Lecture-02

20/08/2023

Isomerism, tautomerism and

optical activity
ISOMERISM
 ISOMERISM
• The isomers are of 2 types:
⮚structural isomers and
⮚stereoisomers.
• Structural isomers have the same molecular
formula but possess different structures.
❖chain isomers
❖positional isomers
❖functional-group isomers
 ISOMERISM
• Stereoisomers, on the other hand, have the
same molecular formula and the same
structure but differ only in spatial
configuration.
• Stereoisomers are of 2 types:
❑geometrical and
❑optical.
Isomerism: Relation of two or more compounds that composed of
same kind and number of atoms but differ each other structural
rearrangement.

Tautomerism: Each of two or more isomer of a compound which exist

together in equilibrium and are readily interchange by migration of an
atom or group within the molecules.
Tautomerism
Stereoisomers are isomeric molecules that have the same molecular formula and
sequence of bonded atoms (constitution), but differ in the three-dimensional
orientations of their atoms in space. There are four different 2,3- disubstituted
butanes (n 2 asymmetric carbons, hence 2n 4 stereoisomers). Each is shown in a
box as a perspective formula and a ball-and stick model, which has been rotated to
allow the reader to view all the groups. Two pairs of stereoisomers are mirror
images of each other, or enantiomers. Other pairs are not mirror images; these are
diastereomers
Epimers are a specific type of stereoisomer that have multiple
stereocenters, but only differ from one another by the configuration
at ONE of the stereogenic centers. D-Glucose and two of its epimers
are shown as projection formulas. Each epimer differs from D-glucose
in the configuration at one chiral center (shaded pink).
 Optical rotation

The direction in which the light is rotated (or in other words, the optical rotation) is a specific
property of the molecule. It should, however, be emphasized that the optical rotation is not at all
related with the two D and L forms of a compound. Thus, D-glucose is dextrorotatory and D-fructose
is levorotatory.
 Optical rotation
The orientation of the electric field is called the polarization of the light wave. When many
waves of light are traveling in the same direction, they each have a different polarization,
randomly oriented with respect to one another. When light passes through a polarizing filter,
only photons of a particular polarization are allowed to pass through the filter, giving rise to
plane-polarized light.

In 1815, French scientist Jean Baptiste Biot was exploring the nature of light by passing plane
polarized light through various solutions of organic compounds. In so doing, he discovered that
solutions of certain organic compounds (such as sugar) rotate the plane of plane-polarized
light. These compounds were therefore said to be optically active. He also noted that only
some organic compounds possess this quality. Compounds lacking this ability were said to be
optically inactive. The rotation of plane-polarized light caused by optically active compounds
can be measured using a device called a polarimeter. The light source is generally a sodium
lamp, which emits light at a fixed wavelength of 589 nm, called the D line of sodium. This light
then passes through a polarizing filter, and the resulting plane-polarized light continues
through a tube containing a solution of an optically active compound, which causes the plane
to rotate. The polarization of the emerging light can then be determined by rotating the
second filter and observing the orientation that allows the light to pass.
Specific Rotation: When a solution of a chiral compound is placed in a polarimeter, the
observed rotation (symbolized by the Greek letter alpha, α) will be dependent on the
number of molecules that the light encounters as it travels through the solution. If the
concentration of the solution is doubled, the observed rotation will be doubled. The same is
true for the distance that the light travels through the solution (the pathlength). If the
pathlength is doubled, the observed rotation will be doubled. In order to compare the
rotations for various compounds, scientists had to choose a set of standard conditions. By
using a standard concentration (1 g/mL) and a standard pathlength (1 dm) for measuring
rotations, it is possible to make meaningful comparisons between compounds. The specific
rotation for a compound is defined as the observed rotation under these standard
conditions.

The following equation can be used to

calculate the specific rotation:

and the problem provides all of the necessary values to plug into this equation. We just need
to make sure that the units are correct: Concentration (c) must be in units of grams per
milliliter. The problem states that 0.300 g is dissolved in 10.0 mL. Therefore, the -
concentration is 0.300 g/10.0 mL = 0.03 g/mL. Pathlength (l ) must be reported in decimeters
(where 1 dm = 10 cm). The problem states that the pathlength is 10.0 cm, which is equivalent
to 1.00 dm. Now, simply plug these values into the equation:
When 0.575 g of monosodium glutamate (MSG) is dissolved in 10.0 mL of water and
placed in a sample cell 10.0 cm in length, the observed rotation at 20°C (using the D line of
sodium) is +1.47°. Calculate the specific rotation of MSG.
 Optical rotation
• When a monosaccharide is dissolved in water, the
optical rotatory power of the solution gradually
changes until it reaches a constant value.
• This gradual change in specific rotation is known
as mutarotation or changing rotation.
• A freshly prepared aqueous solution of α-D-
glucose, for instance, has a specific rotation of
+112.2°.
• And when this solution is allowed to stand, the
rotation falls to +52.7° and remains constant at
this value.
The value of optical rotation for α-D-glucose is
(+112.2°). A fresh solution of β-D-glucose, on the
other hand, has a rotation value of +18.7°; on
standing, it also changes to the same value,
+52.7°.
The value of optical rotation for α-D-glucose is (+112.2°). A fresh
solution of β-D-glucose, on the other hand, has a rotation value of
+18.7°; on standing, it also changes to the same value, +52.7°.