PHARMACEUTICAL ANALYSIS Seminar on Fundamental principle of ORD curves

Presented by
Ms. TEJASWINI royal
M. Pharm. 1st year

Department -:
Pharmacology KCP College of pharmacy Bangalore.

Introduction -:
ORD refers to the change in optical rotation with the change in wavelength of light source. i.e. applied only in optically active compounds. Optical rotation caused by compound changed with wavelength of light was first noted by Biot in 1817. ORD curves in recent years are made use in structural determination by comparing the curve obtain from compound believed to have related structures particularly applied to carbonyl compounds.

E.g.. ORD curves have been used to locate the position of carbonyl groups in steroid molecules. Djerassi & Klyne have suggested that rotatory dispersion curves (i.e. plot of optical rotation against wavelength.) should be classified in to two main types. Plane curves & cotton effect curves.

OPTICAL ACTIVITY -: certain organic compounds when placed in the path of plane polarized light, the plane of polarization is rotated, the property of compounds to rotate plane polarized light is optical active. When a ray of monochromatic polarized light strikes a solution, several phenomenons occurs like 1. Reflection on the surface. 2. Refraction. 3. Rotation of plane polarization 4. Absorption.

 

Enantiomers are optically active An asymmetric environment can also confer optical activity to a molecule Optically active molecules have different refractive indices, and different extinction coefficients for L and R circularly polarised light

For a compound to be optically active it must be devoid of the following properties 1. Plane of symmetry. 2. Center of symmetry. 3. Alternating rotation reflection axis of symmetry.

1. Plane of symmetry -: It is the plane, which divides a molecule such that one half forms the mirror images of other e.g. Mesotartaric acid 2. Center of symmetry -: it is the point in the compound from which a line drawn from one side & extended equally in the opposite side reaches the same group. e.g. diketo dimethyl piperazine

3. Alternating rotation reflection axis of symmetry -: A molecule possess n-fold-alternating axis of symmetry, if then rotated through an angle 3600/n about the axis followed by a reflection in a plane perpendicular to the axis, the molecule is same as original one. e.g. 1, 2, 3, 4 tetramethyl cyclobutane. The isomer that rotates the plane polarized light to the left is called levoisomer (-) & to the right is called as dextroisomer (+)

Rotation of plane polarized light (FRESNELS EXPLANATION) -: According to Fresnel, a plane polarized light may be considered as the combination of two circularly polarized light of which one is right circularly polarized light (RCPL) & other is left circularly polarized light (LCPL) which are in equal & opposite in nature. A circularly polarized light (CPL) is one whose plane of polarization rotates continuously & in the same sense around the axis of the polarization of the wave & it may be described as right handed screw or helix twisting around the direction of propagation, where LCPL wave describe the left handed screw.

The figure below represents how the electric vector of RCPL (ER) & that of LCPL(EL) combined to give a plane polarized wave (E)

El ER

Plane of polarization

RCPL + LCPL = PPL

The two circularly polarized light vibrate in opposite direction with the same angular velocity if refractive index is same

The two circularly polarized light vibrate in opposite direction with same angular velocity if refractive index is same.

Zero resultant

Specific rotation (Rotatory power) -:

It is the rotation produced by a solution in 10 cm length tube having 1 gm of substance in 100 ml.

The specific rotation depends on following factors:Nature of substance. Length of the column. Conc. of the sol. Temp of the sol. Nature of the solvent. Wavelength of the light used.

Optical Rotatory dispersion -: Definition -:

ORD is defined as the rate of change of specific rotation or rotary power with change in wavelength. Light is an electromagnetic radiation and consist of vibrating electric and magnetic vector perpendicular to each other. The branch of physics dealing with nature, sources, properties and effects of light is called optics.

CIRCULAR BIREFRENGENCE -:
The two equal & opposite beams of CPL of a PPL when passes through an optically active compound it result in characteristic phenomenon is called circular birefringence

The angle of rotation per unit path length is,

=( L R)
If RCPL travels faster rotatory,

is positive & the medium is dextro

where as if LCPL travels faster then medium is levo rotatory.

is negative & the