Isomerism

Isomerism
Isomers are compounds that have the
same moleular formula but have different
arrangements of atoms in space.
E.g. Butane and 2-methyl propane

Chain isomers
Same formula
Same functional
group

Hydocarbon chain
has different
branches
Always name for
longest straight chain

Position isomers
Same formula
Same Functional
group
Same chain
Functional group in a
different place on
chain
Put number into name

Functional Group Isomers

Same molecular
formula
The difference is in
the atoms of the
functional group

Stereoisomers
Isomers have the same structural formula

i.e
same formula
Same chain
Same functional groups

So what is left?

Geometric isomers
This is specific to
alkenes
Only compounds with
C=C double bonds
can show this
Parts of the molecule
are on different sides
of the double bond.

E.g. Z or cis

E.g. E or trans

Optical isomers
Specific to compounds
with four different
groups on the same
carbon atom

E.g.

called Chiral carbons

Four groups allows
two different
arrangements in space

Non-superimposable mirror images

or

Enantiomers

Same molecular formula but different

arrangement of their atoms.

Atoms are
bonded in a
different order.

CHAIN
ISOMERISM

POSITIONAL
ISOMERISM

Atoms are bonded in the same

order but arranged differently in
space.

FUNCTIONAL
GROUP
ISOMERISM

GEOMETRIC
ISOMERISM
Rotation prevented
by double bond.

OPTICAL
ISOMERISM
Non- superimposable
mirror images.

Super-imposability
Object are super-imposable on each other if they can perfectly
overlap with each other if they were in the same place.

Here is a molecule gazing into the mirror

Here is its mirror image come to life

Here is the molecule sat next to its mirror image

Can they super-impose?

Apparently not the molecule is chiral

How many different groups are there attached to

the central carbon atom?
Does the molecule have a plane of symmetry?

Chiral
carbon

Chiral
carbon

Optical isomers are:

Mirror images;
Non superimposable;
Chiral*;
Exclusive to asymmetrical compounds;
No plane of symmetry;
Simplest example has 4 different groups
attached to a central carbon atom;
This carbon atom is known as the chiral centre;
Referred to as enantiomers;
Optically active.
* Chiral means hand in greek*

Use the molymods

Which of these compounds can exist as
optical isomers?
CH3CHCHCH3
CH3CH(Cl)CH2CH3
CH3CH(OH)CH3

Spot the chiral carbon (there may be one, none or many)

Check your answers

*
2-bromobutane

Check your answers

Aspirin
No chiral carbon atoms

Check your answers

Aspartame

Check your answers

Chloroethanoic acid
No chiral carbon atoms

Check your answers

2,3-dimethyl pentane

Check your answers

Propene
No chiral carbon atoms

Check your answers

Thirosine

Check your answers

Binol
No chiral carbon atoms

Check your answers

Thalidomide

Check your answers

*
*
** *
Glucose

Check your answers

Phenylalanine

Check your answers

Glycine
No chiral carbon atoms

Check your answers

* *

9-tetrahydrocannabinol

Check your answers

*
*

Cytosine

Check your answers

*
Methionine

Check your answers

Glycerol
No chiral carbon atoms

Check your answers

* *
** **
Cholesterol

Plane Polarised Light

ANALOGY:

Insert a vertical slit

plane polarised string

Add a second slit

The real thing - plane polarised light

Light is also made up of vibrations - this time,
electromagnetic.
Polaroid has the ability to screen out all the
vibrations apart from those in one plane and so
produce plane polarised light.
If you wear one pair of Polaroid sunglasses and hold
another pair up in front of them so that the glasses
are held vertically rather than horizontally, you'll find
that no light gets through - you will just see darkness.
This is equivalent to the two slits at right angles in
the string analogy. The polaroids are described as
being "crossed".

Optical isomers
detector

Chiral cmpds have

the same properties
as each other.

Except for
Optical activity
Interaction with
biological systems;
i.e. enzyme action

Second Parallel
Polarising filter

Plain
Sample in
solution
Plane Polarised Light
Polarising filter
Bulb
Monochromatic
light source

Optical isomers
detector

Chiral cmpds have

the same properties
as each other.

Except for
Optical activity
Interaction with
biological systems;
i.e. enzyme action

Second
Non-parallel
Polarising filter

Plain
Sample in
solution

Polarising filter
Bulb
Monochromatic
light source

Optical isomers
detector

The polarising filters

are perpendicular so
no light should get
through.

Second
Non-parallel
Polarising filter

Sample in
solution

However,

With the optical

isomer in place light is
transmitted.

