ISOMERISM X

ISOMERISM
Isomeric substances are different compounds with the same

molecular formula
Isomer: Gk: isos = same (equal), meros = part
Isomers contain equal Nos. of the same kinds of atoms but

the atoms are joined to each other in different ways
TYPES OF ISOMERISM
Two main types of isomerism exist:
1. Structural (Constitutional) isomerism
2. Stereoisomerism
Constitutional isomers:
Are isomers that have the same molecular formula but

different connectivity, meaning that their atoms are
connected in a different order
Therefore, structures are different (different structural formulae)
Hence structural (constitutional) isomers:
 May also have different chemical properties
 Have different physical properties

Examples of constitutional isomers
1,1-dichloroethane 1,2-dichloroethane
The two structures have the same mol. formula (C2H4Cl2) but the
order of attachment of the atoms is different (Connectivity of
atoms is different)
 The structures are different
 i.e., They have different structural formula
Structural isomerism can exist in compounds of the same family
(alkanes, alkenes, alcohols etc)
Such compounds have different physical properties.
The chemical properties are similar but not identical (e.g., rates
of reaction will be different)
Examples
and
Bp = -0.5oC
Bp = -11.7oC
and
-6.3oC Cis 2-butene 3.7oC
Trans 2-butene 0.9oC
It can also exist in compounds of different families
and
Aldehyde Ketone
Both physical and chemical properties are different
Propanal bp 48.8oC Propanone bp 56oC
Oxidation reaction ?
What other chemical reactions are different?
Try the following:
Write all the possible structural isomers of butene,

C4H8
•Draw and name all structural isomers of C7H14F2

Stereoisomerism
Stereochemistry is the chemistry of space
It deals with the spatial arrangements of atoms/groups of

atoms in a molecule
Stereoisomers are molecules that have the same molecular

formula, same connectivity of atoms but different spatial
arrangement of atoms (groups)
There are two kinds of stereoisomers:
 Geometric (Cis-Trans) isomers

 Optical isomers
Geometric (Cis-Trans)
Results from restricted rotation about C=C bonds (also in
compounds with C=N, N=N) or the presence of a ring
structure
Differ in all their physical properties and in many of their
chemical properties
Pairs of geometric isomers are referred to as Cis- and Trans
isomers
Example
Cis-but-2-ene Trans-but-2-ene
More examples of geometric isomers
Cis-1,2-dimethylcyclopropane trans-1,2-dimethylcyclopropane
Cis-1,4-dimethylcyclohexane Cis-1,4-dimethylcyclohexane
Cis and trans isomers can not be inter-converted without
breaking one or more bonds
Geometric (cis-trans) isomers have different physical

properties, e.g., Bps, Mps, etc.
Geometric (cis-trans) isomers have similar chemical properties

since they are members of the same family
However, their chemical properties are not identical since their

structures are not identical
E.g., they react at different rates

Optical isomers
Optical isomers are stereoisomers that differ in their action on

plane polarized light
They may rotate plane polarized light by equal amounts but in
opposite directions
May rotate polarized light by different amounts
May not rotate polarized light at all
However, optical isomers have similar chemical and physical
properties
So how would we know whether two compounds are the same
compound or not?
Consider these compounds
and
If two compounds superimpose on each other they are the

same, if not they are different
In 1874 Jacobus Van’t Hoff and Joseph Le Bell said that if 4
different groups are attached to a carbon atom, two different
compounds can be formed from a given formula
The two compounds will not superimpose on each other (non
superimposable)
The two compounds are related to each other as the left
hand is related to the right hand
What’s the relationship between the two hands?
If you put the left hand in front of a mirror, what you see in the
mirror (mirror image) is your right hand
The left and right hands do not superimpose on each other
Compounds that are related in this way are said to be chiral
Chiral: GK- kheir = hand

A chiral molecule is a molecule that will not superimpose on its
mirror image.
Chiral molecules are said to posses handedness
Chiral means ‘’being left or right-handed’’
A molecule that is superimposable on its mirror image is achiral
Achiral molecules don’t have handedness (they superimpose on
their mirror images)
The carbon atom with 4 different groups attached is called a
chiral carbon (or asymmetric carbon)
Actually, it’s the whole molecule that is chiral

The two compounds are non superimposable mirror reflections
of each other
Compounds related in this way, are called enantiomers

a and b are enantiomers
Enantiomers are non-superimposable mirror images of each other
Enantiomers occur only in compounds whose molecules are chiral
Just as an object has one, and only one, mirror image, a chiral
molecule can have one, and only one, enantiomer.
If enantiomers are different compounds, there must be
differences between them
Differences do exist but can be detected only by devices that are

themselves asymmetric, the most common being polarized light
So enantiomers have similar Mps, Bps and reactivity toward

symmetric chemical substances
Polarized light
• What is it?
• If polarized light passes through an asymmetric compound, the
plane rotates
• The mirror image will rotate the light by the same degrees but in
opposite direction
• A compound that rotates polarized light is said to be optically
active
• The angle between the original and final planes of rotation is
called the optical rotation
• This depends on
• Wavelength of light used
• Length of light path
• No of optically active molecules/unit length of light
• Temperature
• Nature of solvent
• Structure of the compound
• Rotations of a pair of enantiomers are equal in magnitude but
opposite in sign
• If the plane of polarization is rotated clockwise the sign of rotation
is taken as positive and the compound is said to be dextrorotatory
(L. Dexter = right) (e.g., (+)-lactic acid
• If the rotation is anticlockwise the sign is negative and the
compound is said to be levorotatory (e.g., (-)-lactic acid)
(+)-lactic acid (-)-lactic acid

