EXPERIMENT 1

CONFORMATION AND OPTICAL ISOMERISM

OBJECTIVE

To explain the concept of conformation and optical isomerism

INTRODUCTION

Isomers are molecules that have the same molecular formula, but have a different
arrangement of the atoms in space. That excludes any different arrangements which
are simply due to the molecule rotating as a whole, or rotating about particular bonds.

Stereochemistry is the study of the relative spatial arrangement of atoms that

form the structure of molecules and their manipulation. The study of stereochemistry
focuses on stereoisomers, which by definition have the same molecular formula and
sequence of bonded atoms, but differ in the three-dimensional orientations of their
atoms in space. In this experiment, we focus on the two aspect of stereochemistry
which are conformation and optical isomerism.

Conformations are different spatial arrangement of a molecule that are

generated by rotation about single bond. In alkanes, the distribution of electrons in
sigma molecular orbital is symmetrical around the internuclear axis of the C-C bond.
Thus, it permits the possibility of free rotation about the C-C single bond. Due to this
rotation, different spatial arrangements of carbon atoms in space are observed which
can change into one another. Alkanes can thus have an infinite number of
conformations by rotation around C-C single bonds. There are difference
fundamentals of conformation with the example of ethane. The rotations will result in
an infinite number of spatial arrangements of hydrogen atoms attached to one carbon
atom with respect to the hydrogen atoms attached to the other carbon atom. These
different arrangements are better known as conformational isomers.

Optical isomerism is one form of stereoisomerism. Optical isomers are effect on

plane polarised light. Optical isomerism occurs when substances have the same
molecular formula and structural formula, but one cannot be superimposed on the
other. Simply, they are mirror images of each other.
APPARATUS

Molecular model set

PROCEDURE

Molecular model is used to draw all the structures of the molecule.

DISCUSSION

Part A: Conformation

Cyclohexane has two limiting conformations, the chair conformation and the boat
conformation. The stability of boat conformation is much less stable than the chair.
The first reason is that the Newman projections along either of the horizontal C-C
bonds in the boat conformation show eclipsing. The another reason is the two
hydrogens shown, the socalled bowsprit hydrogens, come within such a short
distance of one another that a repulsive force is set up. Thus, we will concentrate
upon the chair which constitutes is more than 99.9% of cyclohexane molecules. In
the chair conformation there are two types of hydrogen. Six hydrogens are joined to
their carbons by bonds which are parallel to an axis through the centre of the ring
and are designated axial hydrogens The remaining six hydrogens project around the
equator of the axis and are designated equatorial hydrogens The chair form can flip
through the boat to give another chair in which the axial and equatorial hydrogens
have exchanged places. This occurs very rapidly at room temperature and explains
why the 1H NMR spectrum of cyclohexane only contains one peak, the average
value for axial hydrogen and equatorial hydrogen.

Conformational isomers can be classified into two different types which are
eclipse conformation and staggered conformation. For eclipse conformation is the
conformation in which hydrogen atoms attached to two carbons areas nearest to
each other as possible. For staggered conformation is the conformation in which
hydrogen atoms attached to two carbons are as far as possible with respect to each
other. The staggered conformation is thus relatively more stable in comparison to
eclipse conformation as there are minimum repulsive forces, minimum energy due to
many separations between the electron clouds of C-H bonds.

Substituents on the chair conformation prefer to be in the equatorial position.

The reason is that when substituents are in the axial position, there tends to be more
unfavorable interactions with other axial atoms on the same side. These unfavorable
interactions are called 1,3-diaxial interactions. When substituents are in the
equatorial position, they are farther away from each other. This increases the stability
of the conformation. The methyl in the equatorial position is more stable because it
avoids interaction with the hydrogen atoms. The larger the group is, the more it will
tend to remain in the equatorial position. Therefore, when trying to determine which
chair is more stable, place the larger group in the equatorial position.

Part B: Optical Isomerism

The optical isomerism molecules there must be four groups and the four
groups all must be different. Molecules like this are said to be chiral. The different
forms are called enantiomers. Optical isomers can occur when there is an
asymmetric carbon atom. An asymmetric carbon atom is one which is bonded to four
different groups. It forms a chiral centre of the molecule.

The absolute configuration R and S are used to describe the configuration of

a chirality center. We must prioritize all four groups connected to the chirality center.
Then, rotate the molecule so that the fourth priority group is on a dash to determine
whether the chirality center is R or S. R indicates that a clockwise circular arrow that
goes from higher priority to lower priority. S indicates that an anticlockwise circular
arrow that goes from higher priority to lower priority.

The R and S stereoisomers are non-superimposable mirror images, which

means when reflecting them on a mirror plane, they do not become the exact same
molecule when overlaying them.

Optical isomers can rotate the plane of plane-polarised light. Simple

substances which show optical isomerism exist as two isomers known as
enantiomers. When a solution is viewed from above, the (–) enantiomer rotates the
plane anticlockwise which is to the left-handed side. For the (+) enantiomer rotates
the plane clockwise which is to the right-handed side. A mixture containing equal
concentrations of the (+) and (–) enantiomers is not optically active which it will not
rotate the plane of polarisation.
CONCLUSION

In conclusion, for the conformation, the stability of the chair conformation is more
stable that chair conformation. Besides, chair conformation will be more stable in the
equatorial position when comparing to axial position.

For the optical isomerism, there must be having chiral central for the optical
isomerism. The absolute configuration R indicates that a clockwise circular arrow and
S indicates that anticlockwise circular arrow that goes from higher priority to lower
priority.

REFERENCE

Francis A. Carey & Robert M.Giuliano (2014). Organic Chemistry. New York:
McGraw-Hill Company,Inc.

Janice Gorzynski Smith (2014). Organic Chemistry. New York: McGraw-Hill

Company,Inc.

John D. Robert & Marjorie C. Caserio (2019). Configurational Isomers. Retrieved

from https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book
%3A_Basic_Principles_of_Organic_Chemistry_(Roberts_and_Caserio)/05%3A_Ster
eoisomerism_of_Organic_Molecules/5.02%3A_Configurational_Isomers

QUESTION

1. When the compound does not have a plane symmetry, is it optically active?
Explain.
For the optically active isomer, it must not contain any element of
symmetry, it should not have any axis or any plane of symmetry. Because
the carbons of the optical isomerism molecules attached to four different
groups and the molecules like this are said to be chiral. It is unsymmetrical
then checking for chiral carbon atoms. If it contains chiral carbons then it
is optically active. The final and the most important test is that the optically
active molecule should be non-superimposable on its mirror image.
Hence, the compound does not have a plane symmetry is optically active.