Polarising filter
Bulb
Monochromatic
light source

Optical isomers
detector

One enantiomer or optical

isomer rotates the beam of
plane polarised light
clockwise.
i.e. it is dextrorotatory
e.g. d-glucose
e.g. (+) glucose
The second polariser must be
rotated clockwise to stop light
being transmitted again.

Second
Polarising filter

Sample in
solution

Polarising filter
Bulb
Monochromatic
light source

Optical isomers
detector

One enantiomer or optical

isomer rotates the beam of
plane polarised light
anticlockwise.
i.e. it is laevorotatory
e.g. l-glucose
e.g. (-) glucose

The second polariser must

be rotated anticlockwise to
stop light being transmitted
again.

Second
Polarising filter

Sample in
solution

Polarising filter
Bulb
Monochromatic
light source

Optical isomers
Implications for
pharmaceutical
compounds.

e.g lactic acid

e.g. thalidomide.
Preparation
Dosage
Side effects
Pairs of optical isomers
= Enantiomers

A racemic mixture (racemate) has equal

quantities of both the enantiomers.
This will have no effect on the plane of
polarized light.

Distinguishing between optical isomers

How can you tell that the plane of

polarisation has been rotated?

Optically active sample:

You can easily tell whether the plane of polarisation has been
rotated clockwise or anti-clockwise, and by how much.

Optical isomerism: True or false

All molecules with a chiral carbon are chiral

True

Optical isomerism: True or false

All solutions that contain optical isomers
(enantiomers) will rotate plane polarized light
False

If there is an equal concentration of opposite

enantiomers the solution will be racemic and
therefore optically inactive

Optical isomerism: True or false

All amino acids are chiral molecules
False

The R-group of glycine is a hydrogen atom and

therefore glycine does not have a chiral carbon

Optical isomerism: True or false

A molecule can have more than one chiral
carbon atom
True

Optical isomerism: True or false

All chiral molecules have a chiral carbon
False

Remember binol which is chiral due to steric

hindrance rather than any chiral carbon atoms

Optical isomerism: True or false

Different enantiomers have very similar physical
and chemical properties. However, they will rotate
plane polarized light in opposite directions.

True

Optical isomerism: True or false

Any carbon atom in a ring cannot be a chiral carbon
because 4 groups cannot be attached to it
False

A carbon atom that is part of an asymmetrical ring,

and has two different atoms or groups bonded to it,
will be chiral

Optical isomerism: True or false

All chiral molecules lack a plane of symmetry
True

1960s Europe

Many babies were born with a disability that was unknown

(truncated limbs)

What is the cause?

Epidemiologists study patterns in
disease and illness and try to
identify common factors that may
be a cause.

The facts:
All mothers who give birth to disabled babies had taken the
new wonder drug thalidomide to alleviate the symptoms of
morning sickness (common factor)
Not all mothers who took thalidomide during pregnancy gave
birth to disabled babies
Do you think thalidomide is to blame? Explain

3 The case thalidomide

Thalidomide was found to be the cause of the disabilities if it

was taken during a particular stage of pregnancy
Thalidomide was marketed as a racemic mixture (not
enantiomerically purified)
Remember, different enantiomers can have very different
biochemical properties

The enantiomers of thalidomide

The R-enantiomer does

not have any teratogenic
effects in humans

The S-enantiomer has

teratogenic effects in
humans

The mechanism of teratogenicity

The exact mechanism of teratogenicity is
unknown
The most widely accepted hypothesis is
that the S-enantiomer acts as a DNA
intercalator
DNA intercalators are planar molecules
that are able to slip in between base pairs
in DNA molecules and cause mutations
reading errors
Developing fetuses have a high rate of cell
division and new tissues are formed
(differentiation)

DNA intercalation:
S-thalidomide from above

S-thalidomide from the side

The planar S-thalidomide is

able to slip in between the
planar base pairs in DNA
It is possible that the
molecule would be held in
place by intermolecular of
attraction forces to the base
pairs
It is thought that Rthalidomide may not be
able to fit or bind as
effectively

Thalidomide survivors

Darren Mansell and Louise Medus-Mansell

Thalidomide discussion
Is it true to describe thalidomide sufferers as victims? If
so, is this a helpful / appropriate description?
Would it help anyone if scientists proved the mechanism of
thalidomide teratogenicity?
The pharmaceuticals company that developed thalidomide
(Grunenthal) tested thalidomide on rats. Should animal
testing be allowed? Explain
Do thalidomide survivors deserve compensation? Why or
why not? If so, who should give them compensation?
Should pharmaceuticals companies still try to develop
drugs to alleviate the symptoms of morning sickness?
Explain

Jun 2010

Jan 13

Jan 12

Jan11