A mixture that contains equal amounts of a pair of enantiomers
is called a racemic mixture or racemate or a (+)(-) mixture (e.g.,
(+)-lactic acid)
A racemate is optically inactive
If you want to compare the optical rotations of two or more

compounds, you have to use standard conditions
Under these conditions (std conditions) the optical rotation is

called the specific rotation
Specific rotation: The angle in degrees through which polarized

light is rotated when it is passed through a 10cm tube of solution
of concentration 1g/ml
Compounds with multiple asymmetric centres
Compounds that contain two or more asymmetric carbons exist

in more than two stereoisomeric structures
Some are pairs of enantiomers, others may be symmetric and

therefore optically inactive
Many natural products contain two to ten asymmetric centres

and molecules e.g., starch and proteins contain hundreds of
asymmetric centres
The number of stereoisomers having the same structural
formula is called the isomer number for that structure
Generally the isomer number will be equal to 2n, where n is the
number of asymmetric centres
Consider the compound below:
The compound above has two chiral carbons, so its isomer

number is 2n = 22 = 4. ie the compound has 4 stereoisomers
a and b are enantiomers, c and d are enantiomers
On the other hand, a and c are diastereomers, a and d are
diastereomers, b and c are diastereomers, b and d are
diastereomers
Diastereomers are stereoisomers that are not mirror images.

Now let us look at tartaric acid:
The four expected stereoisomers can be drawn as follows:
a and b are enantiomers. Identical
A close look, however, shows that the c and d structures are

identical, as can be seen by rotating one structure 180°.
The c and d structures are identical because the molecule has a
plane of symmetry and is therefore achiral.
The symmetry plane cuts through the C2–C3 bond, making one
half of the molecule a mirror image of the other half
A plane of symmetry (mirror plane) is an imaginary line that
bisects a structure into two equal halves such that one half is
the mirror image of the other
Because of the plane of symmetry, the molecule is achiral,

despite the fact that it has two chirality centers.
Compounds that are achiral, yet contain chirality centers, are
called meso (me-zo) compounds.
Meso compounds are optically inactive
Thus, tartaric acid exists in three stereoisomeric forms: two
enantiomers and one meso form.
c
a and b are enantiomers, a and c are diastereomres, b and c
are diastereomers, c is a meso compound
Frequently substances have special symmetry properties
and when this is so, the 2n formula does not apply
Optical isomerism is also possible in cyclic compounds
Consider 1,2-dibromocyclopentane
The stereoisomers of 1,2-dibromocyclopentane are:
a b c
a and b are enantiomers, a and c are diastereomers, b and c are
diastereomers, c [s a meso compound
Notice that a (or b) and c are geometric isomers
Geometric isomers are also diastereomers
Try these
For each of the following, draw all stereoisomers:

Show all stereoisomers that are related as enantiomers,
diastereomers, or meso
 dibromocyclopentane
 3-phenyl-2-butanol
 2-(methylamino)-1-phenylpropan-1-ol
Why bother with Isomerism?
• Nearly all organic molecules of living organisms
have handedness
• So too, almost all foods that we eat
• What difference does this make?
• Life and death !!

• Each enzyme in the body comes in only one shape
• Mechanism of catalysis is the so called ‘’Lock and

Key’’
• Only one form of the food can fit onto this
• Suppose you ate food that is the enantiomer!!

Also many of the drugs we take and biological
compounds we have are optically active
compounds

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ISOMERISM

Isomeric substances are different compounds with the same

Isomers contain equal Nos. of the same kinds of atoms but

Are isomers that have the same molecular formula but

Therefore, structures are different (different structural formulae)

Hence structural (constitutional) isomers:

 May also have different chemical properties

 Have different physical properties

Both physical and chemical properties are different

Propanal bp 48.8oC Propanone bp 56oC

Write all the possible structural isomers of butene,

•Draw and name all structural isomers of C7H14F2

Stereochemistry is the chemistry of space

It deals with the spatial arrangements of atoms/groups of

Stereoisomers are molecules that have the same molecular

There are two kinds of stereoisomers:

 Geometric (Cis-Trans) isomers

Geometric (cis-trans) isomers have different physical

Geometric (cis-trans) isomers have similar chemical properties

However, their chemical properties are not identical since their

E.g., they react at different rates

Optical isomers are stereoisomers that differ in their action on

If two compounds superimpose on each other they are the

Chiral: GK- kheir = hand

Actually, it’s the whole molecule that is chiral

Compounds related in this way, are called enantiomers

Differences do exist but can be detected only by devices that are

So enantiomers have similar Mps, Bps and reactivity toward

(+)-lactic acid (-)-lactic acid

A racemate is optically inactive

If you want to compare the optical rotations of two or more

Under these conditions (std conditions) the optical rotation is

Specific rotation: The angle in degrees through which polarized

Compounds that contain two or more asymmetric carbons exist

Some are pairs of enantiomers, others may be symmetric and

Many natural products contain two to ten asymmetric centres

Consider the compound below:

The compound above has two chiral carbons, so its isomer

Diastereomers are stereoisomers that are not mirror images.

The four expected stereoisomers can be drawn as follows:

a and b are enantiomers. Identical

A close look, however, shows that the c and d structures are

Because of the plane of symmetry, the molecule is achiral,

The stereoisomers of 1,2-dibromocyclopentane are:

For each of the following, draw all stereoisomers:

• So too, almost all foods that we eat

• What difference does this make?

• Life and death !!

• Mechanism of catalysis is the so called ‘’Lock and

• Only one form of the food can fit onto this

• Suppose you ate food that is the enantiomer!!

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