ISOMERISM

TYPES OF ISOMERISM
CHAIN ISOMERISM

STRUCTURAL ISOMERISM
Same molecular formula but
different structural formulae

POSITION ISOMERISM

FUNCTIONAL GROUP
ISOMERISM

GEOMETRICAL ISOMERISM

STEREOISOMERISM
Same molecular
formula but atoms
occupy different
positions in space.

Occurs due to the restricted

rotation of C=C double bonds...
two forms E and Z (CIS and
TRANS)
OPTICAL ISOMERISM
Occurs when molecules have a
chiral centre. Get two nonsuperimposable mirror images.

Note: structural isomerism also known as constitutional isomerism

STRUCTURAL ISOMERISM - CHAIN

different arrangements of the carbon skeleton

similar chemical properties
slightly different physical properties
more branching = lower boiling point
Example: Two structural isomers of C4H10.
BUTANE
straight chain

Higher b.pt

2-METHYLPROPANE
branched

Lower b.pt

STRUCTURAL ISOMERISM - POSITIONAL

molecule has the same carbon skeleton

molecule has the same same functional group... BUT
the functional group is in a different position
have similar chemical properties / different physical properties
Example
POSITION
1 OF A DOUBLE BOND IN ALKENES

1
2
CH3CH
2CH2CH=CH2

PENT-1-ENE
double bond between
carbons 1 and 2

2
3
CH3CH
2CH=CHCH3

PENT-2-ENE
double bond between
carbons 2 and 3

There are no other isomers with five Cs in the longest chain but there are three
other structural isomers with a chain of four carbons plus one in a branch.

STRUCTURAL ISOMERISM - POSITIONAL

Example 2OF A HALOGEN IN A HALOALKANE
POSITION

1-CHLOROBUTANE
halogen on carbon 1
1

2-CHLOROBUTANE
halogen on carbon 2

There are 2 more structural isomers of C4H9Cl but they have a longest chain of
3

STRUCTURAL ISOMERISM - POSITIONAL

RELATIVE
ExamplePOSITIONS
3
ON A BENZENE RING

1,2-DICHLOROBENZENE
ortho dichlorobenzene

1,3-DICHLOROBENZENE
meta dichlorobenzene

1,4-DICHLOROBENZENE
para dichlorobenzene

STRUCTURAL ISOMERISM FUNCTIONAL GROUP

molecules have same molecular formula

molecules have different functional groups
molecules have different chemical properties
molecules have different physical properties

ALCOHOLS and ETHERS

ALDEHYDES and KETONES

ACIDS and ESTERS

MORE DETAILS FOLLOW

STRUCTURAL ISOMERISM FUNCTIONAL GROUP

ALCOHOLS and ETHERS

Name
Classification

ETHANOL
ALCOHOL

METHOXYMETHANE
ETHER

STRUCTURAL ISOMERISM FUNCTIONAL GROUP

ALDEHYDES and KETONES

Name

PROPANAL

PROPANONE

Classification

ALDEHYDE

KETONE

STRUCTURAL ISOMERISM FUNCTIONAL GROUP

CARBOXYLIC ACIDS and ESTERS

Name

PROPANOIC ACID

Classification

CARBOXYLIC ACID

METHYL ETHANOATE
ESTER

Sometimes more than one type of isomerism occurs in the same molecule.
The more carbon atoms there are, the greater the number of possible isomers

STEREOISOMERISM
Molecules have the SAME MOLECULAR FORMULA but the atoms are
joined to each other in a DIFFERENT SPACIAL ARRANGEMENT - they
occupy a different position in 3-dimensional space.
There are two types...

GEOMETRICAL ISOMERISM
OPTICAL ISOMERISM

GEOMETRICAL ISOMERISM IN ALKENES

Introduction

an example of stereoisomerism
found in some, but not all, alkenes
occurs due to the RESTRICTED ROTATION OF C=C bonds
get two forms...

CIS (Z)
Groups/atoms are on the
SAME SIDE of the double bond

TRANS (E)
Groups/atoms are on OPPOSITE
SIDES across the double bond

GEOMETRICAL ISOMERISM
RESTRICTED ROTATION OF C=C BONDS
Single covalent bonds can easily rotate. What appears to be a different structure is
not. It looks like it but, due to the way structures are written out, they are the same.

ALL THESE STRUCTURES ARE THE SAME BECAUSE C-C BONDS HAVE FREE ROTATION

Animation doesnt
work in old
versions of
Powerpoint

GEOMETRICAL ISOMERISM
RESTRICTED ROTATION OF C=C BONDS
C=C bonds have restricted rotation so the groups on either end of the bond are
frozen in one position; it isnt easy to flip between the two.
Animation doesnt
work in old
versions of
Powerpoint

This produces two possibilities. The two structures cannot interchange easily
so the atoms in the two molecules occupy different positions in space.

GEOMETRICAL ISOMERISM IN ALKENES

CIS-TRANS

CIS /
TRANS

Should only be used when there are two Hs and two

non-hydrogen groups attached to each carbon.
cis

non-hydrogen groups / atoms on the

SAME side of C=C bond

trans

non-hydrogen groups / atoms on

OPPOSITE sides of C=C bond

GEOMETRICAL ISOMERISM
Isomerism in butene
There are 3 structural isomers of C4H8 that are alkenes*. Of these ONLY
ONE exhibits geometrical isomerism.

