleosides and plant hormones . protines. alkaloids. steorides. This includes naturally occuring as well systhetic substance belonging to terpens.Applications of ORD ‡ In the recognition of optical activity ‡ Measurement of the optical rotation of a pure compound may be used as one of the physical constants & which will also distinguish (+) or (-) isomer ‡ In qualatative analysis ‡ In ORD techniques can be applied to any optically compound giving rise to a measurable CE. amino acids.

‡ In quantitative analysis ‡ Optical rotation may be used in quantative analysis of optically active compounds ‡ It is possible to quantify any compound among the mixture or 2 substance at single wavelength where both substance are optically active and when a concentration of one substance is known ‡ Quantification of an optically active compound from an optically inactive compound can be carried out .

when attached to an asymmetric molecule even though they arc symmetric by themselves ‡ Eg: Aryl. conjugated double bonds and hetero aromatic rings ‡ Presence of carbonyl groups and acetonyl groups in a compound can be easily established by ORD curves. chemical analysis . nitrate. ‡ Eg: Spectrophotometry.‡ In structural elucidation: ‡ Recognition of functional groups ‡ The functional groups which absorb light in the UV/Visible region give characteristic ORD curves. sulfoxides. When it is found to be very difficult to establish by any other methods. xanthate.

Cholestane-2-one. And Cholestane-3-one .one.‡ Determination of location and Position of Functional groups in a compound ‡ ‡ It is possible to locate the position of functional groups in a compound by using ORD curves Eg: Cholestane-l-.

.one and cholestane-3-one. differences in amplitude). because the curves arc more closely placed and moreover the 'shapes of the curves are similar (but.‡ By taking the ORD curves for above compounds we can easily distinguish cholestane-lone from cholestane-2-one. but it is not possible to distinguish cholestane-2.

keeping the c-3 hydroxyl group intact.‡ Applications of optical rotatary dispersion -With respect to structure: ‡ One of the applications of the ORD is a tool in structural elucidation. By this we can conclude that the second hydroxyl group in rubijervine is situated at C-l2 position . the location of the hydroxyl groups in rubijervine was not fully confirmed. the ORD curve of this ketone proved to be typical of the 12-keto steroid type. yielded a ketone. Partial oxidation of the alkaloid. especially in the location of functional grous ‡ The structure of a molecule affects the shape of the ORD curve ‡ As we are able to predict the location of functional groups by ORD curves based on the shape of dispersion curves. One such example is rubijervine.

‡ Addition or deletion of functional groups also affects the shape of the curve and cotton effect ‡ Ex: introduction of a single methyl group at <2-3or C4 in cholestanone or the introduction of 2 methyl groups at C2 does not change the sign of the cotton effect curve in 3cholestanone. But introduction of a gem dimethyl group at C4 leads to formation of 4. 4-dimethyl cholestanone and inversion of the CE .

When the standard ORD curves or dispersion curves of known compounds are with us we can assign the exact configuration of unknown compound ‡ Eg: Degradation product of penta cyclic diterpene Cofestol gave an opposite (inverted) ORD curves to that of 4a-ethyl.‡ Applications of ORD with respect to configuration: ‡ It is the arrangement of atoms or groups in space around an asymmetric carbon". 5a-cholestan-3-one. So the written configuration is ascertained for the degradation product (ketone B) in the vicinity of the chromophore . whose configuration is well established.

Therefore configurational changes in the vicinity of an active chromophore can be identified by ORD curves ‡ As the structure affects the shape of the dispersion curve. so does the configuration in the vicinity of the chromophore ‡ The cis and trans androstan-17 -ol-3-ones.‡ A change in the configuration in the vicinity of the chromophore brings the change in the shapes of the ORD curves. The curves for both cis and trans isomers are shown in the figure and clearly indicates that the position of ketone chromophore and its configuration in the vicinity of ketone group .

Actually. while the structure II displays a positive cotton effect (ring B being in the positive sector). .‡ Applications of ORD with respect to conformation: ‡ Conformation of (+)-cis-l O-methyl-2-decalone. it gives a negative CE and so has the conformation l. This is illustrated in fig. This may exist in either of the two conformations (I and II) that exhibit different contributions (positive or negative) to the cotton effect and hence can be identified ‡ The application of the CE reveals that the conformation 1 should give the negative CE (ring B being in the negative sector).

Eliel ORD and CD in chemistry and biochemistry ± Pierre Crabbe Instrumental method of analysis ± Galen W.Kalsi ‡ ‡ ‡ ‡ .References Stereochemistry of carbon compounds-Ernest L. Lindon ‡ Organic chemistry ± vol.Ewing Application of optical activity to stereochemistry determination by M. L.S.Legrand and M J Rougler ‡ Spectroscopy by John C. 2 I. Finar ‡ Spectroscopy of organic compounds-P.

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