* YOU CAN GET ALKANES WITH FORMULA C4H8 IF THE CARBON ATOMS ARE IN A RING

OPTICAL ISOMERISM
- is a form of stereoisomerism that occurs when compounds have
non-superimposable mirror images
CHIRAL CENTRES

C*

the two different forms are known as optical isomers or

enantiomers
This usually happens when a molecule contains a C atom with
four(4) different groups attached (chiral / asymmetric carbon [often
shown by an asterisk (*)).
Such molecules are said to be chiral or optically active

OPTICAL ISOMERISM

Left and right hands are an example

of non-superimposable mirror images.

Note: superposable and superimposable are identical in

meaning

19

For chiral molecules the mirror image is

a different molecule (the mirror image is
non-superimposable).

OH

OH

COOH
CH3

(-) lactic acid

in sour milk

HOOC
H3C

(+) lactic acid

in muscles

Chiral and Achiral

*

chiral molecules (optically active)

achiral molecules (not optically active)

TASK

21
Some of the following molecules
are optically active.
For each one, decide whether it is
optically active or not.

a) propan-2-ol

e) butanone

b) 2-chlorobutane

f) 2-methylbutanoic acid

c) 1-chlorobutane

g) butan-2-ol

d) 3-methylhexane

h) 1-chloro-3-methylpentane

propan-2-ol

CH3

CH

22

CH3

OH

NOT OPTICALLY ACTIVE

2-chlorobutane

CH3

CH

CH2 23 CH3

Cl

CH2CH3

CH2CH3

CH3
Cl

H3C
Cl

OPTICALLY ACTIVE

1-chlorobutane

CH2

CH2

24

CH2

Cl

NOT OPTICALLY ACTIVE

CH3

3-methylhexane

CH3 CH2 CH CH2 25 CH2 CH3

CH3

CH2CH 2CH 3

CH2CH 2CH 3

CH3
CH2CH3

CH3
CH3CH2

OPTICALLY ACTIVE

26

butanone

CH3

CH2

CH3

NOT OPTICALLY ACTIVE

27

propan-2-ol

CH3

CH

CH3

OH
NOT OPTICALLY ACTIVE

CH3 28 O

2-methylbutanoic acid
CH3

CH3

CH2

CH

CH2CH3

CH2CH3

H
COOH

H
HOOC

OPTICALLY ACTIVE

OH

CH3

butan-2-ol
CH3

CH3

CH2

OH

29

CH

CH3

CH2CH3

CH2CH3

H
OH

H
HO

OPTICALLY ACTIVE

CH3

1-chloro-3-methylpentane
CH3

CH3

CH2

CH3

30

Cl

CH

CH2

CH2

CH2CH3

CH2CH3

H
CH2CH2Cl

H
CH2ClCH2

OPTICALLY ACTIVE

CH3

31

Molecules that are optical isomers are

called enantiomers.
Enantiomers have identical chemical
and physical properties, except:
Their effect on plane polarised light;
Their reaction with other chiral molecules

OPTICAL ISOMERS - DIFFERENCE

isomers differ in their reaction to plane-polarised light

plane polarised light vibrates in one direction only
one isomer rotates light to the right, the other to the left
rotation of light is measured using a polarimeter
rotation is measured by observing the polarised light coming out towards
the observer
If the light appears to have turned to the right turned to the left
DEXTROROTATORY LAEVOROTATORY
d or + form
l or - form

Racemate
a 50-50 mixture of the two enantiomers (dl) or () is a racemic mixture.
The opposite optical effects of each isomer cancel each other out

Examples
Optical activity is common in biochemistry and
pharmaceuticals
Most amino acids exhibit optical activity
many drugs must be made of one optical isomer to be
effective
- need smaller doses (safer and cost effective)
- get reduced side effects
- improved pharmacological activity

OPTICAL ISOMERISM
The polarimeter
A

B
C

E
F

A
B
C
D
E
F

Light source produces light vibrating in all directions

Polarising filter only allows through light vibrating in one direction
Plane polarised light passes through sample
If substance is optically active it rotates the plane polarised light
Analysing filter is turned so that light reaches a maximum
Direction of rotation is measured coming towards the observer

If the light appears to have

turned to the right
turned to the left
DEXTROROTATORY(+)
LAEVOROTATORY(-)

35

Chiral molecules often react differently

with other chiral molecules.
This is like the idea that a right hand
does not fit a left handed glove the
molecule must be the correct shape to
fit the molecule it is reacting with.
Many natural molecules are chiral and
most natural reactions are affected by
optical isomerism.

36

For example, most amino acids (and

some proteins) are chiral, along with
many other molecules.
In nature, only one enantiomer usually
occurs (e.g. all natural amino acids
rotate polarised light to the left).

37

Many drugs are optically

active, with one enantiomer
only having the beneficial
effect.
In the case of some drugs, the
other enantiomer can even be
harmful, e.g. thalidomide.

 In the 1960s thalidomide was given to pregnant

38
women to reduce the effects of morning
sickness.
This led to many deformaties in babies and early
deaths in many cases.

NH

O
O

H2C

NH

O
C

C
N

CH2

CH2

H2C

S thalidomide (effective drug)

R thalidomide (dangerous drug)

The body racemises each

enantiomer, so even pure S is
dangerous as it converts to R in
the body.
39

40

Thalidomide was banned worldwide

when the effects were discovered.